公开(公告)号：DE1518546A1

公开(公告)日：1969-01-30

申请号：DE1518546

申请日：1965-04-10

Applicant: BASF AG

Inventor： SIEGFRIED WINDERL DR ,  HERWIG HOFFMANN DR ,  CHRISTOF PALM DR ,  HEINZ NOHE DR ,  KARL BAER DR ,  HARTWIG HARDERS DIPL-MATH DR

IPC: B01J23/16 ,  B01J23/30 ,  B01J23/68 ,  B01J23/70 ,  B01J23/88 ,  B01J23/887 ,  B01J23/888 ,  B01J23/89 ,  C01B21/26

Abstract: 1,136,744. Ammonoxidation of olefin hydrocarbons. BADISCHE ANILIN- & SODAFABRIK A.G. 7 April, 1966 [10 April, 1965], No. 15500/66. Heading C2C. [Also in Division B1] Acrylonitrile or methacrylonitrile are produced by reacting propylene or isobutylene, ammonia and oxygen or gases containing molecular oxygen in the vapour phase in the presence of a catalyst comprising a mixture of metal oxides, the analysis of which mixture gives: (A) 0À1 to 20% by weight of arsenic pentoxide, (B) 1 to 50% by weight of tungstic trioxide, and (C) 1 to 50% by weight of molybdenum trioxide, the three components (A), (B) and (C) constituting up to 45% by weight of the active components of the catalyst which also contains (D) at least one of the metals lead, alkali metals and metals of atomic numbers 22 to 30 inclusive in combined form, each of the metals of this group (D), calculated as the oxides, being present in an amount of 0À1 to 10% by weight and, if desired, (E) up to 40% by weight of silver calculated as silver oxide and the total amount of the components of groups (D) and (E) in the catalyst being up to 55% by weight of the active components. The preferred catalyst compositions comprise arsenic pentoxide, tungstic trioxide and molybdenum trioxide in association with the following combinations of compounds of the group (D) metals: lead, chromium, cobalt and zinc; manganese, iron and zinc; or potassium, vanadium, chromium and cobalt optionally in the presence of silver oxide. The catalyst may be supported on a suitable carrier such as silica gel representing 30 to 80% by weight of the resulting mixture. The process is carried out at a temperature in the range 400‹ to 580‹ C. under fixed or fluidized bed conditions using molar ratios of propylene to oxygen and ammonia of 1: 0À5 to 1: 3 and 1: 0À5 to 1: 5 respectively in the presence of an inert gas and steam, if desired. Acetonitrile may also be obtained in low yield as a by-product.

公开(公告)号：DE1543337A1

公开(公告)日：1969-12-11

申请号：DE1543337

申请日：1966-03-22

Applicant: BASF AG

Inventor： KARL BAER DR ,  HERWIG HOFFMANN DR ,  HERMANN SUESSENGUTH DR

IPC: C07C209/48 ,  C07C85/12

公开(公告)号：DE1442567A1

公开(公告)日：1968-11-21

申请号：DE1442567

申请日：1964-05-13

Applicant: BASF AG

Inventor： KARL BAER DR ,  HEINRICH SPERBER DR ,  OTTO GOEHRE DR ,  GERHARD LEIBNER DR

IPC: B01J21/04 ,  B01J21/08 ,  B01J23/72 ,  B01J23/882 ,  B01J35/02 ,  B01J35/04 ,  B01J35/08 ,  B01J37/00

Abstract: In Examples 5 and 8, nitrobenzene is hydrogenated to aniline in presence of hollow silica beads impregnated with copper, at temperatures of 280 DEG -290 DEG C.ALSO:Catalysts or catalyst carriers in the form of hollow beads are prepared by spraying a hydrogel containing at least 30% by weight of water and/or a suspension and/or a solution of metal compounds at a pressure of 10 to 100 atmospheres into a tower-shaped vessel, and cocurrently introducing a gas at 300 DEG to 700 DEG C. in amounts of 4 to 18 cubic meters per kgm. of initial material. Hydrogels of silicic acid, alumina, silicates and titania are mentioned, Al, Mg, Zr or Zn salts may be added in preparing a silicic acid hydrogel. The metal compounds may be compounds of Cu, Ag, Zn, Mg, Al, Sn, Pb, V, Cr, Mo, W, Mn, Fe, Ni, Co, Pt or Pd. The hollow beads may be treated with halogen or a phosphoric acid. Examples relate to (1), (5) silica gel; (2), (3) alumina gel; (4) aluminium phosphate; (6) alumina + Co + Mo; (7) Mo + P + V; (8) silica gel + Cu.ALSO:Catalysts or catalyst carriers in the form of hollow beads are prepared by spraying a hydrogel containing at least 30% by weight of water and/or a suspension and/or a solution of metal compounds at a pressure of 10 to 100 atmospheres into a tower-shaped vessel, and cocurrently introducing a gas at 300 DEG to 700 DEG C. in amounts of 4 to 18 cubic meters per kgm of initial material. Hydrogels of silicic acid, alumina, silicates and titania are mentioned. Al, Mg, Zr or Zn salts may be added in preparing a silicic acid hydrogel. The metal compounds may be compounds of Cu, Ag, Zn, Mg, Al, Sn, Pb, V, Cr, Mo, W, Mn, Fe, Ni, Co, Pt or Pd. The hollow beads may be treated with halogen or a phosphoric acid. Examples relate to (1), (5) silica gel (2), (3) alumina gel; (4) aluminium phosphate; (6) alumina +Co+Mo; (7) Mo+P+V; (8) silica gel +Cu. A reactor for hydrogenation of nitrobenzene has diameter to height ratio 1:4 and has twenty two-component nozzles arranged at three levels above the grate at the bottom of the reactor. The upper portion of the vessel is widened to 1 1/2 times and includes a cyclone; reaction gases leaving by the cyclone are recycled via a heat exchanger, condenser, gas-liquid separator, preheater and pump. Cooling tubes are arranged in the catalyst layer at a distance from the wall of the reactor.