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
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions

Definitions

• the present invention relates to a process for the synthesis of olefins from synthesis gas, in the presence of at least one Fischer-Tropsch catalyst in a reaction onskolonne.
• the catalysts used are generally those which contain nickel, cobalt, iron or ruthenium, in particular iron, iron and cobalt, iron / cobalt spinels or cobalt / manganese spinel, as well as copper promoted cobalt catalysts.
• GB 1 512 743 In GB 1 512 743, GB 1 553 361, GB 1 553 362 and GB 1 553 363 are catalytic
• catalysts may additionally contain an alkali metal (Group 1A of the Periodic Table), magnesium oxide or zinc oxide as promoters.
• US 4,199,523 discloses a Fischer-Tropsch catalyst containing at least 60% iron. Furthermore, this catalyst may contain promoters such as copper, silver or alkali metals and / or other additives such as zinc oxide, manganese oxide, cerium oxide, vanadium oxide and chromium oxide.
• Chang et al. US 4,418,155 describe a process for converting synthesis gas to hydrocarbons enriched with linear ⁇ -olefins by contacting the synthesis gas at about 260-345 ° C with a catalyst, this catalyst containing a ZSM-5. Type zeolite on which in turn metals such as iron, cobalt or ruthenium, are deposited.
• US Pat. No. 5,100,856 describes copper / potassium-promoted iron / zinc catalysts which show improved activity, selectivity and stability in the synthesis of ⁇ -olefins from carbon monoxide and hydrogen.
• composition of the hydrocarbons formed in the Fischer-Tropsch process can be greatly influenced by the choice of the catalyst used, the reactor types and the reaction conditions.
• WO 02/092216 e.g. a Fischer-Tropsch process on a monolithic catalyst support in a reactor, which is described in several reaction chambers, in which the chemical reaction and the physical separation of the products takes place.
• the product streams that are discharged from the various chambers differ in their composition.
• gasoline, kerosene and diesel are discharged separately from the reactor.
• the object of the present invention is achieved by a process for the synthesis of olefins from synthesis gas in the presence of at least one Fischer-Tropsch catalyst in a reaction column, wherein the synthesis gas is introduced below a zone A of the reaction column in the reaction column, and the olefins below the feed be removed from the synthesis gas.
• the reaction column used according to the process of the invention comprises at least one top zone, one zone A and one bottom zone.
• top zone, zone A and bottom zone are arranged in the predetermined order from top to bottom in the reaction column.
• Zone A comprises at least one reaction zone and one distillation zone.
• the synthesis gas is introduced below zone A but above the bottom zone and the olefins are taken below the feed of the synthesis gas.
• the reaction zone of the Fischer-Tropsch catalyst is located and there takes place the Fischer-Tropsch synthesis.
• the zone of the chemical reaction and the zone of physical separation are not spatially separated.
• the combination zone is thus a combined reaction and distillation zone.
• the synthesis gas is introduced below the zone A in the reaction column.
• the synthesis gas now comes into contact with the Fischer-Tropsch catalyst and it forms a first hydrocarbon mixture a; Unreacted synthesis gas and volatile components of the hydrocarbon mixture formed now rise in the next reaction zone, there takes place another Fischer-Tropsch reaction and it forms a hydrocarbon mixture b; this process is repeated.
• the volatility of the hydrocarbons formed decreases as the chain length increases; they then exist in the liquid phase and flow off into the respective reaction zone (s) below; there can in turn take place with existing synthesis gas chain extension; This process is repeated.
• This hydrocarbon mixture has, depending on the synthesis gas used, the Fischer-Tropsch catalyst and the process parameters (such as geometry of the reaction column, temperature profile of the reaction column, pressure, etc.) a certain molecular weight distribution and a certain average molecular weight. Preferably, this molecular weight distribution is narrower compared to those of conventional Fischer-Tropsch hydrocarbons.
• zone A reaction and distillation zones alternate. In a further embodiment of zone A, combination and distillation zones alternate.
• zone A there is a single combination zone.
• synthesis gas is introduced in addition to the introduction of synthesis gas below the zone A at one or more points within the zone A.
• synthesis gas is introduced in addition to the introduction of synthesis gas below the zone A at one or more points within the zone A.
• water - in liquid form - is supplied above or within zone A.
• the Fischer-Tropsch catalyst located in the reaction or combination zone forms a fixed bed, a fluidized bed, a suspension or a bubble column, preferably a fixed bed or a bubble column.
• the Fischer-Tropsch catalyst in the form of packing, e.g. correspondingly provided with catalyst Raschig rings, Pallringen, saddles to introduce into the column. It is also possible to use packings containing Fischer-Tropsch catalyst or to use pocket bags filled with Fischer-Tropsch catalyst, so-called Bales or Texas tea bags.
• the packages themselves are usually made of sheet metal, expanded metal, wire mesh or knitted fabric, which preferably have a cross-channel structure. In these cases, combination zones are usually formed.
• Zone A internals with a distillative separation effect are used. This can be done, for example, via floors, for example, valve floors, floor panels or related types, such as, for example, tunnel floors or Thormann floors, or screen floors. But it can also packs, which usually consist of sheet metal, expanded metal, wire mesh or knitted fabrics, and which are preferred have a cross-channel structure can be used. Examples are the packings Sulzer MELAPAK, Sulzer BX, Montz B1 types or Montz A3 grades. But it is also possible random packing, so for example Raschig rings, Pall rings, saddle body, etc. use.
• zone A has from 5 to 150 trays, preferably from 15 to 100 trays.
• a distillation zone consists of 1 to 30 trays, a reaction zone of a tray or a combination zone of 1 to 5 trays. This applies in particular to the case in which the reaction and distillation zones or the combination and the distillation zones alternate.
• a combination zone consists of 20 to 100 trays.
• a reaction zone which is provided with packings or with Fischer-Tropsch catalysts in the form of catalyst-provided packings or with active distillation packs or tissue pockets filled with Fischer-Tropsch catalyst, consists of 20 to 100 theoretical plates.
• the zone A contains one to three distillation zones, each with 10 to 100 trays.
• the zone A contains a combination zone.
• low boilers can be taken off via the top zone of the reaction column.
• these low-boiling components contain inert gases, such as nitrogen, which may be present in the synthesis gas, but also possibly formed carbon dioxide, low-boiling paraffins, in particular methane, low-boiling olefins, such as e.g. Ethene, etc.
• low boilers which are formed which contain, for example, any resulting low-boiling paraffins, low-boiling olefins and / or water, are taken off from zone A via a side draw.
• the liquid product taken off via the side take-off can be two-phase. It can be a phase separation be made and the organic phase are returned to the column. In this way, targeted water can be removed from the reaction zone.
• the hydrocarbon mixture formed is removed from the reaction column below the feed of the synthesis gas. This can be done by a side take. However, it is also possible to remove the hydrocarbon mixture formed via the bottom of the column.
• a portion of the hydrocarbon mixture formed is removed via a side draw from zone A and the other part of the hydrocarbon mixture formed is removed below the feed of the synthesis gas.
• reaction column used comprises a top zone, a zone A and a bottom zone.
• the reaction column used comprises, in addition to a top zone, a zone A and a bottom zone, a distillation zone B which is located between the zone A and the bottom zone.
• a distillation zone B which is located between the zone A and the bottom zone.
• internals can be installed with distillative separation effect or packs included.
• the configurations of the internals or packages are analogous to those of the distillation zones of zone A.
• the reaction column used comprises, in addition to a top zone, a zone A and a bottom zone, a distillation zone C which is located between the top zone and the zone A.
• a distillation zone C which is located between the top zone and the zone A.
• internals can be installed with distillative separation effect or packs included.
• the configurations of the internals or packages are analogous to those of the distillation zones of zone A.
• the reaction column used comprises, in addition to a top zone, a zone A and a bottom zone, a distillation zone B located between the zone A and the bottom zone and a distillation zone C located between the top zone and the zone A.
• a distillation zone B located between the zone A and the bottom zone
• a distillation zone C located between the top zone and the zone A.
• internals with distillative separation effect can be installed or packings can be contained.
• the configurations of the internals or packages are analogous to those of the distillation zones of zone A.
• the synthesis gas used according to the method of the invention can be prepared by well-known methods (such as described in Weissermel et al., Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, 15-24), such as reaction of coal or methane with water vapor, or by proportioning of Methane be made with carbon dioxide. Usually this has a ratio of carbon monoxide to hydrogen of 3: 1 to 1: 3. Preferably, a synthesis gas is used which has a mixing ratio of carbon monoxide to hydrogen of 1: 0.5 to 1: 2.5.
• the catalysts used are those Fischer-Tropsch catalysts which preferably catalyze the formation of olefins, in particular ⁇ -olefins.
• iron, iron and cobalt, iron / cobalt-spinel or cobalt / manganese spinel-containing Fischer-Tropsch catalysts are considered, but also copper-promoted cobalt Fischer-Tropsch catalysts.
• the catalysts described in GB 1 512 743, GB 1 553 361, GB 1 553 362, GB 1 553 363, US 4,199,523, US 4,418,155, US 5,100,856 are incorporated herein by reference.
• the inventive method is usually carried out at 150 to 350 ° C.
• the pressure is in this case at 1 to 60 bar, preferably at 10 to 50 bar.
• the gas hourly space velocity (GHSV) is usually 100 to 30,000 parts by volume of feed stream per part by volume of catalyst per hour (l / l »h).
• the product obtained in the process according to the invention which removes below the feed of the synthesis gas from the reaction column, represents a mixture of a plurality of hydrocarbons.
• This mixture has a certain average molecular weight and a certain molecular weight distribution.
• this product contains at least 50% by weight of olefins, preferably ⁇ -olefins.
• the olefins obtained usually have 4 to 20 carbon atoms, preferably 5 to 14.
• a product which contains at least 50% by weight of olefins having 5 to 7 carbon atoms, of which in turn at least 50% by weight are one or more ⁇ -olefins, in particular 1-pentene and 1-hexene.
• a product which contains at least 50% by weight of olefins having 8 to 14 carbon atoms, of which in turn at least 50% by weight are one or more ⁇ -olefins.
• a product which contains at least 50% by weight of olefins having 15 to 20 carbon atoms, of which in turn at least 50% by weight are one or more ⁇ -olefins.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2005
  • 2005-11-28 DE DE102005056784A patent/DE102005056784A1/de not_active Withdrawn
• 2006
  • 2006-11-23 CN CNA2006800445704A patent/CN101316914A/zh active Pending
  • 2006-11-23 EP EP06819684A patent/EP1957614A1/de not_active Withdrawn
  • 2006-11-23 CA CA002630380A patent/CA2630380A1/en not_active Abandoned
  • 2006-11-23 RU RU2008126153/04A patent/RU2008126153A/ru not_active Application Discontinuation
  • 2006-11-23 BR BRPI0619015A patent/BRPI0619015A2/pt not_active IP Right Cessation
  • 2006-11-23 US US12/095,127 patent/US20090005464A1/en not_active Abandoned
  • 2006-11-23 WO PCT/EP2006/068780 patent/WO2007060186A1/de active Application Filing
  • 2006-11-28 AR ARP060105238A patent/AR057191A1/es unknown
• 2008
  • 2008-05-07 NO NO20082131A patent/NO20082131L/no not_active Application Discontinuation

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