Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
  • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
  • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof

Definitions

• the invention relates to a process for the selective hydrogenation of dienes, especially of serving in reformate streams (feed streams) on one nickel-containing precipitation catalyst.
• the invention further relates to a method for the production of high-purity aromatics or aromatic mixtures.
• the reformate produced by catalytic reforming of naphtha represents a very important source of aromatics for the production of pure aromatics.
• Essential components of the reformate are aromatic compounds such as benzene, toluene, xylene and ethylbenzene.
• the boiling range of the hydrocarbon mixture lies between 60 and 180 ° C. Except for the saturated ones
• the untreated contain hydrocarbons and aromatic compounds Reformate streams components such as olefins and diolefins.
• FR-A 2 720 754 discloses that in pyrolysis gasoline Serve selectively on a palladium impregnation catalyst at approx. 150 ° C and can be hydrogenated about 15 bar.
• This task is accomplished by a process for the selective hydrogenation of Serve resolved in the feed streams containing diene, which is characterized by is that such a diene containing feed current on a nickel-containing Precipitation catalyst at a temperature between 40 and 100 ° C, one Pressure between 3 and 20 bar and a WHSV between 1 and 10 kg / (lxh) is hydrogenated in the presence of free hydrogen.
• nickel-containing precipitation catalysts such as are known per se from EP-A 0 672 452
• a very effective selective Allow hydrogenation of dienes, being hydrogenated with this catalyst under high reformate load and low pressure and low temperature conditions is carried out. It is with the method according to the invention possible that when operating under low pressure and temperature conditions and high reformate throughput of hydrogen compared to hydrogenated dienes is fed into the hydrogenation reactor in a quantity-controlled manner.
• the nickel precipitation catalysts used according to the invention are in EP-A 0 672 452. These are catalysts that are in the essentially 65 to 80% nickel, calculated as nickel oxide, 10 to 25% Silicon, calculated as silicon dioxide, 2 to 10% zirconium, calculated as Zirconium oxide and 0 to 10% aluminum, calculated as aluminum oxide, included with the proviso that the sum of the silicon dioxide content and aluminum oxide is at least 15% (percentages in% by weight, based on the total mass of the catalyst).
• the catalysts used according to the invention preferably contain 70 to 78% nickel, 10 to 20% silicon, 3 to 7% zirconium and 2 to 10% Aluminum.
• Catalysts are preferably used which only have nickel as catalytic contain active metal. In particular those catalysts that are free of Palladium can be used.
• the catalysts can contain promoters in amounts of up to 10%. These are compounds such as CuO, TiO 2 , MgO, CaO, ZnO and B 2 O 3 . However, catalysts which do not contain any promoters are preferred.
• the preparation of the catalysts used according to the invention is carried out of aqueous acidic solutions of nickel, zirconium and optionally Aluminum salts.
• Organic and inorganic salts come as salts such as acetates, sulfates, carbonates, but preferably nitrates of the above Metals into consideration.
• the total content of metal salts is generally 30 to 40% by weight. Because the later precipitation of the metals from the solution done practically quantitatively, the concentration of the individual components depends in the solution only on the content of the catalyst to be produced Component.
• the aqueous solution is obtained by adding a mineral acid, preferably nitric acid adjusted to a pH below 2.
• This solution is, advantageously with stirring, in an aqueous basic Solution, the silicon compounds and, if desired, aluminum compounds contains, registered.
• This solution contains, for example, alkali metal hydroxide or preferably soda, usually in amounts of 15 to 40 wt .-%, based on the solution.
• the pH is generally over 10.
• SiO 2 can also be used as the silicon compound.
• the silicon content of the solution is expediently 0.5 to 4% by weight.
• the solution may contain aluminum compounds in the form of oxidic solids, although it is preferred to add aluminum salts only to the acidic solution.
• the acidic addition to the basic solution is generally carried out at 30 to 100 ° C., preferably at 60 to 80 ° C. It is usually carried out over a period of 0.5 to 4 hours.
• catalysts which contain promoters are desired, it is expedient to one of the solutions described soluble metal salts as precursors for add the promoters, co-precipitate these metals and with the so obtained To further process the precipitate.
• the promoters can also be added as solids in the precipitation solution.
• the precipitated product is isolated, for example by filtration. In the This is usually followed by a washing step, in particular where appropriate Alkali metal ions and nitrate ions entrained during the precipitation be washed out.
• the solid thus obtained is then dried, for which depending on the amount of dry goods, for example, a drying cabinet or a spray dryer can be used. Generally is the drying temperature 100 to 200 ° C. Before the next step if desired, the solid can use the above promoters be added.
• the dried product is then preferably calcined, which is usually at temperatures of 300 to 700 ° C, preferably 320 to 450 ° C, over a period of 0.5 to 8 hours.
• the calcined solid is added to the intended use Shaped bodies, for example by extrusion into strands or by Tableting.
• the calcined solid is known per se Peptizing agents such as nitric acid or formic acid in amounts of in generally 0.1 to 10% by weight, based on the solid to be molded, added.
• Graphite e.g. Graphite can be used.
• the so Moldings obtained are usually at temperatures from 300 to 700 ° C, preferably 350 to 500 ° C, over a period of 1 to 8 Hours calcined.
• the feed streams preferably used in the process according to the invention contain about 15 to about 90% by weight aromatics and up to about 5000 wppm dienes.
• the most preferred feed streams are reformate streams.
• the hydrogen in the hydrogenation stage is regulated in this way fed in that about as much hydrogen is supplied as for the hydrogenation the servant is required.
• the control is preferably carried out in such a way that per mole of diene structure in the feed stream 1 to 1.3, preferably 1 to 1.2, especially about 1.2 moles of hydrogen is fed.
• a catalyst which is 65 to 80 % By weight nickel, 10 to 25% by weight silicon, 2 to 10% by weight zirconium, Contains 0 to 10% by weight aluminum - all components calculated as oxides and percentages in% by weight, based on the total mass of the Catalyst - with the proviso that the sum of the content of silicon dioxide and alumina is at least 15%.
• the aromatic content of the mixture to be hydrogenated before the selective hydrogenation by one or more upstream distillation, extraction and / or Extractive distillation levels is increased.
• the described nickel-containing precipitation catalysts show also a high selectivity in the hydrogenation of dienes in aromatics rich hydrocarbon mixtures if the process is designed that the catalyst with a low pressure and temperature levels high feed current, especially reformate throughput is loaded, and the amount of hydrogen is regulated in relation to the dienes to be hydrogenated the reactor is fed.
• the use of the hydrogenation stage according to the invention is particularly suitable in Combination with a downstream extractive distillation of the hydrogenated Product for processing and obtaining the valuable aromatics.
• the organic used Solvent consists of a high-boiling polar liquid (Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A3, page 490, publisher Chemistry).
• DE-A 20 40 025 discloses that N-substituted morpholines are known as such a selective solvent are particularly suitable.
• the preferred The solvent for the extractive distillation stage is NFM (N-formylmorpholine).

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Medicines Containing Material From Animals Or Micro-Organisms (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Studio Devices (AREA)
• Image Processing (AREA)

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• 1996
  • 1996-03-04 DE DE19608241A patent/DE19608241A1/de not_active Withdrawn
• 1997
  • 1997-02-27 CN CN97194233A patent/CN1083878C/zh not_active Expired - Fee Related
  • 1997-02-27 RU RU98118235/04A patent/RU2180678C2/ru not_active IP Right Cessation
  • 1997-02-27 JP JP53141997A patent/JP3852952B2/ja not_active Expired - Fee Related
  • 1997-02-27 ES ES97905112T patent/ES2140963T3/es not_active Expired - Lifetime
  • 1997-02-27 AT AT97905112T patent/ATE186942T1/de active
  • 1997-02-27 KR KR10-1998-0706916A patent/KR100437978B1/ko not_active IP Right Cessation
  • 1997-02-27 DE DE59700760T patent/DE59700760D1/de not_active Expired - Lifetime
  • 1997-02-27 BR BR9707831A patent/BR9707831A/pt not_active IP Right Cessation
  • 1997-02-27 CA CA002248020A patent/CA2248020C/en not_active Expired - Fee Related
  • 1997-02-27 EP EP97905112A patent/EP0885273B1/de not_active Expired - Lifetime
  • 1997-02-27 WO PCT/EP1997/000960 patent/WO1997032944A1/de active IP Right Grant
  • 1997-02-27 US US09/142,217 patent/US6118034A/en not_active Expired - Lifetime
  • 1997-02-27 PT PT97905112T patent/PT885273E/pt unknown
  • 1997-03-04 TW TW086102534A patent/TW432042B/zh not_active IP Right Cessation
• 1999
  • 1999-11-30 GR GR990403108T patent/GR3032014T3/el unknown

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