• 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:

    公开号:SU919591A3
    申请号:SU782667703
    申请日:1978-09-22
    公开日:1982-04-07
    发明作者:Биола Жорж；Фон Жан；Дома Жан-Клод
    申请人:Рон-Пуленк Агрошими (Фирма)；
    IPC主号:
    专利说明:

    (5) METHOD FOR OBTAINING A MIXTURE OF M-CHLORINIANES
    - I -,. , -. .
    This invention relates to a process for the preparation of chloroanilines, in particular 3.5 Aichloroaniline from cooTetcTBybtUHX polychloroanilines or polychloronitrbenzenes containing more chlorine atoms.
    A known method for producing a mixture of m-chloroanilines by dehalogenating aromatic halogen-containing compounds, specifically polychloroanilines or 10 polychloronitrobenzenes, in the vapor phase under the action of hydrogen at 280–20 ° C in the presence of a copper or silver catalyst on alumina l.
    The disadvantage of the method is that when using the above catalyst on an elu mini oxide carrier, private regeneration of the catalyst due to the formation of carbonaceous deposits due to the complete decomposition of part of the reactants is necessary.
    The purpose of the invention is to simplify the process.
    The goal is achieved by the fact that according to the method of obtaining these 25
    these m-chloroanilines, involving the dehalogenation of the corresponding polychloroanilines or polychloronitrobeisols in the vapor phase with hydrogen in the presence of a catalyst — copper supported on an alumina carrier — use a catalyst supported on an additional 0.2-30% by weight of magnesium or chromium
    Di-, tri-, or tetrachloroanilines are preferably used as polychloroanilines. Preferred polychloronitrobenzene are 1-nitro-2,3., 5-tetra-, chloro- or 1-nitro-2,3,5 6-tetrachloro-benzene or pentachloronitrobenzene.
    The following abbreviations are used in the examples: tetrachloronitrobenzene (TTHNB); tetrachloroaniline (TTHA); trichloroaniline (THA); dichloraniline (DHA); chloraniline (HA); pentachlorobenzene (PCB) i aniline (A).
    Example 1. Preparation of two catalysts. 100 g of alumina granules (20-100 µm), having a specific surface of 300, are impregnated with an aqueous solution of Mg (NO) ii6Hrjp magnesium nitrate to obtain a final content of 5 ppm of magnesium relative to the target catalyst (or about 5.25 carrier with respect to the carrier). The impregnated carrier is then calcined at 950 ° C for three hours. It is operated in the same way with another sample of alumina, similar to the first one, but impregnated with an aqueous solution of chromium oxide (fCrOg) to obtain the final content: anionic chromium 10 wt. (or about 11.1 wt.% with respect to the carrier). The impregnated carrier is then calcined under the same conditions, 4to and previous. From each of these modified carriers, the catalyst is then prepared according to the classical method by impregnating the modified carrier with a solution of copper chloride (P) to obtain a final copper content of 6 wt. in relation to the aggregate of the carrier, the phase is active, or about 6, C pW in relation to the carrier. The impregnated carrier is then dried at. Thus, the resulting catalysts are designated respectively: a catalyst with magnesium 1, a catalyst with Chromium 2. Example 2. Preparation of a catalyst for a fluidized bed, the carrier of which is obtained according to the second variant. Prepare a solution of oxychloride oxychloride-III by exposure to 100, 36% (d 1.18), for 192.3 g in the presence of a reducing agent, and mixed with a solution containing g of aluminum oxyoxide A1i (OH) 5CJ. The mixture is precipitated by cooling, by adding hexamethylenetetramine to the aqueous solution. The resulting product is then dispersed for small droplets in the oil with the help of a pump and a jet of the corresponding diameter. By varying the flow rate of the pump and the diameter of the nozzle, the particle size distribution of the droplets formed can be adjusted as desired. They coagulate in heated oil, taking a spherical shape. After heating for 21 hours, in a oil bath, microbeads from 9 1 are divided, washed with water, dried for 12 hours, then calcined for an hour, to allow chromium-alumina to form a solid solution. This carrier is then impregnated with copper chloride solution using a known method, then dried at 200 ° C. The resulting catalyst, containing 10% chromium and 6% copper, is indicated by figure 3. Example 3. 8 the bottom of the tubular reactor is placed 100 g of catalyst 1, obtained according to example 1, in the form of granules with a size of 20-100 microns, which is a modified substrate from alumina oxide with a specific surface of 00 m tg containing 5 wt.% magnesium containing the active phase containing l weight. copper in the form of copper chloride. 100 g of steam-2, 3), 5-tetrachloronitrile, and 75 liters of hydrogen are introduced into the reactor within one hour. The temperature in the reactor is of the order and is kept constant by cooling the heat transfer medium. The contact time of the gaseous mixture with the catalyst is 3 s. The whole operation lasts about four hours. From the upper dehalogenation zone, the products formed during the reaction are sent to a column for washing with water, which carries with it the anilines and HC1 produced, while the excess hydrogen is released into the atmosphere. Then, it is neutralized with sodium hydroxide solution, the mass recovered at the bottom of the wash column, and the organic part is isolated, which is analyzed by thin layer and lateral bone chromatography. The same experience and under the same conditions was carried out in the presence of catalyst 2G, obtained according to example 1, and representing a modified support containing 10 wt. Cr, and the active phase containing 6 wt. Copper. As a comparison, the results are given for operation under the same conditions in the presence of a catalyst with an unmodified carrier of R (I), which is a carrier of alumina, and active, containing 6 wt. copper. The results of the experiments are summarized in table. 1, which indicates the composition and yield of the target products, expressed in mol% with respect to
    5919591,
    to the original THTHB. The amount of carbon– The results obtained after deposited on the catalyst are listed in Table. 2.. Razheno in wt.% by weight of the catalyst.
    权利要求:
    Claims (1)
    [1]
    aaij.s, 2, 3 0.2 -TTHNB1.0 2.3, 5-TtXA 12.0 22.5 21.7 3.4 S.JrS-TXA1.0-2, ZL-TXA1, 3 35.3 35.7 2J 2,3,5-TXA36,2 tn: 3, MHA3, 5-DHA42.3 33.1 32.0 2.7 8, V 3-XA7.3 carbon (deposition of jfa catalyst) . ,:; ... - -.- -----; The results of the table show a significant decrease in the amount of carbon deposited on the catalyst with a modified carrier according to the invention, which allows a significant extension of the service life of this catalyst. The yield of 3.5 Dichloroaniline is lower than that obtained with a catalyst on a classical carrier, but this is only a minor drawback, since, in industrial production, unreacted gases can be recycled: And the COST of regenerations becomes less high. RIM e p. 4. Analogously to example 3, catalyst 2, i.e., a catalyst containing an oxide of aluminum oxide modified with chromium chromium) and an active phase containing 6% copper are used. 2.0 20 3.2 2, PL, 5-TTHNB 0 „10.2 2,3,4,5-TTHA 8.2 20.218.3 Z. + Z-TXA UO 1.62.9 29.430.6 2.3 , 5-TXA 30.4 3.5-DHA37.3 32.032.5 C on the catalyst, 8.0 3.2 2.6 Hourly% of the spent catalyst in comparative tests (a norm) 8 The results of the table show a two-thirds decrease, hence a significant carbon precipitate on the catalyst deposited on the modified carrier with respect to the nemo-v modified carrier. Example 5. Analogously to example 3, catalyst 2 is used, and only vaporized 3,4-dichloroaniline and hydrogen are introduced into the reactor only in a molar ratio of H (4-DCA, equal to about 5). The process is carried out for three hours at a time of "And 3c. In these conditions, the results are presented in Table 3. Carbon on the catalyst 3.83 The results of the table clearly show the advantage of the method that makes it possible to almost completely convert 3 | dichloroaniline to 3 chloroaniline. Formula of the invention -chloroanilines by dehalogeny matching of polychloroanilines or polychloronitrobenzenes in the vapor phase; at 280–20 ° C with hydrogen in the presence of a copper catalyst supported on an alumina-based carrier, which, in order to simplify the process, uses a catalyst supported on an additional 0.230% by weight of magnesium or chromium. 2, A method according to claim 1, characterized in that DI, tri or tetrachloroaniline are used as polychloroanilines. Sources of information taken into account in the examination 1. Patent of France N 2162782, cl. C 07 C 85/00, published 197A (prototype).
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    同族专利:
    公开号 | 公开日
    ATA683878A|1980-09-15|
    GB2005262B|1982-05-26|
    ES473536A1|1979-05-16|
    FR2403991A1|1979-04-20|
    IL55617D0|1978-12-17|
    IT1099601B|1985-09-18|
    JPS5455526A|1979-05-02|
    US4206148A|1980-06-03|
    IL55617A|1982-01-31|
    IE781901L|1979-03-22|
    BR7806158A|1979-04-17|
    HU184666B|1984-09-28|
    EP0001371A1|1979-04-04|
    AT361903B|1981-04-10|
    CA1130263A|1982-08-24|
    GB2005262A|1979-04-19|
    JPS5838420B2|1983-08-23|
    DK419478A|1979-03-23|
    IE47443B1|1984-03-21|
    DD139357A5|1979-12-27|
    EP0001371B1|1980-10-01|
    IT7828007D0|1978-09-22|
    FR2403991B1|1981-01-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3148217A|1961-11-16|1964-09-08|Gen Aniline & Film Corp|Catalytic hydrogenation of halonitrobenzene compounds|
    US3839193A|1970-04-10|1974-10-01|Universal Oil Prod Co|Hydrocarbon conversion with a trimetallic catalytic composite|
    BE792080A|1971-11-30|1973-05-29|Rhone Progil|DEHALOGENATION OF POLYHALOGENOUS AROMATIC COMPOUNDS|
    US3867312A|1972-02-07|1975-02-18|Ethyl Corp|Exhaust gas catalyst support|
    US3912783A|1972-12-05|1975-10-14|Bayer Ag|Process and catalyst for preparing of 3-halogen-and 3,5-dihalogen-phenols|
    GB1439171A|1973-01-09|1976-06-09|Ici Ltd|Oxyhalogenation process|
    DE2344926C3|1973-09-06|1981-05-07|Bayer Ag, 5090 Leverkusen|Process for the preparation of 3-halophenols or 3,5-dihalophenols|
    GB1458633A|1974-09-17|1976-12-15|Ici Ltd|Process for dehalogenating aromatic compounds|
    DE2503187C3|1975-01-27|1979-05-31|Bayer Ag, 5090 Leverkusen|Process for the preparation of chlorine-meta-substituted anilines|
    FR2334415A1|1975-12-08|1977-07-08|Raffinage Cie Francaise|NEW CATALYSTS, THEIR PREPARATION PROCESS AND THEIR APPLICATION TO THE TRANSFORMATION OF HYDROCARBON FEEDS|FR2487824B1|1980-08-01|1984-08-24|Rhone Poulenc Agrochimie|
    DE3173077D1|1981-01-15|1986-01-09|Ici Plc|Catalyst, catalyst support and oxychlorination process|
    US4433981A|1981-02-18|1984-02-28|Shell Oil Company|CO2 Removal from gaseous streams|
    DE3127026A1|1981-07-09|1983-01-20|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING M-CHLORINE-SUBSTITUTED ANILINE|
    FR2521132B1|1982-02-05|1984-03-16|Rhone Poulenc Agrochimie|
    GB2118542B|1982-02-18|1985-12-04|Mitsui Toatsu Chemicals|Process for preparing of 3,3'-diamino diphenylsulfones|
    FR2532305B1|1982-08-24|1984-12-07|Rhone Poulenc Agrochimie|
    US4692554A|1983-10-18|1987-09-08|Mitsui Toatsu Chemicals, Inc.|Process for producing 1,3-bisbenzene|
    IN170003B|1985-06-28|1992-01-25|Shell Int Research|
    GB8716653D0|1987-07-15|1987-08-19|Shell Int Research|Silver-containing catalyst|
    US5089653A|1991-04-04|1992-02-18|Dow Elanco|Process for the selective reduction of the 4-halogen in 2,4-dihaloanilines|
    FR2774606B1|1998-02-11|2000-03-17|Rhodia Chimie Sa|PROCESS FOR REMOVING HALOGENATED COMPOUNDS FROM GASES OR LIQUIDS|
    US6589494B1|1998-03-31|2003-07-08|Institut Francais Du Petrole|Process for eliminating halogen-containing compounds contained in a gas or liquid using an adsorbent composition based on at least one metallic element|
    US6306795B1|1999-09-07|2001-10-23|Cytec Technology Corp.|Stable highly active supported copper based catalysts|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7729400A|FR2403991B1|1977-09-22|1977-09-22|
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