US20110288353A1 - Metal loaded catalyst and preparation method thereof - Google Patents

Metal loaded catalyst and preparation method thereof Download PDF

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Publication number
US20110288353A1
US20110288353A1 US13/131,226 US200913131226A US2011288353A1 US 20110288353 A1 US20110288353 A1 US 20110288353A1 US 200913131226 A US200913131226 A US 200913131226A US 2011288353 A1 US2011288353 A1 US 2011288353A1
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Prior art keywords
carrier
active component
catalyst
metal active
primary metal
Prior art date
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US13/131,226
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English (en)
Inventor
Wei Dai
Jing Peng
Haibo Yu
Hui Peng
Genshuan Wei
Maolin Zhai
Zuwang Mao
Yi Le
Wei Mu
Haijiang Liu
Yunxian Zhu
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority claimed from CN200810227414A external-priority patent/CN101733172A/zh
Priority claimed from CN2009100824212A external-priority patent/CN101862653B/zh
Priority claimed from CN200910083212A external-priority patent/CN101875009B/zh
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Assigned to BEIJING RESEARCH INSTITUTE OF CHEMICAL INDUSTRY, CHINA PETROLEUM & CHEMICAL CORPORATION, CHINA PETROLEUM & CHEMICAL CORPORATION reassignment BEIJING RESEARCH INSTITUTE OF CHEMICAL INDUSTRY, CHINA PETROLEUM & CHEMICAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAI, WEI, LE, YI, LIU, HAIJIANG, MAO, ZUWANG, MU, WEI, PENG, HUI, PENG, JING, WEI, GENSHUAN, YU, HAIBO, ZHAI, MAOLIN, ZHU, YUNXIAN
Publication of US20110288353A1 publication Critical patent/US20110288353A1/en
Abandoned legal-status Critical Current

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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
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    • 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
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    • B01J23/681—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
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    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina

Definitions

  • the invention relates to a supported metal catalyst, a method for preparing the same, and use of the same in a reaction for converting an organic compound.
  • Catalysts are basis of modern petrochemical industry, and supported metal catalysts, as an important class of catalysts, are widely used in applications such as oil refining, basic chemical feedstock preparation, fine chemicals industry, and the like.
  • Ni/SiO 2 —Al 2 O 3 or Pd/molecular sieve catalysts have been used in hydrocracking to produce gasoline and other fuels
  • Pt/Al 2 O 3 catalysts have been used in the catalytic reforming of naphtha to prepare high octane number gasoline, arenes and liquefied petroleum gas, and isomerization of light gasoline, alkanes or xylenes
  • Ni/Al 2 O 3 catalysts have been used in methanation
  • Ag/Al 2 O 3 catalysts have been used in the reaction for preparing ethylene oxide from ethylene
  • Pd/Al 2 O 3 catalysts have been used in the selective hydrogenation of olefins, alkynes in pyrolysis gasoline or dienes, etc.
  • a supported metal catalyst consists typically of a carrier, a primary metal active component and an optional secondary metal active component.
  • the carrier is a framework supporting the active components and also functions to enhance utilization rate of the active components, enhance heat stability of the catalyst, provide active centers, and the like. Commonly used carrier materials include alumina, silica, molecular sieves, active carbon, magnesia, titania, diatomite, and the like.
  • the primary metal active component is generally a metal element with catalytic activity, and typically an element from Group VIII, such as Pd, Pt, Ni, and the like.
  • the secondary metal active component may be used to modify the activity or selectivity of the catalyst, and commonly used secondary metal active components include Cu, Ag, Au, and the like.
  • a supported metal catalyst is typically produced by an impregnation-calcination process comprising contacting sufficiently a solution containing a metal active component precursor (typically, a solution of a salt) with a prepared carrier, to support the metal active component precursor on the carrier; and drying and then calcining at a high temperature the carrier having metal active component precursor supported thereon, to decompose the metal active component precursor into corresponding oxides.
  • so-prepared catalyst is typically subjected to a pre-reduction treatment, i.e., reducing the metal oxides with hydrogen gas to elementary metal prior to use.
  • U.S. Pat. No. 5,968,860 discloses a method for preparing a hydrogenation catalyst useful in the gas phase production of vinyl acetate from ethylene, which method comprises supporting a Pd active component precursor and the like on a carrier and reducing the Pd active component precursor-supported carrier with sodium borohydride, hydrazine or formic acid at room temperature, wherein an ultrasonic wave activating step is included in the preparation.
  • the resultant catalyst sample has a higher selectivity.
  • Chinese patent application CN 1579618 describes a method for preparing a supported metal catalyst, which method uses microwave radiation as heat source and a polyol as reducing agent and protecting agent, and can be used to rapidly prepare a multi-component supported catalyst having a supporting amount of from 1 wt % to 99 wt % and a particle size of metal particles controllable to 0.5 to 10 nm.
  • Chinese patent application CN 1511634 describes a method for preparing a catalyst useful in the selective hydrogenation of ethyne to ethylene.
  • the method uses a radio-frequency plasma to activate and decompose a Pd precursor supported on Al 2 O 3 at mild conditions and then carries out H 2 reduction, to give a catalyst characterized by high low-temperature activity and high selectivity.
  • U.S. Pat. No. 6,268,522 utilizes UV light reduction process to prepare a hydrogenation catalyst. Irradiating a carrier having an active component precursor and a sensitizing agent impregnated thereon with UV light will cause reduction in the surface layer portion so that the active component will be distributed in an eggshell shape, and the shell thickness can be controlled via the conditions, e.g. UV radiation wavelength, radiation power and irradiating time. After extracting the un-reduced active component precursor with a solvent, the resultant sample exhibits good activity and selectivity in the reaction for the gas phase production of vinyl acetate from ethylene.
  • microwave and UV light belong to electromagnetic radiation.
  • Microwave is an electromagnetic wave having a wavelength ranging from 1 to 1000 mm, and it heats a system through rapid turn of polar molecules under the action of high frequency electric field and is a heating method per se.
  • UV light is an electromagnetic wave having a wavelength ranging from 10 to 400 nm, and its photons have an energy range in accordance with that required to excite molecules so that they can be selectively absorbed by the molecules to excite the molecules and cause chemical reactions.
  • Ultrasonic wave is mechanical vibration, and it applies some influence on the performance of a catalyst through the action of vibration energy on the catalyst.
  • Plasma belongs to low-energy, charge-born particles, and it decomposes and activates an active component precursor through complex chemical reactions between the large amount of charge-born particles and the active component precursor.
  • the plasma treatment is an activating method replacing for the calcination step, microwave and ultrasonic wave essentially provide heat source to the chemical reduction process, and only UV radiation can cause reduction reaction of the active component precursor.
  • UV light has a poor penetrating ability for a solid, it can act on only the surface layer of the catalyst and can hardly be used in the production of a mass of product.
  • these methods involve complicated operations, and generally require the use of a large amount of compounds as reducing agent, protecting agent or solvent. Taking into account the economic issues involved in the preparation of a mass of a catalyst, it is difficult for these methods to be used in commercial production.
  • the inventors have diligently conducted studies. As a result, the inventors have found that it is possible to utilize ionizing radiation reduction process to prepare a supported metal catalyst, and that the resultant catalyst has excellent performance.
  • the present invention has been made on this basis.
  • An object of the invention is to provide a supported metal catalyst comprising a carrier and supported thereon a primary metal active component and an optional secondary metal active component, wherein the primary metal active component is in elementary state and is formed by reducing a precursor of the primary metal active component by means of ionizing radiation.
  • Another object of the invention is to provide a method for preparing the supported metal catalyst, comprising reducing a precursor of the primary metal active component by means of ionizing radiation to form the primary metal active component in elementary state supported on the carrier.
  • Still another object of the invention is to provide use of the catalyst of the invention in a conversion process of an organic compound.
  • FIG. 1 is transmission electron microscope (TEM) photographs showing the dispersion of Pd particles in catalysts prepared in inventive examples and comparative examples.
  • FIG. 2 is the XPS spectrum of the Pd/Al 2 O 3 catalyst from Example 1.
  • FIG. 3 is the XPS spectrum of a Pd/Al 2 O 3 catalyst prepared though a known technique.
  • Ionizing radiation is a generic term covering all radiations capable of ionizing a substance, and includes high-energy electromagnetic radiations having a wavelength of less than 10 ⁇ 8 meter and high-energy particle radiations, such as X-ray, ⁇ -ray, electron beam, high-energy proton, and the like.
  • ⁇ -ray is a most commonly used ionizing radiation, and is generally generated by a 60 Co or 137 Cs radiation source.
  • ionizing radiation has energy much higher than the exciting energy of molecules so that it can ionize directly molecules, thereby generating a series of active particles and causing reactions such as reduction.
  • reduction reaction caused by ionizing radiation has been used to prepare nanometer elementary metal powder dispersed in a solution system.
  • ionizing radiation reduction process in the preparation of a supported metal catalyst has unique advantages: (1) ionizing radiation reduction process can be carried out at normal temperature or low temperature, and the reaction progress can be easily controlled by absorbed dose rate and absorbed dose; (2) ⁇ -ray and electron beam have strong penetrating ability so that they can be used in large-scale preparation; (3) when causing the reduction of the active component precursor to the elementary active component, the energy of the ionizing radiation is also absorbed by the carrier, thereby altering the energy state of the carrier surface, resulting in that the formed elementary active component bonds tightly to the carrier; (4) the operation of ionization irradiating is simple, and the existing large-scale industrial irradiation sources can be used directly in the production of catalysts.
  • the invention provides a supported metal catalyst, comprising a carrier and supported thereon a primary metal active component and an optional secondary metal active component, wherein the primary metal active component is in elementary state and is formed by reducing a precursor of the primary metal active component by means of ionizing radiation.
  • the supported metal catalyst of the invention comprises:
  • a primary metal active component which is one of the elements of Group VIII and Group IB, in an amount ranging from 0.01 wt % to 20 wt %, based on the total weight of the carrier;
  • an optional secondary metal active component which is at least one metal chosen from Group VIII elements, Group IB elements, Bi, Sb, In, Cs and Rb, in an amount ranging from 0 wt % to 20 wt %, based on the total weight of the carrier;
  • the component b) being different from the component a).
  • the catalyst of the invention comprises a primary metal active component present in its elementary state, which is preferably one member chosen from Group VIII elements and Group IB elements, more preferably from Pd, Pt and Ni, and still more preferably Pd.
  • the content of the primary metal active component ranges from 0.01 wt % to 20 wt %, preferably from 0.01 wt % to 10 wt %, and more preferably from 0.02 wt % to 1 wt %, based on the total weight of the carrier.
  • the catalyst of the invention comprises optionally a secondary metal active component, which is present in the catalyst in elementary state or in an oxidized state.
  • the secondary metal active component is preferably at least one metal chosen from Group VIII elements, Group IB elements, Bi, Sb, In, Cs and Rb, and more preferably from Ag, Au, Cu, Bi, In, Cs, Rb and Group VIII elements other than the component a).
  • the content of the secondary metal active component ranges from 0 wt % to 20 wt %, and preferably from 0 wt % to 10 wt %, based on the total weight of the carrier.
  • the catalyst of the invention also comprises optionally other auxiliary agents that are commonly used in hydrogenation catalysts to adjust catalytic performance, such as alkali metal, alkali earth metal, halogen, etc., of which content ranges from 0 wt % to 5 wt %, based on the total weight of the carrier.
  • auxiliary agents that are commonly used in hydrogenation catalysts to adjust catalytic performance
  • alkali metal, alkali earth metal, halogen, etc. of which content ranges from 0 wt % to 5 wt %, based on the total weight of the carrier.
  • the carrier used in the catalyst of the invention is chosen from Al 2 O 3 , SiO 2 , TiO 2 , MgO, diatomite, molecular sieves, clays, and mixtures thereof.
  • the carrier is of pellet shape, spherical shape, tablet shape, tooth-spherical shape, strip shape, or unusual strip shape such as trilobal shape.
  • a carrier having a specific surface area of from 1 to 200 m 2 /g is used.
  • the catalyst of the invention has an appearance exhibiting light grey, grey, black, bluish light grey, bluish grey or bluish black.
  • the primary metal active component in elementary state is formed by reducing a primary metal active component precursor in the presence of the carrier by means of ionizing radiation. More details about the ionizing radiation reduction will be further discussed hereinbelow.
  • the catalyst of the invention is ones suitable for the selective hydrogenation of ethyne to ethylene and/or the selective hydrogenation of propyne and propadiene to propylene, comprising:
  • an optional secondary metal active component which is at least one selected from the group consisting of Group VIII metals other than palladium, Group IB metals, Bi, Sb, Pb, In, Cs, Rb, K and Mg, in an amount ranging from 0 to 20 wt %, based on the total weight of the carrier.
  • the primary metal active component, palladium is present on the surface of the carrier, and the thickness of the palladium layer is preferably from 1 to 500 ⁇ m.
  • the content of palladium is from 0.01 to 1 wt %, and preferably from 0.01 to 0.4 wt %, based on the total weight of the carrier.
  • the average particle size of palladium is from 1 to 100 nm, preferably from 1 to 40 nm, and more preferably from 1 to 10 nm.
  • the secondary metal active component is not specifically limited with respect to its distribution and state.
  • the secondary metal active component may be distributed on the surface of the carrier, or in the carrier; and it can be present in elementary state and/or in oxidized state.
  • the content of the secondary metal active component is from 0 to 20 wt %, preferably from 0 to 5 wt %, and more preferably from 0.001 to 2 wt %, based on the total weight of the carrier.
  • the weight ratio of the primary metal active component, palladium, to the secondary metal active component is from 0.01-50.
  • the catalyst suitable for the selective hydrogenation of ethyne further comprises other auxiliary agents that are commonly used in hydrogenation catalysts to adjust catalytic performance, such as halogen, in a usual amount.
  • the catalyst of the invention is ones suitable for the hydrogenation of an unsaturated hydrocarbon, in particular the hydrogenation of C4 and/or C5 unsaturated hydrocarbon(s), comprising:
  • elementary Pd as primary metal active component of which content ranges from 0.01 wt % to 1 wt %, and preferably from 0.01 wt % to 0.8 wt %, based on the total weight of the carrier, and which is formed by ionizing radiation reducing a palladium precursor;
  • At least one chosen from alkali metals and alkali earth metals optionally, at least one chosen from alkali metals and alkali earth metals, and preferably one or two chosen from Li, Na, K, Mg, Ca and Ba, of which content ranges from 0 wt % to 3 wt %, based on the total weight of the carrier.
  • the primary metal active component, palladium is present on the surface of the carrier, and the thickness of the palladium layer is preferably from 1 to 500 ⁇ m.
  • the content of palladium is from 0.01 to 1 wt %, preferably from 0.01 to 0.8 wt %, and more preferably from 0.01 to 0.6 wt %, based on the total weight of the carrier.
  • the average particle size of palladium is from 1 to 100 nm, preferably from 0.5 to 40 nm, and more preferably from 1 to 15 nm.
  • the component 2) is generally in a chemical valence state lower than its chemical valence in its normal oxide, and is preferably at least one of Ag, Pb and Cu, and its content ranges from 0.01 wt % to 5%, and preferably from 0.01 wt % to 3 wt %, based on the total weight of the carrier.
  • the component 3) is generally present in the form of metal salt or oxide, and is preferably at least one of K, Na and Ca, and its content in terms of metal ranges from 0 wt % to 3 wt %, and preferably from 0.01 wt % to 2 wt %, based on the total weight of the carrier.
  • the catalyst of the invention is ones suitable for the selective hydrogenation of pyrolysis gasoline, comprising:
  • a secondary metal active component which is at least one chosen from Sn, Pb, Cu, Ga, Zn, Ag, Sb, Mn, Co, Mo, W, Si and P, and preferably Sn and/or Pb, and content of which ranges from 0 wt % to 3 wt %, and more preferably from 0 wt % to 2 wt %, based on the total weight of the carrier; and
  • the invention provides a method for the preparation of the supported metal catalyst of the invention, comprising applying an ionizing radiation on a system comprising a primary metal active component precursor, a carrier, a free radical scavenger and water, to reduce at least the primary metal active component precursor to the primary metal active component in elementary state.
  • the step of applying an ionizing radiation to carry out the reduction is conducted in any of the following manners:
  • the primary metal active component precursor is first supported on the carrier, then the carrier having the primary metal active component precursor supported thereon is combined with an aqueous solution containing the free radical scavenger so that the carrier is wetted with or immerged in the solution, and then the carrier is irradiated with the ionizing radiation.
  • the carrier is directly mixed with an aqueous solution containing the free radical scavenger and the primary metal active component precursor, and then the carrier immerged in the solution is irradiated with the ionizing radiation.
  • the primary metal active component precursor is a corresponding metal compound of the metal active component, and its examples include, but are not limited to, chlorides, nitrates, acetates, sulfates and organometallic compounds.
  • the primary metal active component precursor may be supported on the carrier by a process commonly used in catalyst preparation, for example, spray coating, incipient-wetness impregnation, over-saturated impregnation, and the like.
  • a process commonly used in catalyst preparation for example, spray coating, incipient-wetness impregnation, over-saturated impregnation, and the like.
  • the impregnation may be conducted in one or more steps.
  • the solvent used during the impregnation including, but are not limited to, water, hydrochloric acid, nitric acid, acetic acid, alcohols, and mixtures thereof; and preferably water.
  • the concentration of the solution used in the supporting operation may vary widely.
  • the concentration of the metal active component in the solution ranges from 0.1 mg/ml to 200 mg/ml.
  • the acidity/basicity of the supported product may influence the subsequent radiation reduction process.
  • the acidity/basicity of the supported product it can be adjusted by using the following methods:
  • the carrier (2) treating the carrier with a fixing agent before loading the primary metal active component precursor; or treating the carrier having the primary metal active component precursor supported thereon with a fixing agent after loading the primary metal active component precursor but before carrying out the radiation reduction, with the fixing agent being a basic compound, and preferably an aqueous solution of NaOH, potassium hydroxide, sodium bicarbonate or sodium carbonate, or ammonia water.
  • the treatment may be conveniently carried out, for example, by spray coating the fixing agent on the carrier with/without the supported primary metal active component precursor.
  • the fixing agent converts a soluble metal salt into an insoluble metal compound fixed on the surface of the carrier.
  • the carrier having the primary metal active component precursor supported thereon may be calcined at a high temperature so as to convert the metal active component precursor into oxides.
  • the carrier In the case where the ionizing radiation reduction is carried out in the above-mentioned manner c), it is preferred to treat the carrier with said fixing agent, prior to the radiation reduction.
  • the fixing agent may be combined with the carrier by spray coating.
  • the ionizing radiation reduction is carried out in the presence of an aqueous medium containing the free radical scavenger.
  • an aqueous medium containing the free radical scavenger containing the free radical scavenger.
  • e aq ⁇ hydrated electron
  • hydrogen atom .H
  • hydroxyl free radical .OH
  • hydrated hydrogen ion H 3 O +
  • e aq ⁇ is a strong reducing agent and can reduce most of metals in oxidized state to elementary metal.
  • Metal atoms formed through the reduction grow on the surface of the carrier and are finally stabilized by the carrier, thereby forming metal particles having catalytic activity.
  • the radiolysis of water generates simultaneously oxidizing free radicals such as .OH, which may re-oxidize the metal atoms just generated in the radiation reduction process.
  • an amount of the free radical scavenger is included in the irradiated system, and the free radical scavenge reacts with the oxidizing free radicals such as .OH to form a more stable free radical or a reducing free radical, thereby improving the reduction ability of the system.
  • the free radical scavenger useful in the preparation method according to the invention may be chosen from: C1-C6 alcohols and derivatives thereof, such as ethanol, ethylene glycol, isopropyl alcohol, tert-butyl alcohol, ascorbic acid and formic acid.
  • the free radical scavenger is preferably isopropyl alcohol or ethylene glycol.
  • the reaction medium of the ionizing radiation reduction is a solution of the free radical scavenger in water, which contains from 0.5 vol % to 98 vol %, preferably from 1 vol % to 70 vol %, and more preferably from 2 vol % to 60 vol % of the free radical scavenger.
  • the ionizing radiation used in the present method may be chosen from ⁇ -ray, X-ray and electron beam.
  • the radiation source may be chosen from 60 Co ( ⁇ source), 137 Cs ( ⁇ source), X-ray source and electron accelerator (electron beam), preferably from 60 Co, X-ray source and electron accelerator, and more preferably 60 Co.
  • the absorbed dose required to reduce completely the primary metal active component precursor may vary from 0.01 to 1 ⁇ 10 5 kGy, and preferably from 5 to 100 kGy. A person skilled in the art can readily determine the suitable dose required to reduce completely the primary metal active component.
  • the absorbed dose rate of the ionizing radiation may vary from 1 to 1 ⁇ 10 7 Gy/min, preferably from 10 to 10000 Gy/min, and more preferably from 20 to 100 Gy/min.
  • the ionizing radiation reduction process may be carried out at room temperature or a lower temperature, and preferably at room temperature.
  • the secondary metal active component or its precursor may be supported on the carrier before, during or after the ionizing radiation reduction.
  • the secondary metal active component or its precursor and the primary metal active component precursor are supported, simultaneously or successively, on the carrier by, for example, spray coating process or impregnating process, and then the ionizing radiation reduction is carried out.
  • the carrier is mixed with an aqueous solution containing the secondary metal active component or its precursor, the free radical scavenger, and the primary metal active component precursor, and then the resultant mixture is irradiated with the ionizing radiation, to obtain the catalyst comprising the primary metal active component and the secondary metal active component.
  • the secondary metal active component is supported on the carrier having the primary metal active component supported thereon by, for example, spray coating process or impregnating process.
  • the timing for supporting the secondary metal active component or its precursor may be selected according to the desired form of the secondary metal active component and considering the simplicity of the preparation method, and this is within the knowledge of a person skilled in the art. The preferences given when discussing the supporting of the primary metal active component precursor are applicable similarly to the secondary metal active component or its precursor.
  • auxiliary agents used to adjust the catalytic performance such as halogen
  • the carrier may be supported before, during or after the ionizing radiation reduction.
  • auxiliary agents used to adjust the catalytic performance, such as halogen
  • the timing and manner for supporting the auxiliary agents may be readily determined by a person skilled in the art.
  • the carrier having subjected to the ionizing radiation reduction or the carrier having subjected to the ionizing radiation reduction and the further supporting of the secondary metal active component and/or the other auxiliary agents is washed with a suitable amount of de-ionized water and then dried, or directly dried without the washing, to give the catalyst of the invention.
  • the drying may be carried out under air atmosphere or under vacuum, and preferably under air atmosphere.
  • the temperature for the drying may ranges from 40 to 200° C., and preferably from 50 to 120° C.
  • the drying time may ranges from 3 to 48 hours, and preferably from 5 to 24 hours.
  • the invention relates to the use of the present catalyst in an organic compound conversion reaction.
  • the organic compound conversion reactions include, but are not limited to, selective hydrogenation of ethyne in an ethylene stream to ethylene; selective hydrogenation of propyne and propadiene in a propylene stream to propylene; hydrogenation of an unsaturated hydrocarbon, especially hydrogenation of C4 and/or C5 unsaturated hydrocarbon; selective hydrogenation of alkynes in a pyrolysis gasoline; catalytic reforming; hydrocracking; and isomerization.
  • the catalyst of the invention has a primary metal active component in metal elementary state so that the catalyst can be used directly, without needing the reduction with hydrogen gas prior to use;
  • the catalyst of the invention in contrast to the catalysts prepared through a calcination decomposition process, is prepared at a normal temperature so that the high-temperature sintering of active component particles and/or carrier material is avoided, and the catalyst of the invention has generally higher activity and selectivity;
  • the present method provides a catalyst having more uniformly dispersed and more tightly bonded metal particles and better reaction performance
  • the method for preparing the catalyst of the invention is simple, and can significantly reduce energy consumption and gaseous pollutant emission, compared to the conventional methods;
  • the ⁇ -ray, X-ray or electron beam used in the ionizing radiation reduction process according to the invention have strong penetrating ability, and the existing large-scale industrial irradiation sources can be used directly in the production of a mass of a catalyst.
  • Catalyst A 17 ml of solution of PdCl 2 in hydrochloride acid having a Pd content of 2 mg/ml was diluted with 30 ml of de-ionized water and then neutralized with 1 N NaOH solution to pH value of 3.0. So-obtained solution was uniformly spray coated on 100 g of Al 2 O 3 carrier.
  • the carrier was sufficiently wetted with 20 ml of 50% solution of isopropyl alcohol in water, and then irradiated under vacuum with a 60 Co ⁇ radiation source at a dose rate of 30 Gy/min for 15 h. The irradiated sample was washed with de-ionized water four times, and then dried at 60° C. for 12 hours, to give Catalyst A.
  • Catalyst A has a grey appearance, a Pd content of 0.034 wt %, and an average diameter of Pd particles of 3.3 nm.
  • Catalyst B has a grey appearance, a Pd content of 0.033 wt %, and an average diameter of Pd particles of 5.4 nm.
  • Catalyst D 13.5 ml of solution of PdCl 2 in hydrochloride acid having a Pd content of 10 mg/ml and 35 ml of de-ionized water were combined and spray coated on 100 g of Al 2 O 3 carrier. After drying, 27 ml of AgNO 3 aqueous solution having a Ag content of 5 mg/ml and 10 ml of 3N NaOH solution were successively spray coated on the carrier.
  • the carrier was sufficiently wetted with 20 ml of 50% solution of isopropyl alcohol in water, and then irradiated under vacuum with a 60 Co ⁇ radiation source at a dose rate of 30 Gy/min for 15 h. The irradiated sample was dried at 60° C. for 12 h, to give Catalyst D.
  • Catalyst D has a dark grey appearance, a Pd content of 0.135 wt %, a Ag content of 0.135 wt %, and an average diameter of Pd particles of
  • Catalyst E has a black appearance, a Pd content of 0.3 wt %, and an average diameter of Pd particles of 4.7 nm.
  • Catalyst F has a light yellow appearance and a Pd content of 0.034 wt %.
  • Catalyst G has a yellow appearance and a Pd content of 0.135 wt %.
  • the dispersion of Pd particles on the surface of the Catalysts C, D, E and G was observed through a transmission electron microscope (TEM), and the results are shown in FIG. 1 .
  • the TEM results show that in the Catalysts C, D and E from the Examples, Pd particles are uniformly dispersed on the carrier surface, while in the Catalyst G from the Comparative Example, the Pd particles on the surface exhibit agglomeration and sintering phenomenon.
  • Catalysts A, B and F were used in hydrogenation test of a pyrolysis gas from an ethylene plant as follows. 1 ml of each of the catalysts was loaded into a stainless steel tubular reactor with an internal diameter of 7.8 mm. The atmosphere in the reactor was replaced with nitrogen gas, then a feed gas, together with hydrogen gas, was passed through the reactor.
  • the feed gas had a composition by mole of: 36.5% methane, 8% ethane, 38% ethylene, 10% propylene, 0.8% ethyne, 0.4% propyne, 0.2% propadiene, as well as a minor amount of butenes, butadiene, pentanes, and the like, and the hydrogen gas was used in an amount of about 16 mol %, relative to the feed gas.
  • the test was conducted at a space velocity of 10000 h ⁇ 1 .
  • Catalysts C, D and G were used in a side-line evaluation test in a C3 fraction liquid phase selective hydrogenation industrial scale plant.
  • a fixed bed reactor was used, catalyst loading amount was 92 ml, reaction pressure was 2 MPa (gauge), and space velocity was 70 h ⁇ 1 .
  • the feed at the reactor inlet comprised 2.3 mol % MAPD, 92.5 mol % propylene, and 5.2 mol % propane.
  • Temperature at reactor inlet and H 2 /MPAD ratio were adjusted to obtain a selectivity as high as possible, provided that the MAPD was completely removed by the hydrogenation.
  • the calculations of MAPD conversion and propylene selectivity were as described above.
  • Catalyst H has a Pd content of 0.035 wt % and a Ag content of 0.7 wt %.
  • Catalyst I 6.0 ml of 3.5 mg/ml solution of AgNO 3 was uniformly spray coated on 30 g of Al 2 O 3 carrier. After drying, the carrier was calcined at 550° C. for 8 h to decompose AgNO 3 . 5.25 ml of 2 mg/ml solution of PdCl 2 was adjusted with 1 N NaOH solution to pH 3, and the resultant solution was uniformly spray coated on the Ag-containing carrier.
  • the carrier was wetted with 10 ml of 30% solution of ethylene glycol in water, and then irradiated under vacuum with a 60 Co ⁇ radiation source at a dose rate of 30 Gy/min for 25 h. The irradiated sample was washed with de-ionized water four times and dried at 50° C. for 12 h, to give Catalyst I.
  • Catalyst I has a Pd content of 0.035 wt % and a Ag content of 0.7 wt %.
  • Catalyst J has a Pd content of 0.035 wt % and a Pb content of 0.7 wt %.
  • Catalyst K has a Pd content of 0.035 wt %, a Ag content of 0.035 wt % and a Bi content of 0.01%.
  • Catalyst L has a Pd content of 0.035 wt % and a Ag content of 0.7 wt %.
  • the catalyst contained Al 2 O 3 as a carrier, and Pd and Ag as active components, with Pd content being 0.035 wt % and Ag content being 0.7 wt %.
  • the catalysts from Examples 7 to 10 and Comparative Examples 3 to 4 were used in post-hydrogenation simulation experiment of ethylene as follows. 1 ml of each of the catalysts was loaded into a stainless steel tubular reactor with an internal diameter of 7.8 mm. The atmosphere in the reactor was replaced with nitrogen gas, and then a feed gas that simulated an overhead stream from a deethanizer, together with hydrogen gas, was passed through the reactor. The feed gas had a composition by mole of: 7% ethane, 92.64% ethylene, and 0.36% ethyne, and the molar ratio of hydrogen gas to alkyne was 2:1. The test was conducted at a space velocity of 10000 h ⁇ 1 .
  • the catalysts were evaluated with respect to their performance in selective hydrogenation of ethyne, with Catalysts H, I, J and K from the Examples being evaluated directly, and the comparative Catalyst L and BC-H-20 being evaluated after having been reduced in hydrogen gas flow at 150° C. for 2 h.
  • the conversion and selectivity for hydrogenating ethyne to ethylene at 120-130° C. achieved by each of said catalysts are given in Table 4 below.
  • the calculations of the conversion and selectivity of ethylene are as described above.
  • Catalyst M has a Pd content of 0.20 wt % and a Cu content of 0.50 wt %, based on the total weight of the catalyst.
  • Catalyst N has a Pd content of 0.20% and a Ag content of 0.1%, based on the total weight of the catalyst.
  • Catalyst O has a Pd content of 0.20%, a Pb content of 0.1%, and a Ca content of 0.2%, based on the total weight of the catalyst.
  • Catalyst P 25 ml of 10 mg/ml solution of Pd(NO 3 ) 2 and 5 ml of 10 mg/ml solution of Pb(NO 3 ) 2 was added into 20 ml distilled water to prepare a mixed solution, and then the mixed solution was spray coated on 100 g of alumina carrier, followed by the spray coating of 10 ml of 3N NaOH solution. 20 ml of 50% solution of isopropyl alcohol in water was added to the carrier having Pd and Pb loaded thereon and uniformly mixed, and then the excess solution was decanted. The mixture was irradiated under vacuum with a 60 Co ⁇ radiation source at a dose rate of 30 Gy/min for 15 h. The irradiated sample was dried at 120° C. for 6 h, to give Catalyst P. Catalyst P has a Pd content of 0.25% and a Pb content of 0.05%, based on the total weight of the catalyst.
  • Catalyst Q was prepared according to the method described in Chinese patent CN 1229312C.
  • Catalyst Q has a Pd content of 0.25% and a Pb content of 0.05%, based on the total weight of the catalyst.
  • Catalysts M, N, O, P and Q prepared in Examples 12 to 15 and Comparative Example 5 were used in hydrogenation experiment of C4 fraction conducted in a fixed bed reactor.
  • the loading amount of the catalysts was 50 ml.
  • Evaluation conditions were as follows: reaction temperature at inlet: 40° C., reaction pressure: 3.0 MPa (absolute), liquid hourly space velocity: 20-30 h ⁇ 1 , hydrogen/unsaturated hydrocarbon ratio: 1.5 (mol/mol).
  • the evaluation experiment results are given in Table 5 below.
  • the evaluation experiment results show that, compared to the supported catalyst prepared by the conventional method, the catalysts according to the invention prepared by means of radiation reduction process exhibit higher catalytic activity in the olefin hydrogenation and can be operated at higher olefin load.
  • the catalysts according to the invention may be used at markedly reduced amount and contain markedly reduced amount of noble metal, compared to the catalyst prepared by the conventional method.
  • 70 ml aqueous solution of PbCl 2 having a Pd content of 0.36 wt % and a pH value of 4.0 was prepared (during the preparation, 1N NaOH solution was used to adjust the pH value).
  • the above PbCl 2 solution was spray coated on 100 g of alumina carrier. After air drying, the carrier was dried in an oven at 120° C. for 24 h.
  • 70 ml Pb(NO 3 ) 2 solution having a Pb content of 0.72 wt % was prepared and spray coated on the alumina carrier containing Pd. After left in stand for 20 min, a solution prepared from 20 ml of water and 20 ml of isopropyl alcohol was added to the carrier containing Pd.
  • Catalyst T has a Pd content of 0.25 wt % and a Pb content of 0.50 wt %.
  • Catalyst U was prepared by a procedure similar to that described in Example 18, which has a Pd content of 0.25 wt % and a Sn content of 0.40 wt %.
  • Catalyst V was prepared by a procedure similar to that described in Example 18, which has a Pd content of 0.25 wt %, a Sn content of 0.40 wt % and a Mg content of 2.0 wt %.

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Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
CN200810227414A CN101733172A (zh) 2008-11-26 2008-11-26 一种负载型金属催化剂及其制备方法和应用
CN200810227414.2 2008-11-26
CN200910082421.2 2009-04-17
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CN113333004A (zh) * 2021-06-20 2021-09-03 浙江工业大学 一种负载型铜基催化剂的制备方法及应用
CN113784778A (zh) * 2019-02-25 2021-12-10 英国贝尔法斯特女王大学 烷烃氧化的方法和装置
CN114349590A (zh) * 2022-01-10 2022-04-15 上海巽田科技股份有限公司 一种合成芳香族化合物的方法
CN114744224A (zh) * 2022-04-21 2022-07-12 浙江理工大学 一种氮掺杂碳纳米管负载镍钴复合纳米线的制备与应用

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CN113784778A (zh) * 2019-02-25 2021-12-10 英国贝尔法斯特女王大学 烷烃氧化的方法和装置
CN113333004A (zh) * 2021-06-20 2021-09-03 浙江工业大学 一种负载型铜基催化剂的制备方法及应用
CN114349590A (zh) * 2022-01-10 2022-04-15 上海巽田科技股份有限公司 一种合成芳香族化合物的方法
CN114744224A (zh) * 2022-04-21 2022-07-12 浙江理工大学 一种氮掺杂碳纳米管负载镍钴复合纳米线的制备与应用

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