• 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:
    Addition of oxidic compounds of molybdenum and/or tungsten, cerium and optionally cobalt and/or chromium to iron-potassium-vanadium oxide catalysts useful in the dehydrogenation of hydrocarbons to the corresponding more unsaturated hydrocarbons results in an improved catalyst.
    公开号:SU1077556A3
    申请号:SU782600799
    申请日:1978-04-12
    公开日:1984-02-29
    发明作者:Ханс Риссер Грегор
    申请人:Шелл Интернейшнл Рисерч Маатсхаппий Б.В. (Фирма)；
    IPC主号:
    专利说明:

     h: l
    01
    35
    The invention relates to the production of a catalyst for the dehydrogenation of ethylbenzene to styrene.
    A known catalyst for the dehydrogenation of ethylbenzene to styrene, the oxides of iron, potassium and chromium tl.,
    Closest to the present invention is a catalyst for dehydrogenating ethylbenzene to styrene containing oxides, iron, potassium, and / or potassium carbonate and vanadium oxide.
    A disadvantage of the known catalyst is its relatively low activity and selectivity in the dehydrogenation of ethylbenzene to styrene.
    The purpose of the invention is to increase the activity and selectivity of the catalyst.
    This goal is achieved by the fact that the catalyst containing iron oxide, potassium oxide and / or potassium carbonate and vanadium oxide, additionally contains molybdenum oxide and / or tungsten oxide and cerium oxide with the following content of components, wt.%:
    Potassium oxide and / or
    potassium carbonate 5-16,6
    Vanadium oxide 0.18-9
    Molybdenum oxide and / or oxide ox. Fra .-:
    0.15-9. 0.37-38.5 Else
    The proposed catalyst is prepared by dry blending of molybdenum trioxide, trivalent cerium carbonate, divalent cobalt carbonate, vanadium pentoxide, potassium carbonate and red iron oxide having a specific surface of about 5 and an average particle size of about 3 microns. Then an aqueous solution containing potassium carbonate in an amount sufficient to create the required final concentration of this component in the catalyst is added to this mixture, after which the mixture is ground on runners play granulate. The resulting granules are dried at. 20 min, and then calcined at a temperature of about 60 minutes,
    The proposed catalyst composition may include chromium oxide, which is added in a known manner to iron oxide catalysts in order to prolong their life. Considerations regarding the need for environmental protection and toxicity may interfere with
    the use of chromium compounds in the composition of dehydrogenation catalysts even to the detriment of some reduction in the service life of the catalyst. However, in those cases when chromium is still used in catalysts, it is introduced in the form of chromium oxide or in the form of chromium compounds, which can decompose upon calcination to form the corresponding oxide.
    for example, in the form of chromium nitranes, hydroxides and acetates.
    Example 1 The following ingredients are mixed dry, g: chromium tri-Oktecb 67.5} divalent cobalt carbonate 59.3, vanadium pentoxide .82.5 trivalent cerium carbonate 249.3; molybdenum trioxide 65; potassium carbonate 250.9 red iron oxide (having a surface area of 5 m- / g and an average particle size of 1 micron) 1968,
    To the mixture obtained, add 256 g of potassium carbonate dissolved in 256 g of water over 5 minutes,
    5 The resulting mixture is ground for 15 minutes and then granulated. The granules are dried pru 200c for 20 minutes, then calcined at 815.C for 60 minutes,
    Q The resulting catalysis ator has the following composition, weight,%: KjO 12.5, 0; MoO 2.4} .5,9; CoO 1,2; Cr-6 2.4, iron oxide the rest,
    - The results of the test catalyst are presented in table.
    Example 2 The following ingredients are mixed dry, g: chromium trioxide, 67.5J, bivalent cobalt carbonate 4.0, pentoxide
    0 vanadi 4.9; cerium carbonate SHgO 15.6; trekko Mo libden 4, i; potassium carbonate 25.0.9J red oxide of iron (having a surface area of 5 and medium 5 of the scientific research institute, particle size 1 µm) 2295.0, To the mixture was added 256 g of potassium carbonate dissolved in 256 g of water for 5 minutes. Next, the mixture is ground to
    0 mill for 15 min., Then, granularit. The granules are dried at 20 minutes and calcined at 60 minutes. The catalyst obtained has the following composition, wt.%: 12.6; 0.18, MoOg 0.15, 0.37; , 08; 2.40} iron oxide - the rest.
    The results of testing the catalyst are presented in the table,
    Example 3, Mix the following ingredients dry, g: chromium oxide 67.5 / divalent cobalt carbonate 59.3} thioxide 5 vanadium 246.9 trivalent cerium carbonate 5 249.3} molybdenum trioxide 65.0 potassium carbonate 250.9 ; red iron oxide (having a surface area of 5 and an average particle size of 1 m) is 1803.0. 256 g of potassium carbonate dissolved in 256 g of water are added to the mixture over a period of 5 minutes. The mixture is then ground in a mill for 15 minutes and then granulated. The granules are dried for 20 minutes and then calcined at 815 ° C for a bo Min. The resulting catalyst has the following composition, wt.%: ClO 12.6, 205 9.0 MoO; 5 2.4 L Ce OzB / E; . CoO 1,2, SG (,, iron oxide else. The results of testing the catalyst are presented in Table. Example 4. The following ingredients are mixed dry, g: chromium trioxide 67.5; carbonate — bivalent cobalt 59.3; vanadium oxide 82.3J ceric carbonate SHjjO 249.3, three molybdenum oxide 243.8, carbonate kaly 250, O, V red iron oxide (having a surface area of 5 and a particle size of 1 mm) 1789, To the mixture was added 256 g of potassium carbonate, dissolved 256 g of water for 5 minutes and then granulated. The granules are dried for 20 minutes and then dried. potassium is heated at 815 ° C for 60 minutes, the resulting catalyst has the following composition, wt .-%: 12.6; 3.0, MoOz 9.0, SegOz 5, CoO 1,2 / CrjO 2.4, iron oxide The results of the test of the catalyst are presented in the table, Example 5. The following ingredients are mixed with dry, g: chromium trioxide 67.5; divalent cobalt carbonate 59.3, vanadium pentoxide, 82.3, trivalent cerium carbonate -5 N "O , 1627, molyblenum trioxide 65, potassium carbonate 250.9 (Red iron oxide, having a surface area of 5 and an average particle size) 590. To the resulting mixture was added 256 g of carbon that potassium, dissolved in 256 g of water, for 5 minutes. The mixture is ground in a mill for 15 minutes and then granulated. The granules are dried for 20 minutes and then calcined at 815 s for 60 minutes. The resulting catalyst has the following composition, wt.%: 12.6, VgOs 3.0 MoO-j 2,4v CejOj 38.5, CoO 1,2} 2.4 iron oxide the rest. The results of the test catalyst are presented in the table. Example 6. The following ingredients are mixed dry, g: vanadium pentoxide 41.2, trivalent cerium carbonate 126.7; molybdenum trioxide 32.5, potassium carbonate 250.9I is red iron oxide, having - a surface area of 5 and an average particle size of IpiM) 2218, to the paramilitary mixture add 256 g of potassium carbonate dissolved in 256 g for 5 minutes. The mixture is ground in a mill for 15 minutes and then granulated. The granules are dried at 200 ° C. for 20 minutes and then calcined for 60 minutes. The resulting catalyst has the following composition, wt.%: 12.6, 1.5 Mob 1,2, 3, exhaust iron oxide - the rest. The results of the test catalyst are presented in the table. Example 7. The following components are dry blended, g: vanadium pentoxide 41.7 molybdenum trioxide 32.5, cerium carbonate - 5H 126.7; chromium trioxide 33.8; cobalt carbonate 2471,. red oxide of iron with a specific surface of 5 and an average particle size of 1 U m 828. To the mixture obtained, add 256 g of potassium carbonate dissolved in 256 g of water for a period of time exceeding 5 minutes. The mixture is ground for 15 minutes and granulated. The granules are dried for 20 minutes and then calcined at 315C B for 60 minutes. The composition of the obtained catalyst and the results of its testing are shown in the table. Example 8 The following components are dry blended, g: vanadium pentoxide 82.3 molybdenum trioxide 63.01 cerium carbonate 5 KjO 249.3; cobalt carbonate 59.3; chromium trioxide 562.5; red iron oxide with a specific surface area of 5 and an average particle size of 1 (C m 1490. JK of the resulting mixture is added 256 g of potassium carbonate dissolved in 256 g of water over a period of more than 5 minutes and then granulated. The granules are dried at 2OO®C in for 20 minutes and then calcined at 815 s for 60 minutes Composition of the obtained catalyst, the results of its testing are shown in Table 1. Example 9.- The following components are subjected to dry-mixing), g: vanadium pentoxide 41.7, molybdenum THROXIDE 32.5, carbonate tse-
     126.7 / cobalt carbonate 14.8, chromium trioxide 33.8i is red iron oxide with a specific surface area of 5 mV g and an average particle size of l / jUM 2383.
    To the mixture was added 101 g of potassium carbonate, dissolved in 256 g of water over a period of more than 5 minutes. The mixture is ground for 15 minutes and then granulated. The granules are dried for 20 minutes and then calcined for 60 minutes. The composition of the obtained catalyst and the results of its testing are shown in the table.
    PRI me R 10. The following components are subjected to dry: mixing, g: vanadium pentoxide 1, 7, molybdenum trioxide 32.5; cerium carbonate 5 126.7J chromium carbonate 67.5, cobalt carbonate 29, red iron oxide with a specific surface 5 and an average particle size of 1 U m 2027.
    To the mixture obtained, 337 g of potassium carbonate in 256 g of hot water are added. The mixture is ground for 15 minutes and then granulated. The granules are dried at 200 ° C for 20 minutes and then calcined at a temperature of about 815 ° C for 60 minutes. The composition of the obtained catalyst and the results of its testing are shown in the table.
    Example 11. The catalyst was prepared according to the procedure of Example 10 / in particular, tungsten trioxide was used instead of molybdenum trioxide. The composition of the catalyst and the results of its testing are shown in the table.
    The catalysts of Examples 1-11 were tested for catalytic activity and selectivity during the dehydration of ethylbenzene to styrene. For this purpose, the catalyst granules are placed in a fixed-bed reactor, with a bed of about 100. cm, and a pre-heated mixture of water vapor and ethylbenzene is passed in a molar ratio. . 12: 1 through a catalyst bed whose temperature is maintained at; the level required to provide the desired degree of ethylbenzene conversion. This tegperature depends on the activity of the catalyst.
    During the process, a pressure in the range from 0 to 37.4 units is used. the absolute pressure (Pq), the flow rate of the liquid (ethylbenzene) passing through the specified volume of catalyst per hour, varies in the range from 0.65 to 1.8. Condensed liquid reaction products are analyzed for styrene, ethylbenzene, benzene, and toluene. These results recalculate the values characterizing the activity and selectivity of the catalyst (the values obtained are presented in the table). The value is used to denote the temperature required for up to 70% conversion of ethylbenzene, and s / j (, v- to indicate selectivity at 70% conversion. The value is a measure of the activity of the catalyst, because the higher the temperature , the lower the catalytic activity.
    5.9
    11.0
    5.9
    5.9
    38.5
    3.0
    3.0
    5.9
    3.0
    610
    93.8 .618 92.5 652 88.0 652 88.0 617 92.5 615 95.2
    , 0 1.2 629 94.6, 2 10.0 618 93.0, 3 1.2 620 92jO Example
    1.2 - 3.0
    16.6 1.5 2.3 2.7 12.6 3.0 12.6
    Table continuation
    2.4
    618 93.8
    1.2 609 94.6
    2.4 591 87.2 Content of ingredients in the catalyst, wt. %, 0 1 V, j05 I MoOS | WO, F Selective Temperature, pa, T (, c) C
    权利要求:
    Claims (1)
    [1]
    A CATALYST FOR DEHYDRATING ETHYLBENZENE IN STYROL, containing iron oxide, potassium oxide and / or potassium carbonate and vanadium oxide, characterized in that, in order to increase the activity and selectivity of the catalyst, it additionally contains molybdenum oxide and / or oxide tungsten and cerium oxide in the following components content ·, wt.%:
    Potassium oxide and / or car- bon at potassium 5-16.6 Oxide vanadium 0.18-9 Oxide molybdenum and / or tungsten 0.15-9 Oxide cerium 0,37-38,5 £35 Oxide gland Rest ω s in
    类似技术:
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    同族专利:
    公开号 | 公开日
    NL186370C|1990-11-16|
    IT1095580B|1985-08-10|
    PT67893A|1978-05-01|
    JPS53129190A|1978-11-10|
    AU3501478A|1979-10-18|
    JPS5728291B2|1982-06-16|
    US4144197A|1979-03-13|
    BE865830A|1978-10-10|
    IT7822246D0|1978-04-12|
    MX147003A|1982-09-22|
    PT67893B|1979-11-14|
    FR2387199B1|1980-08-08|
    ZA781576B|1979-03-28|
    YU40034B|1985-06-30|
    CA1115260A|1981-12-29|
    NL7803708A|1978-10-17|
    FR2387199A1|1978-11-10|
    DE2815874B2|1980-05-29|
    TR19704A|1979-10-11|
    ES468716A1|1979-10-01|
    DE2815874C3|1981-09-24|
    IN148558B|1981-04-04|
    DE2815874A1|1978-10-19|
    NL186370B|1990-06-18|
    YU87278A|1982-10-31|
    GB1557143A|1979-12-05|
    AR223460A1|1981-08-31|
    BR7802256A|1979-01-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3179707A|1962-03-21|1965-04-20|Monsanto Co|Dehydrogenation of ethylbenzene|
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    US4467046A|1982-01-07|1984-08-21|Smith James L|Dehydrogenation catalyst|
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    US4440967A|1982-07-29|1984-04-03|Monsanto Company|Catalyst and reverse disproportionation process|
    US4474897A|1982-07-29|1984-10-02|Monsanto Company|Catalyst useable in a reverse disproportionation process|
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    US4419526A|1982-07-29|1983-12-06|Monsanto Company|Catalyst and reverse disproportionation process|
    US4439628A|1982-07-29|1984-03-27|Monsanto Company|Catalyst and reverse disproportionation process|
    US4439627A|1982-07-29|1984-03-27|Monsanto Company|Catalyst and reverse disproportionation process|
    US4511672A|1982-07-29|1985-04-16|Monsanto Company|Catalyst and reverse disproportionation process|
    US4448894A|1982-07-29|1984-05-15|Monsanto Company|Catalyst and reverse disproportionation process|
    US4490477A|1982-07-29|1984-12-25|Monsanto Company|Catalyst and reverse disproportionation process|
    EP0101913A3|1982-08-03|1986-07-30|BASF Aktiengesellschaft|Dehydrogenation catalyst|
    US4404123A|1982-12-15|1983-09-13|Mobil Oil Corporation|Catalysts for para-ethyltoluene dehydrogenation|
    US4758543A|1987-07-01|1988-07-19|The Dow Chemical Company|Dehydrogenation catalyst|
    US4804799A|1987-08-28|1989-02-14|The Dow Chemical Company|Dehydrogenation catalyst|
    US5258347A|1989-07-20|1993-11-02|The Dow Chemical Company|Process of oxidizing aliphatic hydrocarbons employing a molybdate catalyst composition|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US78764677A| true| 1977-04-14|1977-04-14|
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