• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    1445494 Oxidation catalysts MONSANTO CO 18 March 1974 [19 March 19731 11861/74 Heading B1E [Also in Division C2] Catalysts are made by a process which comprises heating a pentavalent vanadium compound in an acid medium with sufficient reducing agent to reduce at least 50 atom% of the vanadium to the tetravalent state, using as the sole reducing agent a halogen free trivalent phosphorous compound. The precursor may be calcined. Preferably the reduction to tetravalent vanadium is performed in a closed system at a temperature above 100‹C.
    公开号:SU1271366A3
    申请号:SU742005050
    申请日:1974-03-18
    公开日:1986-11-15
    发明作者:Раффелсен Хэролд；Ли Роберто；Джосеф Долен Томас
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for preparing catalysts for the oxidation of hydrocarbons, in particular to a method for preparing a phosphorus-vanadium catalyst for the oxidation of butane to maleic acid) ;. The aim of the invention is to simplify the process by using phosphorous acid or phosphorus trichloride as a reducing agent in a certain ratio to vanadium pentoxide. PR and ME 1. A phosphorus vanadium oxygen catalyst is obtained by slowly adding 133.08 g of five vanadium oxides to a mixture of 450 ml of water, 50.6 g of 85% phosphoric acid and 91.7 g of 99.4% phosphoric acid (the ratio phosphoric acid :: forforist acid 1: 2.5 J. The atomic ratio of phosphorus to vanadium is approximately 1.06: 1. The amount of phosphorous acid corresponds to approximately 50% excess of 1: and the phosphorous acid required to convert pyvalent vanadium to tetravalent vanadium. a mixture of vanadium and phosphorus compounds in autokl The autoclave containing vanadium and phosphorus compounds is heated to 145 ° for 3 hours. After cooling and opening, the phosphoric anadic oxygen precursor is found in an aqueous suspension. The precursor is separated from water and washed several times. Then I mix 20% by weight of water based on the weight of the precursor with the precursor in order to form a viscous putty, which is extruded through a matrix with a diameter of 5.556 mm and cut into granules with a length of 5.556 mm. Shiva air ,, LOAD vayut to 90 ° C in an oven, vsharivayut all remaining water and calcined at 500 C for 4 hours to images audio fosforvanadiykislorodnogo catalyst. The 50 cm granule catalyst is placed in a fixed glass bed reactor with an outer diameter of 25.4 mm. Using this reactor, results are obtained that can be compared with results obtained in industrial reactors. The catalyst is conditioned by passing 6,6 mol% of butane in the air mixture over the catalyst at a space velocity of 1327 at 16 h. Maleic angled grind is obtained using 3 mol,% of butane at an air pressure of 2 h at a space velocity of 2800 at 440 ° С After 50 hours, the yield of maleic anhydride is 39%, Example 2. The catalyst according to example 1 is obtained, except that 133.08 g of vanadium thioxide are added to a mixture of 450 ml of water, 84.4 g of 85% phosphoric acid and 66.04 g of 99.4% phosphoric acid (P ; | P 1 S1) to obtain 10% phosphorous acid in excess of the stoichiometry of the amount required to produce tetravalent vanadium. The resulting putty is extruded through a matrix with a diameter of 5.556 mm and cut into granules with a length of 5.556 mm. After drying and calcining, the granules are placed in a fixed-tube reactor with a diameter of 12.7 I-IM. Then maleic angi, drid at 440 ° C using 5 mol% of butane in an air mixture at a space velocity of about 2800 is obtained. After 50 hours, the yield of maleic anhydride is 35%. EXAMPLE 3 A catalyst according to npfiMepy 2 is obtained, except that instead of forming putty from. the washed precursor is dried the precursor on the steam bath and crushes B 45325 mesh powder of Standard Stage С111А (0.350, 44 km). This blend is placed in a reactor with a diameter of 33.35 mm with a glass fluidized bed and a mixture of 4 mol% of butane and air is passed through the catalyst at 463 ° C and a space velocity of 400 / h. After 12 hours, the yield of maleic anhydride is as follows. EXAMPLE 4 A catalyst is prepared as described in example 2, except that instead of filtering the precursor from the aqueous suspension, the precursor is suspended in the aqueous suspension on a steam bath and evaporated to dryness. The remaining dry precursor is then ground into powder and placed in a reactor with a fluidized bed of laboratory scale, I1-1 o: P13y feed 5 mol,% butane in air mixture at a space velocity of 400 cm after 12 h, 35.3% maleic anhydride is obtained at 463 ° C, Example 5. A catalyst is prepared as described in Example 1, except that 51 g of phosphorus trichloride are added to 450 ml of water (hydrolysis produces porous acid and hydrochloric acid and 41.5 g of 85% phosphoric acid (p3 +. pS-F, Q) 133 g vanadium pyatioxide, due to a precursor is formed with an atomic ratio of phosphorus to vanadium of about 1.05: 1. After 50 hours at 440 ° C, 32% maleic anhydride is obtained using 3 mol% of butane in air at a space velocity of about 2800. Example 6 is obtained by adding 266.2 g (1.46 mol). Vanadium hydroxide to a mixture of 900 ml of water. 168.7 g (1, 46 mol of 85% phosphoric acid and 132.0 g (1.60 mol of 100% phosphorous acid. The ratio (atomic) of phosphorus and vanadium corresponds to 1.05, and the ratio (atomic) of trivalent phosphorus and pyvalent corresponds to approximately 1.10. The amount of phosphorous acid is 10% in excess with respect to the phosphorous acid needed to convert pentavalent vanadium to tetravalent vanadium. A mixture of vanadium and phosphorus compounds is loaded into an autoclave, which is then heated to, followed by sealing. The temperature is increased to overheating within 146-148 ° C for 5.5 hours. The resulting aqueous suspension (sludge) of the catalyst precursor is cooled to 35 ° C, the water is evaporated on a steam bath to form a thick mass. The last extrusion is passed through a die plate with a diameter of 0.56 cm. The extrude is cut into pieces about 0.56 cm long. These pieces of 0.56 cm X 0.56 cm in size are dried in air at room temperature, calcined at 500 ° C for 4 hours , receiving phosphorus vanadium oxygen catalyst. The catalyst is conditioned and used to produce maleic anhydride as in Example 1, except that the maleic anhydride is obtained at a temperature of 420 liters; and the product yield is 30%. EXAMPLE 7 A catalyst was prepared analogously to Example 6, except that 295.7 g (1.62 mol)) Vanadium pyatoxide was added to 1000 ml of water, 206.2 g (0.79 mol) 85% of phosphoric acid and 146.7 g TI (1.79 mol) of 100% phosphorous acid (P / U 1.10, 1.00; 10% excess relative to the required phosphorous acid). The mixture for sealing in an autoclave at 100 ° C is heated to 150 ° C for 5.5 hours. The catalyst is conditioned and used to produce maleic anhydride as in Example 1, with a yield of the target product in an amount of 30%. EXAMPLE 8 A catalyst is prepared as described in Example 2, except that 340.00 g of vanadium pyatoxy is added to a mixture of 1150 ml of water, 280.18 g of 85% phosphorous acid and 169.63 g of 99, 4% phosphorous acid to obtain about 10% phosphorous acid in excess of the stoichiometric amount required for the preparation of tetravalent vanadium and the ratio of phosphorus: vanadium to 1.20. The contents of the autoclave are dried at 150 ° C. The dried precursor is sieved through a sieve with 35 holes and compressed into cylinders. After calcining, the pellets are placed in the reactor for 4 hours. Maleic anhydride is obtained at 452 ° C using 2 mol% of butane in an air mixture at a space velocity of 1400 cm / cm / / h. After 240 hours, the yield of maleic anhydride is 41%.
    权利要求:
    Claims (1)
    [1]
    A METHOD FOR PREPARING A PHOSPHOROVANADIUM CATALYST FOR THE OXIDATION OF BUTANE IN MALEIC ANHYDRIDE by reacting vanadium-dium pentoxide with phosphoric acid in the presence of a reducing agent at an elevated temperature, followed by separation of the obtained precipitate, molding it, drying and calcining, differs in that the method is different. phosphorous acid or phosphorus trichloride in a 10-50% excess with respect to vanadium pentoxide is used as a reducing agent, and the reaction is carried out at 145-150 ° C for 3-5.5 hours.
    with
    1271366 AZ
    类似技术:
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    同族专利:
    公开号 | 公开日
    AU6677474A|1975-09-18|
    FR2222132B1|1978-09-08|
    DE2412913C2|1982-08-26|
    FR2222132A1|1974-10-18|
    NL163135B|1980-03-17|
    DE2412913A1|1974-09-26|
    JPS49126587A|1974-12-04|
    ES424314A1|1976-06-01|
    US3907707A|1975-09-23|
    ES433333A1|1976-10-16|
    BE812462A|1974-09-18|
    NL7403502A|1974-09-23|
    CA1025176A|1978-01-31|
    BR7402085D0|1974-11-05|
    JPS532631B2|1978-01-30|
    NL163135C|1980-08-15|
    GB1445494A|1976-08-11|
    IT1007659B|1976-10-30|
    DD114057A5|1975-07-12|
    DD111364A5|1975-02-12|
    引用文献:
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    US4172084A|1977-05-31|1979-10-23|Standard Oil Company|Production of maleic anhydride from four-carbon hydrocarbons using catalysts prepared by hydrothermal techniques|
    CA1140912A|1979-07-30|1983-02-08|Ramon A. Mount|Process for preparing phosphorus-vanadium-oxygencatalysts|
    US4283307A|1980-06-02|1981-08-11|Denka Chemical Corporation|Catalyst structure for the partial oxidation of n-butane to produce maleic anhydride|
    US4317778A|1980-12-29|1982-03-02|Standard Oil Company |Preparation of maleic anhydride using fluidized catalysts|
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    CA1197230A|1982-06-30|1985-11-26|Dennis E. Dria|Preparation of improved mixed vanadium phosphorusoxide catalysts and their use in oxidation processes|
    US4569925A|1982-07-01|1986-02-11|Exxon Research & Engineering Co.|Process for preparing a vanadium phosphorus oxygen catalyst composition by an organic solution method|
    US4626412A|1984-12-14|1986-12-02|Monsanto Company|Method and apparatus for carrying out catalyzed chemical reactions and for studying catalysts|
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    法律状态:
    优先权:
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    US342325A|US3907707A|1973-03-19|1973-03-19|Vanadium catalysts made with a trivalent phosphorus compound|
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