WO2008052992A1 - Procédé de fabrication de polyoléfines - Google Patents

Procédé de fabrication de polyoléfines Download PDF

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Publication number
WO2008052992A1
WO2008052992A1 PCT/EP2007/061690 EP2007061690W WO2008052992A1 WO 2008052992 A1 WO2008052992 A1 WO 2008052992A1 EP 2007061690 W EP2007061690 W EP 2007061690W WO 2008052992 A1 WO2008052992 A1 WO 2008052992A1
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WO
WIPO (PCT)
Prior art keywords
zone
polymerization
reaction
olefins
fischer
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PCT/EP2007/061690
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German (de)
English (en)
Inventor
Bram Willem Hoffer
Ekkehard Schwab
Dirk Neumann
Thomas Butz
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Basf Se
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Publication date
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Publication of WO2008052992A1 publication Critical patent/WO2008052992A1/fr

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    • 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
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors

Definitions

  • Polyolefins have been known for a long time. Their properties depend on many factors, such as their molecular weight, molecular weight distribution, their composition, microstructure, etc. Especially copolymers of ethene and higher ⁇ -olefins are particularly suitable for many applications since the two parameters "composition” and "microstructure” provide an even greater possibility of variation in properties than in the case of homopolymers.
  • the individual parameters can be influenced in different ways.
  • the microstructure of polymers can be tailored using suitable organometallic compounds such as metallocenes.
  • z As the molecular weight, inter alia, on the reaction temperature of the polymerization, dosed hydrogen, etc. are set, - also type and proportion of one or more co- or termonomers affects the molecular weight in some considerable.
  • the tailoring of the polymer properties with the aid of the catalyst is relatively complicated because for each combination of monomers and each application, the appropriate catalyst must first be found.
  • the controller z. As the molecular weight over the reaction temperature are quite narrow limits. It is also difficult to find suitable mixtures and amounts of co- and optionally of termonomer, since the various monomers in pure form are rather expensive and must always be kept available, unreacted monomers may need to be separated again, etc.
  • the reaction column used according to the invention for the production of the ⁇ -olefins in the first step comprises at least one top zone, one zone A and one bottom zone. In this case, 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 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 with increasing chain length, they then exist in the liquid phase and flow into the respective underlying reaction zone (s); 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 than the conventional Fischer-Tropsch hydrocarbons.
  • reaction and distillation zones alternate.
  • zone A 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 zone A at one or more points within zone A.
  • synthesis gas is introduced in addition to the introduction of synthesis gas below zone A at one or more points within 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 such as. B. appropriately provided with catalyst Raschig rings, Pallringen, saddles to introduce into the column. It is furthermore 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 packs 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. In the distillation zones of Zone A, internals with a distillative separation effect are used. This can, for example, on floors, such as valve floors, bubble cap or related designs, such. B. tunnel floors or Thormann floors, or sieve plates.
  • packings which usually consist of sheet metal, expanded metal, wire mesh or knitted fabric, and which preferably have a cross-channel structure, can also be used. Examples of these are the packings Sulzer MELAPAK, Sulzer BX, Montz B1 grades or Montz A3 grades. But it is also possible, disordered packing, ie z. B. 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-filled packing 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 optionally formed carbon dioxide, low-boiling paraffins, in particular methane, low-boiling olefins, such as 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 made a phase separation 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 which is located between the zone A and the bottom zone and a distillation zone C which is located between the top zone and the zone A.
  • a distillation zone B which is located between the zone A and the bottom zone
  • a distillation zone C which is 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 process of the invention can be prepared by generally known methods (such as described in Weissermel et al., Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, 15 to 24), such as, for example, conversion of coal or Methane can be produced with water vapor, or by Komproportionierung of methane 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 particularly suitable, but copper-promoted cobalt Fischer-Tropsch catalysts are also suitable.
  • 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 by reference into the present invention.
  • the inventive method is usually carried out at 150 to 350 0 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 typically 100 to 30,000 volumes of feedstream per volume of catalyst per hour (l / hr).
  • the product obtained in the first stage of the process according to the invention which is removed from the reaction column below the feed of the synthesis gas, 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 is obtained 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. In a further particular embodiment, a product is obtained 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.
  • Zone A when starting the process in the zone A of the reaction column, an ⁇ -olefin or a mixture of ⁇ -olefins whose carbon number is at least 1 lower than that of the mainly formed olefin, below Zone A can be separated to introduce.
  • the ⁇ -olefins thus obtained or the mixture of ⁇ -olefins thus obtained is then used in a second stage for the copolymerization with ethene.
  • a particular advantage of the process according to the invention consists in that in each case less than 5% by mass of dienes, aromatics and cyclic compounds are obtained, wherein it is particularly preferred if a total of less than 5% by mass of dienes, aromatics and cyclic compounds is obtained, more preferably less than 1% by mass, most preferably less than 0.1% by mass. Most preferably, less than 10 ppm of these compounds are obtained.
  • the polymerization is operated under inert conditions.
  • any suitable metals or organometallic compounds may be used. These are the expert z. From: L. Corbelli, R. Fabbri, F. Milani, Kunststoffe 34 (1981) 1 1; G. Maglio, F. Dilani, P. Musto, F. Riva, Makromol. Chem. Rapid Comm. 8 (1987) 589; Y. Doi, R.Ohnishi, K. Soga, Makromol. Chem. Rapid. Comm. 4 (1983) 169; L. Abis, G. Bacchilega, F. Dilani, Makromo. Chem. 187 (1986) 1877; C.
  • cocatalysts are the cocatalysts known in the field of metallocenes, such as polymeric or oligomeric alumoxanes, Lewis acids and also aluminum and borates and other so-called non-coordinating anions.
  • metallocenes such as polymeric or oligomeric alumoxanes, Lewis acids and also aluminum and borates and other so-called non-coordinating anions.
  • Particularly suitable cocatalysts are methylalumoxane, triisobutylaluminum (TIBA) -modified methylaluminoxane, and diisobutylalumoxane, trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, triisooctylaluminum, moreover dialkylaluminum compounds such as diisobutylaluminum hydride, diethylaluminum chloride, substituted triarylboron compounds such as tris (pentafluorophenyl) borane, and ionic compounds containing as anion tetrakis (pentafluorophenyl) borate, such as triphenyl methyltetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, N, N-d
  • the polymerization according to the invention is carried out in the gas, liquid or slurry (suspension) phase.
  • the temperature range for this ranges from -20 0 C to +200 0 C, preferably from 0 0 C to 160 0 C, more preferably from +20 0 C to +80 0 C.
  • the pressure range is from 1 to 50 bar, preferably from 3 to 30 bar.
  • polymerization-inert solvents used are: saturated aliphas or (halo) aromatics, such as pentane, hexane, heptane, cyclohexane, petroleum ether, petroleum, hydrogenated benzines, benzene, toluene, xylene, ethylbenzene, chlorobenzene and analogues. These reaction conditions for the polymerization are generally known to the person skilled in the art.
  • the polymerization according to the invention is preferably carried out in the presence of inert organic solvents.
  • Suitable inert organic solvents are, for example, aromatic, aliphatic and / or cycloaliphatic hydrocarbons, such as preferably benzene, toluene, hexane, pentane, heptane and / or cyclohexane.
  • the polymerization is preferably operated as a solution polymerization or in suspension.
  • the process according to the invention is carried out in the gas phase.
  • the polymerization of olefins in the gas phase was technologically first realized in 1962 (US-A-3,023,203).
  • Corresponding fluidized bed reactors have long been prior art, reference is made to document WO-99/19059-A1, which is incorporated by reference into the application for the purposes of US patent practice.
  • the metal (s), the organometallic compound (s) and, if appropriate, the cocatalyst (s) are also applied to an inorganic support and used in heterogenized form.
  • inert inorganic solids are silica gels, clays, aluminosilicates, talc, zeolites, carbon black, inorganic oxides such as silica, alumina, magnesia, titania, silicon carbide, preferably silica gels, zeolites and carbon black.
  • the said inert, inorganic solids can be used individually or mixed with one another.
  • organic carriers are used individually or mixed with one another or with inorganic carriers. Examples of organic carriers are porous polystyrene, porous polypropylene or porous polyethylene.
  • EP-A1-0 965 599 (which is incorporated by reference as a reference in the present application for the purposes of US patent practice) is particularly suitable for the preparation of supported polymerization catalyst systems, characterized in that a) one or more different transition metal complexes in a mixture of at least two different b) bringing the solution thus obtained into contact with one or more different support materials, the volume of the solution being sufficient to form a slurry with the support material (s), the volume of the solution being approx higher boiling solvent is less than or equal to the total pore volume of the carrier, and c) the lower boiling solvent is removed by more than 90%, the cocatalyst (s) either added together with the one or more metals or transition metal complexes in step a) or already on the support materials used in step b) have been applied or are partly added together with the transition metal complex in step a) and have already been partially applied to the support material (s) used in step b).
  • nonconjugated diene are all dienes known to those skilled in the art whose double bonds have different reactivities with respect to the catalyst system used, such as 5-ethylidene-2-norbornene (ENB), 5-vinylnorbornene, 1, 4-hexadiene and dicyclopentadiene. Preference is given to 5-ethylidene-2-norbornene and 1, 4-hexadiene.
  • the process has the advantage that the ⁇ -olefins can be continuously supplied and that a suitable for the polymerization mixture of ⁇ -olefins must not be achieved by mixing individual expensive ⁇ -olefins, but only the final ⁇ -olefin mixture with a suitable amount of ethene must be mixed. Due to the possible presence of the alkanes formed in the first stage of the process according to the invention, the heat removal is also improved in the polymerization reaction.

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

Abstract

La présente invention concerne une matière première alternative pour la copolymérisation d'éthène/a-oléfine.
PCT/EP2007/061690 2006-11-02 2007-10-30 Procédé de fabrication de polyoléfines WO2008052992A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06123355.7 2006-11-02
EP06123355 2006-11-02

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WO2008052992A1 true WO2008052992A1 (fr) 2008-05-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012056203A3 (fr) * 2010-10-29 2012-10-26 Asa Energy Conversions Ltd Conversion du gaz naturel

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002092216A1 (fr) * 2001-05-17 2002-11-21 Conoco Inc. Support de catalyseur monolithique en nid d'abeilles pour reacteur de distillation catalytique
WO2003099884A1 (fr) * 2002-05-28 2003-12-04 Sasol Technology (Proprietary) Limited Terpolymeres de propylene et leur procede de polymerisation
US20040152851A1 (en) * 2003-01-31 2004-08-05 Weiqing Weng Polymerization process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002092216A1 (fr) * 2001-05-17 2002-11-21 Conoco Inc. Support de catalyseur monolithique en nid d'abeilles pour reacteur de distillation catalytique
WO2003099884A1 (fr) * 2002-05-28 2003-12-04 Sasol Technology (Proprietary) Limited Terpolymeres de propylene et leur procede de polymerisation
US20040152851A1 (en) * 2003-01-31 2004-08-05 Weiqing Weng Polymerization process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012056203A3 (fr) * 2010-10-29 2012-10-26 Asa Energy Conversions Ltd Conversion du gaz naturel
US9243189B2 (en) 2010-10-29 2016-01-26 Asa Energy Conversions Ltd. Conversion of natural gas
EA026636B1 (ru) * 2010-10-29 2017-04-28 ЭйЭсЭй ЭНЕРДЖИ КОНВЕРШНЗ ЛТД. Конверсия природного газа
AU2011322285B2 (en) * 2010-10-29 2017-05-18 Asa Energy Conversions Ltd Conversion of natural gas

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