• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Molybdenum-containing oxidation catalysts used in a fluid-bed reactor have been discovered to become partially deactivated through loss of molybdenum from the catalyst. These partially deactivated catalysts are regenerated in situ by the addition of fluid-bed particles consisting of an essentially inert support material containing molybdenum.
    公开号:SU888803A3
    申请号:SU742055025
    申请日:1974-08-19
    公开日:1981-12-07
    发明作者:Льюис Калахан Джеймс；Фрэнсис Миллер Артур；Гарсайд Шоу Вильфрид
    申请人:Дзе Стандарт Ойл Компани (Инофирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR REGENERATION OF MOLIBDEN-CONTAINING
    one
    The invention relates to the field of petrochemical technology and can be used in oxidation, oxidative dehydrogenation, or oxidative ammonolysis of hydrocarbons.
    It has been established that certain molybdenum containing catalysts are deactivated during their use in oxidative ammonolysis, oxidation or oxidative dehydrogenation reactions in fluidized bed reactors. There are undoubtedly a number of possible causes for catalyst deactivation.
    So, molybdenum-containing catalysts deactivated during the oxidative dehydrogenation of hydrocarbons can be regenerated by. treating the fluidized bed of catalyst particles with air or with a mixture of air and steam at elevated temperature G1.
    Such a regeneration is able to restore the activity of the catalyst | ONLY if the loss of the active catalyst
    caused by the conversion of molybdate to molybdite or the presence of burnable contaminants on the catalyst surface.
    In the process of oxidative ammonolysis, oxidation or oxidative dehydrogenation of a hydrocarbon at a temperature of about 200-600 ° C in a fluidized bed reactor using an oxidation catalyst in a fluidized bed containing molybdenum, this catalyst partially deactivates 3ai molybdenum loss.
    The known method of catalyst regeneration does not eliminate the loss of catalyst activity caused by the loss of molybdenum.
    In order to restore the initial content of molybdenum in the catalyst and to restore its initial activity caused by the loss of the molybdenum component, it is proposed that the 1СЯ perform regeneration in the presence of particles of an inert carrier containing 3 more than 50 weight. molybdenum trioxide at 200-600 ° C. The said particles in contact with the deactivated catalyst may contain any form of molybdenum: metallic molybdenum, oxide, nitrate or halide of molybdenum, with the use of molybdenum oxide being preferred due to the compatibility of the oxide with the oxidation catalyst. The amount of molybdenum in the particle is not critical and varies widely. However, it is necessary that the hour of the inert carrier be introduced into the particle. Preferred are particles that contain more than 50 ve molybdenum component. In addition to the molybdenum component, particles of the fluidized bed added to regenerate the catalyst may contain other elements, such as iron, bismuth or tellurium, which are used to regenerate the catalyst. However, the use of catalysts, consisting essentially of an inert carrier and molybdenum or a molybdenum compound, is optimal. An inert carrier may be selected from any list of carriers, the use of which is not difficult. Such inert carriers give low degrees of conversion (less than 25) of starting materials. Preferred carriers are silica gel, alumina, alumino silicate, zirconia, boron phosphate, silicon carbide or titanium dioxide. Silica gel is a carrier, which is particularly suitable for regeneration. Fluid bed particles used for regeneration are prepared in various ways. A preferred preparation method comprises spray drying an aqueous suspension containing finely ground carrier and finely ground molybdenum or a molybdenum compound. Similarly, a solution of molybdenum compound can be combined with a finely ground carrier, and the resulting suspension is dried and ground to the required size of catalyst particles in a fluidized bed. For best results, the molybdenum should be placed on the carrier during the preparation. To implement 3 of the proposed method, a physical mixture of carrier and molybdenum is used, which is obtained by grinding a dry mixture of silica gel and molybdenum oxide, however, it is preferable to use a preparative technique in which molybdenum sits on. carrier. The regenerative process of the invention occurs by contacting the fluidized bed particles of inert carrier and molybdenum with the spent catalyst, under conditions in which the activity of the catalyst is restored. It is preferable to create conditions similar to those of the reaction with in situ catalyst regeneration, which is particularly preferred since it is associated with minimal interruption of the catalytic process. Preferably, the regeneration is carried out at an elevated temperature (200-600 s). Regeneration has been found to be promoted by the presence of molecular oxygen, usually added in the form of air. Water vapor also contributes to the transfer. Especially preferred is the use of a combination of air and water vapor. The exact mechanism by which catalyst regeneration takes place is not established. However, it is known that part of the molybdenum in the fluidized bed particles somehow passes to the deactivated oxidation catalyst and is inserted into its lattice structure so that the lack of molybdenum in the spent catalyst is replenished and the activity of the catalyst is restored. The proposed regeneration method is used for catalysts that contain and are used in oxidative ammonolysis, oxidation and oxidative dehydrogenation. However, this technology is used for a wide range of other reactions in which molybdenum-containing catalysts are used. For the implementation of the proposed method, carriers are used which have some degree of physical instability after the molybdenum passes to the oxidation catalyst. When the molybdenum concentration falls to a low level, the catalyst is milled and discharged into the stream, leaving
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of regenerating a molybdenum-containing catalyst for oxidizing hydrocarbon processing by treating a fluidized bed of its particles with air or a mixture of air and steam at elevated temperature, characterized in that, in order to restore the initial content of molybdenum in the catalyst and restore its initial activity, the treatment is carried out in the presence of particles of an inert carrier containing more than 50 wt.% molybdenum trioxide at 200-600 ° C.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU888803A3|1981-12-07|Method of regenerating molybdenum-containing catalyst
    ES8403040A1|1984-03-01|Process for improving activity of tellurium containing metal oxide catalysts
    AU2013278857B2|2016-02-04|Regeneration of spent paraffin dehydrogenation catalyst
    RU2638930C2|2017-12-19|Catalytic composition and method of reactivation used for alkane dehydrogenation
    US2901441A|1959-08-25|Preparation of an oxidation catalyst
    KR870000055B1|1987-02-09|Olefin bond isomerisation process
    CA1312324C|1993-01-05|Process for regenerating sulfur contaminated reforming catalysts
    US4043939A|1977-08-23|Reactivation of catalysts useful for nitrogen oxide removal
    KR100566856B1|2006-04-03|Process for Manufacture and Use of Improved Attrition Resistant Catalyst
    US3117076A|1964-01-07|Reactivation of platinum cataysts
    US2728754A|1955-12-27|Continuous ethylene polymerization with catalyst regeneration
    US2880168A|1959-03-31|Maintenance of catalyst activity using methyl cloride
    US4303550A|1981-12-01|Methods for the regeneration of deactivated phosphomolybdic acid based catalysts
    US3252918A|1966-05-24|Catalyst demetallization
    US3234145A|1966-02-08|Catalyst demetallization
    US3122511A|1964-02-25|Cracking catalyst demetallization
    US4267032A|1981-05-12|Demetallization process for a conversion catalyst
    US4962272A|1990-10-09|Treatment of arsine removal catalysts
    US2382472A|1945-08-14|Regeneration of catalysts
    US2471853A|1949-05-31|Catalytic partial oxidation process
    US4071601A|1978-01-31|Selective removal of nitrogen oxides from waste gases using V-Mo-W catalysts
    US2598309A|1952-05-27|Catalytic cracking of hydrocarbon oil
    US2848380A|1958-08-19|Catalytic cracking process and composition
    US3278419A|1966-10-11|Platinum group hydroforming catalyst reactivation process
    US3151088A|1964-09-29|Catalyst demetallization
    同族专利:
    公开号 | 公开日
    DD115656A5|1975-10-12|
    PL93420B1|1977-05-30|
    JPS5857422B2|1983-12-20|
    FR2241516B1|1978-11-24|
    DE2435031C2|1987-11-12|
    NL182202B|1987-09-01|
    JPS5049201A|1975-05-01|
    RO68029A|1980-10-30|
    US3882159A|1975-05-06|
    NL182202C|1988-02-01|
    CA1030555A|1978-05-02|
    IT1019892B|1977-11-30|
    IE39819B1|1979-01-03|
    DE2435031A1|1975-02-27|
    YU36874B|1984-08-31|
    YU228274A|1982-02-25|
    IN142324B|1977-06-25|
    NL7411063A|1975-02-24|
    IE39819L|1975-02-20|
    GB1474058A|1977-05-18|
    FR2241516A1|1975-03-21|
    CS184831B2|1978-09-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2800461A|1952-03-01|1957-07-23|Exxon Research Engineering Co|Method of catalyst preparation and regeneration|
    DE1066571B|1956-10-29|1959-10-08|Reichhold Chemicals, Inc., Detroit, Mich. |Process for the regeneration of an iron-molybdenum catalyst for the oxidation of alcohols to aldehydes|
    CA719280A|1959-07-18|1965-10-05|Schwarzer Klaus|Process for the production of aliphatic nitriles|
    NL298431A|1962-09-26|1900-01-01|
    US3518284A|1967-02-20|1970-06-30|Shell Oil Co|Partial oxidation of organic compounds|
    US3472892A|1967-05-10|1969-10-14|Standard Oil Co|Fluid bed process for synthesis of nitriles by ammoxidation and the recycling of ammonia-rich catalyst from a quench zone to a reaction zone|
    IT810999A|1967-08-01|
    US3629148A|1969-09-24|1971-12-21|Standard Oil Co Ohio|Iron-modified bismuth phosphomolybdate catalyst|
    US3639103A|1970-04-21|1972-02-01|Badger Co|Fluid bed reactors|
    BE765858A|1970-05-22|1971-10-18|Badger Co|PROCESS FOR PREPARING UNSATURATED NITRILS|
    US3658877A|1970-07-13|1972-04-25|Standard Oil Co Ohio|Process for prevention of catalyst hang-up in ammoxidation of olefins to unsaturated nitriles|US4029636A|1974-11-12|1977-06-14|Celanese Corporation|Method for reducing molybdenum trioxide content of gases issuing from reactors containing molybdenum-based catalysts|
    US4168246A|1975-11-28|1979-09-18|Monsanto Company|Production of oxidation catalyst|
    US4052332A|1976-04-20|1977-10-04|E. I. Du Pont De Nemours And Company|Catalyst regeneration with impregnation of bismuth and molybdenum|
    US4052333A|1976-06-25|1977-10-04|Monsanto Company|Catalyst treatment|
    US4202865A|1978-10-30|1980-05-13|United Technologies Corporation|On-line regeneration of hydrodesulfurization catalyst|
    USRE30430E|1979-02-26|1980-11-04|Denka Chemical Corporation|Catalyst treatment|
    US4305886A|1979-08-13|1981-12-15|Uop Inc.|Process for the ammoxidation of alkylaromatic hydrocarbons|
    US4284583A|1979-10-29|1981-08-18|Uop Inc.|Ammoxidation process with external catalyst regeneration zone|
    JPS6333903B2|1980-09-20|1988-07-07|Mitsui Toatsu Chemicals|
    NL8100364A|1981-01-27|1982-08-16|Stamicarbon|CATALYST REACTIVATION.|
    JPS6330065B2|1981-02-05|1988-06-16|Mitsui Toatsu Chemicals|
    DE3217700A1|1981-05-15|1982-12-02|Nitto Chemical Industry Co., Ltd., Tokyo|METHOD FOR IMPROVING THE ACTIVITY OF METAL OXIDE CATALYSTS CONTAINING TELLUR|
    DE3311521C2|1982-07-17|1988-08-18|Skw Trostberg Ag, 8223 Trostberg, De|
    JPH0256939B2|1982-10-26|1990-12-03|Nitto Chemical Industry Co Ltd|
    US4590011A|1983-11-23|1986-05-20|Monsanto Company|Ammoxidation process|
    JPH0529502B2|1984-07-23|1993-04-30|Mitsubishi Petrochemical Co|
    JPH0570503B2|1986-11-28|1993-10-05|Nippon Catalytic Chem Ind|
    US5378668A|1990-07-13|1995-01-03|Ec Erdolchemie Gmbh|Process for reactivating ammoxidation catalysts|
    DE4022416A1|1990-07-13|1992-01-16|Erdoelchemie Gmbh|METHOD FOR REACTIVATING AMMOXIDATION CATALYSTS|
    CN1025551C|1990-11-05|1994-08-03|中国石油化工总公司|Long-term stabilizing method for catalyst activity of acrylonitrile fluidized bed|
    DE4110337A1|1991-03-28|1992-10-01|Siemens Ag|METHOD AND DEVICE FOR REGENERATING CONSUMED DENOXCATALYSTS|
    KR100277241B1†|1993-06-25|2001-02-01|고오사이 아끼오|Process for preparing unsaturated aldehyde and unsaturated carboxylic acid|
    CN1046867C|1994-04-11|1999-12-01|上海石油化工股份有限公司|Reactivating or regenerating method for molybdenum-bismuth-iron system ammoxidation catalyst|
    JP3217794B2|1996-03-12|2001-10-15|旭化成株式会社|Method for producing unsaturated nitrile|
    CN1063098C|1996-08-06|2001-03-14|中国石油化工总公司|Utilizing technology for acrylonitrile fluidized bed waste catalyst|
    UA57721C2|1997-08-11|2003-07-15|Асахі Касеі Кабусікі Кайся|A process for producing acrylonitrile or methacrylonitrile from propane or isobutane|
    US6037290A|1998-04-15|2000-03-14|Lehigh University|In situ regeneration of metal-molybdate catalysts for methanol oxidation to formaldehyde|
    JP3573959B2|1998-05-12|2004-10-06|ダイヤニトリックス株式会社|Regeneration of Molybdenum-Containing Oxide Fluidized Bed Catalyst|
    DE10117357A1|2001-04-06|2002-10-10|Basf Ag|Process for the production of acrylic acid or methacrylic acid by gas phase oxidation of propane or isobutane|
    DE10131297A1|2001-06-29|2003-01-09|Basf Ag|Production of partial oxidation products of an olefinic hydrocarbon, useful for acrolein/acrylic acid from propane, comprises intermittent supplementation of olefin from another source.|
    US7902112B2|2006-10-26|2011-03-08|Dia-Nitrix Co., Ltd.|Fluidized bed catalyst for producing acrylonitrile and process for producing acrylonitrile|
    JP5011167B2|2008-03-03|2012-08-29|ダイヤニトリックス株式会社|Catalyst for producing acrylonitrile and method for producing acrylonitrile|
    CN103154010A|2010-09-14|2013-06-12|科学与工业研究委员会|Organometallic molybdenum acetylide dioxo complex and process for the preparation thereof|
    CN104144910B|2012-02-29|2016-08-17|三菱丽阳株式会社|The manufacture method of acrylonitrile|
    CN103418405B|2012-05-16|2015-04-08|中国石油化工股份有限公司|Replenishment catalyst for maintaining stabilization production of acrylonitrile device|
    JPWO2018169088A1|2017-03-17|2020-01-23|三菱ケミカル株式会社|Catalytic oxidation method and method for producing conjugated diene|
    WO2020172562A1|2019-02-21|2020-08-27|Ascend Performance Materials Operations Llc|Processes for stabilizing antimony catalysts|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US390175A|US3882159A|1973-08-20|1973-08-20|Reactivation of molybdenum containing oxidation catalysts in fluid bed reactors|
    [返回顶部]