• 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:
    Aromatic compounds are nitrated in the vapor phase via a process comprising contacting the aromatic compound with a nitrating agent in the presence of a nitration promotion catalyst which comprises the adduct of: (a) an alumina-silica-metal oxide combination represented by the formula: (Al2O3)a(SiO2)b(M2/nO)c wherein M is a metal cation selected from the group consisting of the lanthanides or rare earths, Groups 1b, 2b, 5b, 6b, 7b, and 8 of the Periodic Table of the Elements, and mixtures thereof, and a, b, and c represent weight percent of the Al2O3, SiO2, and M2/nO components, respectively, in the alumina-silica-metal oxide combination, with a being 0 to 100, b being 0 to 100, and c being 0 to 50, and n represents an integer from 1 to 7 of the valence of the metal cation, with the proviso that the sum of (a + b) must be greater than 0, and (b) a catalytically effective amount of sulfur trioxide.
    公开号:SU1291022A3
    申请号:SU823500650
    申请日:1982-10-20
    公开日:1987-02-15
    发明作者:Н@М@Н Шумахер Игнациус；Ванг Канг-Бо
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    I
    This invention relates to catalysts for the vapor phase nitration of aromatic compounds.
    The aim of the invention is to increase the activity and selectivity of the catalyst due to a certain qualitative and quantitative composition.
    The invention is illustrated by the following examples.
    Examples 1-15. Preparation of catalysts.
    7.0 g (0.093 mol) of cobalt oxide (CoO) powdered and 20.0 g (0.16 mol) of molybdenum oxide (MoOj) together with a sufficient amount of aluminum balls of the appropriate size (6 / 8, with a diameter of 1.0 cm vessel with a capacity of 4.4 liters). The vessel is placed on a ball mill and processed for 3-6 hours. Thoroughly mixed metal oxide powders and 172.0 g (1.68 mol) of alumina are placed in a second wide-mouth vessel of appropriate size (made of polyethylene) without aluminum balls. Alumina / metal oxides are manually stirred by shaking the vessel for 3-5 minutes and then rotated in a ball mill for 1-3 hours. The mixture is passed through a sieve (standard tlHA - 100 mesh) in order to achieve complete mixing The sifter mixture is again placed in a vessel and rotated in a ball mill for another 1-3 hours in case lumps remain after the initial sieving, and in case there are no lumps - only for half an hour to avoid possible stratification.
    A sufficient amount of water is then added to the dry mixture, stirring until a thick slurry is obtained. The slurry is extruded through the mouthpiece of the appropriate sizes to obtain tablets of 0.32 0.32 cm. The tablets are placed in an evaporating bowl-dish and heated for 1-5 hours, usually for 2 hours at 150-250 ° C, usually at 200 ° C, drying pills. The temperature is then increased to 600-1200 ° C, typically SOO-IOOO C for 5-10 hours. At the end of the calcination, the tablets are cooled to room temperature for use and as a combination of alumina-silica-metal oxide.
    910222
    A stainless steel tube with a length of 40.64 cm and an outer diameter of 2.54 cm is used as a reactor. A material consisting of an alumina-silica-metal oxide compound is placed in the reactor and dried for 1 hour under constant flow. dry nitrogen, heating it if necessary to a temperature of 225 ° C. Then, the temperature required for obtaining the catalyst (usually 175 C) is set, sulfur dioxide and nitrogen dioxide (in the nitrogen tray as carrier) are loaded into the reactor in an approximate molar ratio of 2-3 / 1, while the sulfur sulfur dioxide absorbed is reaches the desired value. The reaction time is 1 hour. The parameters and the results are shown in Table. one.
    ten
    )five
    20
    Examples 16-74. Nitration reactions.
    Using the reactor described in Examples 1-15, a series of reactions are carried out to obtain a catalyst in order to confirm the effectiveness of nitration promoters in vapor-phase nitration of aromatic compounds.
    For this purpose, the aromatic compound is preheated, after which it is loaded into the reactor together with the HCL -: cleaned or water-containing streams. Bozdukha. The nitrating agent, i.e. N0J, unless otherwise indicated, is mixed in a stream of nitrogen as a carrier shortly before contact with the heated catalyst with a stream of aromatic compound and air. Products are collected in a series of three cooled vessels, the first of which is cooled in an ice-water bath, and the second and third, respectively, in a dry ice bath. The analyzes were carried out by gas chromatography using a Varian Associates Modef 3700 instrument using a 1.83 m long column with an outer diameter of 0.32 cm, packed with 0.5% phosphoric acid and wt.% SP-1000 / Chromosorb G and programmed per temperature interval SO-210 C with a temperature rise rate of 10 C / min. The parameters and the results obtained are shown in Table. 2
    Examples 75-78. These examples are provided to illustrate the use of catalyst compositions as promoters for vapor phase nitration of disubstituted aromatic compounds, with O or 1,2-dichlorobenzene being used as a typical compound.
     The reactor system described in examples 1-15 is used and operates according to the method described in examples 16-74. The parameters and the results obtained are given in table. 3
    权利要求:
    Claims (2)
    [1]
    1. Catalyst for vapor-phase nitration of aromatic compounds containing alumina and / or silica and sulfur compounds, characterized in that, in order to increase the activity and selectivity of the catalyst, it contains sulfur trioxide with the following content of components, percent by weight:
    Sulfur trioxide 5.1-40-40 Alumina or silica, or a mixture of alumina and silica in bulk
    relation 1: (1-9,6) The rest
    [2]
    2. A catalyst according to claim 1, characterized in that, in order to increase the activity of the catalyst, it additionally contains cobalt oxide, or cobalt oxide and molybdenum oxide in a molar ratio of cobalt: molybdenum 1: (1.47-1.73) or nickel oxide and tungsten oxide in molar ratio nickel: tungsten 1: 1.41 with the following content of components, wt.%:
    )
    Cobalt oxide 16.5
    or cobalt oxide and molybdenum oxide, 13.5-19.5 or nickel oxide and tungsten oxide 17.6 Alumina or silica or a mixture of alumina and silica in a mass ratio of 1: 3.7 The balance and sulfur trioxide in the amount of 5, 1- 14.6% by weight of the specified mixture of metal oxide with alumina and / or silica.
    512910226
    Alumina-silica-metal oxide compound
    Table I
    12.5 8.9
    9J 5.2
    "J
    7.9
    11.8
    10.1
    32.2
    10.6
    11.6
    11.5
    12.3
    5.8
    4.7
    8.4
    b, 1
    2.7
    2.9
    4.8
    5.2
    12.5
    11.2
    19.6
    20.5
    12.1
    8.6
    10.6
    6.0
    1,3
    9.5
    14.2
    12.2
    40.0
    10.0
    11.0
    21.0
    13.6
    5.8
    4.7
    6.7
    5.1
    2.2
    2.4
    4.0
    5.1
    14.6
    12.1
    22.5
    22.5
    (21,4,20,6)
    (14,3,16,6)
    (15.4,17,9)
    (19,7,23,7)
    (29,8,35,9)
    (22.2, 2PO)
    (10.5, 10.5)
    (8.8, 7.3) (11.7, 9.7) (16.5. 13.7)
    Continued table. one
    49.0
    154.0
    53.6
    54.0
    .
    31.0
    1.0
    M
    175
    107.0, 0 -
    62.9 48.8
    26.3 30.0 31.0
     -
    41.0
    31.0
    31.0
    42.0
    58.0
    78.0
    24.0
    28.0
    50.0
    53.5
    26.0
    “,
    60.0 62.0 56.0 46.0 67.4 30.0 36.0 59.0 41.0 60.0 54.0 55.0
    . -
    31.0
    and
    -.
    21.3 31.0
    .
    - - |
    3.0
    1.0
    1.5 1.0 0.5 0.5 1.0
    0.5 "
    and -
    1.0
    - -
    2.0 2.5 2.2
    180 175
    - -
    175
    ". -
    AND
    . . "". -. - -
    table 2
    56 11 (for comparison)
    Ct 23.02 41.20.37 3.082 500.0
    13
    57
    eleven
    cr 12,69 18,60,17 2,5
    58 12 (for
    1291022
    14 Continued table. 2
    320.0
    15
    35
    49.1536,30,79 6,8
    I29I02216
    Continued table. 2
    1.55
    17
    50 29.12 17.9 0.39 5.7 51 57.49 35.6 0.77 8.0
    59,7333,00,72 7,8
    52.89 39.30.85 7.1
    51.02 37.90.82 6.7
    52.27 35.60.77 6.9
    47.91 35.4 0.77 6.3
    129102218
    Continued table. 2
    24.0 2.17 3f, 0 2.48
    31.0
    2.57 2.30 2.22 2.41 2.08
    nineteen
    129102220
    Continued table. 2
    35
    16.80 4.8 0.27
    2.3
    6,049,8,
    23
    1291022
    24
    Continued table. 2
    Continued table. 2
    Continued table. 2
    64 100.0
    Continued table. 2
    91.8
    91.4 99.6
    31
    65 (, 03 IO Pa) 100.0
    1291022
    32 Continued tabl. 2
    99.9
    95.1 95.2
    t p about l and c
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    引用文献:
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    JPS5114499B1|1971-07-13|1976-05-10|
    IL41330A|1973-01-17|1975-07-28|Imi Inst For Res & Dev|Solid catalyst for heterogeneous reactions|
    US3914332A|1973-11-23|1975-10-21|Sun Ventures Inc|Oxidative dehydrogenation of butane|
    US3966830A|1974-03-08|1976-06-29|Teijin Limited|Process for the nitration of halogenated benzene derivatives|
    DE2632234C3|1976-07-17|1978-12-21|Hoechst Ag, 6000 Frankfurt|Process for the production of nitrotoluene mixtures with a predominant content of nitrotoluene|
    SE7707089L|1977-06-20|1978-12-21|Bofors Ab|KIT FOR GAS PHASE NITRATING OF AROMATS|
    US4107220A|1977-11-04|1978-08-15|Monsanto Company|Gas phase nitration of chlorobenzene|
    US4193894A|1979-01-11|1980-03-18|Monsanto Company|Catalyst for oxidation of sulfur dioxide|JPH0422897B2|1982-04-16|1992-04-20|Sumitomo Chemical Co|
    EP0182771B1|1984-11-14|1989-12-27|Monsanto Company|Vapor phase nitration catalysts and processes for the preparation and use thereof|
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    CH683918A5|1991-12-04|1994-06-15|Uetikon Chemie Ag|A process for the preparation of nitrobenzene.|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/313,522|US4415744A|1981-10-21|1981-10-21|Vapor phase nitration of aromatic compounds|
    US06/313,519|US4407729A|1981-10-21|1981-10-21|Catalysts|
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