[go: up one dir, main page]

WO2004026994A1 - Synthese d'hydrocarbures - Google Patents

Synthese d'hydrocarbures Download PDF

Info

Publication number
WO2004026994A1
WO2004026994A1 PCT/IB2003/003937 IB0303937W WO2004026994A1 WO 2004026994 A1 WO2004026994 A1 WO 2004026994A1 IB 0303937 W IB0303937 W IB 0303937W WO 2004026994 A1 WO2004026994 A1 WO 2004026994A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction stage
hydrogen
carbon monoxide
reaction
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2003/003937
Other languages
English (en)
Inventor
André Peter STEYNBERG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sasol Technology Pty Ltd
Original Assignee
Sasol Technology Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sasol Technology Pty Ltd filed Critical Sasol Technology Pty Ltd
Priority to AU2003260828A priority Critical patent/AU2003260828A1/en
Publication of WO2004026994A1 publication Critical patent/WO2004026994A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • 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
    • C10G2/342—Apparatus, reactors with moving solid catalysts

Definitions

  • THIS INVENTION relates to hydrocarbon synthesis. It relates in particular to a process for synthesizing hydrocarbons.
  • a process for synthesizing hydrocarbons which process includes feeding a gaseous feedstock comprising hydrogen and carbon monoxide, into a first reaction stage containing a slurry bed of a solid particulate non-shifting Fischer- Tropsch catalyst suspended in a carrier liquid, with the feedstock entering the slurry bed at a low level; allowing the hydrogen and carbon monoxide to react catalytically as they pass upwardly through the slurry bed, thereby to form liquid hydrocarbon products and, optionally, gaseous products, with the liquid hydrocarbon products thus constituting the carrier liquid of the slurry bed; withdrawing liquid hydrocarbon products from the first reaction stage; cooling gases and vapours exiting the slurry bed, to condense liquid hydrocarbons and reaction water present therein, with the liquid hydrocarbons and reaction water collecting in and being removed from a separator vessel; withdrawing, from the separator vessel, a first stage tail gas which comprises unreacted hydrogen, unreacted carbon monoxide and any gase
  • the hydrogen and carbon monoxide thus react in accordance with so-called Fischer-Tropsch synthesis, to form the liquid hydrocarbon and aqueous products.
  • non-shifting Fischer-Tropsch catalyst a catalyst having a low selectivity for CO 2 , i.e. a catalyst with which the water gas shift reaction (CO+H 2 O ⁇ » CO 2 +H 2 ) is suppressed or inhibited so that, for example, less than 2 % of the CO is converted to CO2.
  • the gaseous feedstock to the first reaction stage may be a synthesis gas stream comprising mainly the hydrogen and the carbon monoxide.
  • the catalyst selected for use in the first reaction stage requires that the ratio of hydrogen to carbon monoxide in the synthesis gas be lower than the usage ratio for the non-shifting Fischer-Tropsch synthesis.
  • the molar ratio of hydrogen to carbon monoxide in the synthesis gas is between 1.8 and 2.0, while the usage ratio is about 2.06.
  • Tail gas recycle from the first reaction stage may be used further to decrease the H 2 /CO molar ratio of the gas stream to the first reaction stage.
  • selectivity-only enhancing promoters are not used with the first stage catalyst, but desirable selectivity performance can be obtained by keeping a sufficient CO partial pressure throughout the first reaction stage. With this approach, the CO conversion in the first reaction stage must inevitably be limited.
  • the use of a highly active catalyst in the first reaction stage in a slurry phase reactor results in a very high reactor productivity, and very efficient removal of the heat generated is achieved by using a slurry phase reactor for the first stage.
  • an autothermal or partial oxidation reformer will be used to generate the synthesis gas. If an autothermal reformer is used, a low steam to carbon ratio is beneficial, i.e. 0.6 or less, and a carbon dioxide containing stream will be fed or recycled to the reformer in order to attain the desired H 2 /CO ratio in the synthesis gas.
  • the first reaction stage may thus include one or more slurry phase reactors, with each slurry phase reactor thus containing a slurry bed of the solid particulate non- shifting Fischer-Tropsch catalyst suspended in the carrier liquid.
  • Each slurry phase reactor will comprise a suitable vessel, e.g. a column, containing the slurry bed of solid catalyst particles, with the gases and vapours being withdrawn from the vessel above the slurry bed.
  • the process may also include separating liquid hydrocarbon products from catalyst particles by passing, in a filtration zone, liquid product through a filtering medium having a plurality of filter openings through which the liquid passes.
  • the gases and vapours which are withdrawn from the vessel are typically cooled to between 25°C and 75°C in order to effect the condensation and separation of the liquid hydrocarbon products and reaction water from the residual tail gas.
  • Each slurry phase reactor will be maintained at normal elevated pressure and temperature conditions associated with Fischer-Tropsch synthesis, e.g. at a predetermined operating pressure in the range 10-50 bar, and at a predetermined operating temperature in the range 160°C to 280°C.
  • the non-shifting Fischer-Tropsch catalyst of the first reaction stage can thus be a cobalt-based Fischer-Tropsch catalyst containing no selectivity-only enhancing promoters, thereby reducing the cost of the catalyst.
  • the catalyst may be a supported cobalt Fischer-Tropsch catalyst.
  • the catalyst may be that obtained by a preparation method as described in ZA96/2759 (US5733839) or ZA99/1265 (PCT/GB99/00527), which are thus incorporated herein by reference thereto.
  • the supported cobalt catalyst may contain a reduction promoter, which may be selected from platinum, palladium or another noble metal such as ruthenium or rhenium. Promoters known in the art to enhance both catalyst activity and selectivity, such as ruthenium and rhenium, may be used with the catalyst in both the first and the second reaction stages.
  • the hydrogen to carbon monoxide (H 2 /CO) molar ratio in the gaseous feedstock entering the first reaction stage may be between 1.4 and 2.0.
  • the H 2 /CO molar ratio in the gaseous feedstock entering the first reaction stage is between 1.5 and 1.7.
  • most of the reactants i.e. most of the hydrogen and carbon monoxide, will be converted in the first reaction stage.
  • the reactants i.e. most of the hydrogen and carbon monoxide
  • typically from 80% to 90% of the reactants in the gaseous feedstock will be converted in the first reaction stage.
  • tail gas which is withdrawn from the first reaction stage, may be recycled so that it forms part of the gaseous feedstock to the first reaction stage.
  • the second reaction stage may include one or more fixed bed reactors, with each fixed bed reactor thus containing a fixed bed of the solid particulate non-shifting Fischer-Tropsch catalyst. While the use of a fixed bed reactor will achieve the highest overall conversion of reactants, a slurry phase reactor containing a slurry bed of catalyst may also be used for the second reaction stage.
  • a slurry phase reactor may be a lower cost alternative, and various design configurations are known in the art to enhance the plug flow behavior of a slurry phase reactor that would improve the conversions that are attainable with this type of reactor, so that such a slurry phase reactor is preferred.
  • the second reaction stage may thus include one or more slurry phase reactors, with each slurry phase reactor thus containing a slurry bed of the solid particulate non-shifting Fischer-Tropsch catalyst.
  • the non-shifting Fischer-Tropsch catalyst of the second reaction stage can also, at least in principle, be any suitable Fischer-Tropsch catalyst; however, it is envisaged that it will also normally be a cobalt based Fischer-Tropsch catalyst. Preferably, it is a supported cobalt catalyst, which may be obtained by methods known in the art. This catalyst may have a higher cost than the first stage catalyst due to the use of a promoter that causes enhanced selectivity performance at low CO partial pressures.
  • the gases and vapours from the first reaction stage reactor are first cooled to between 25°C and 75°C to effect the condensation and separation of liquid hydrocarbon products and reaction water.
  • the residual gas/vapour is then typically compressed and split into a recycle or tail gas stream and a feed stream to the second reaction stage.
  • the feed stream to the second reaction stage is combined with a hydrogen rich stream, and pre-heated to a temperature up to 220°C, typically about 180°C for the case where a fixed bed reactor is selected.
  • This pre- heated gas is then fed to the top of the fixed bed reactor, which is typically a tubular fixed bed reactor. Design features for this type of reactor are well established in the art, and commercial applications as both first and second stage reactors are known.
  • the H 2 to CO molar ratio of the combined gas stream fed into the second reaction stage is higher than that in the first reaction stage, and is typically at least 2.0. Since the H 2 to CO molar ratio of the tail gas from the first reaction stage is less than that desired for the second stage feed gas, it will be necessary to mix this tail gas with a hydrogen rich stream.
  • the hydrogen rich stream may be partially derived by separating a hydrogen- containing stream from a tail gas from either the first or the second reaction stage.
  • hydrogen or a hydrogen-rich gas
  • the gas derived from the first reaction stage prior to reaction thereof in the second reaction stage is mixed with the gas derived from the first reaction stage prior to reaction thereof in the second reaction stage, in order to increase the H 2 /CO ratio of the tail gas feedstream to the second reaction stage.
  • the H 2 /CO ratio of the feedstream to the second reaction stage may be between 1.9 and 2.1 , preferably about 2.0.
  • the second reaction stage operates in a once through mode, with the conversion of the carbon monoxide and hydrogen reactants present in the combined gas stream fed into the second reaction stage exceeding 60% when a slurry phase reactor is used. When a fixed bed reactor is used, the conversion typically exceeds 80%.
  • Plug flow behavior is enhanced when there is less gas backmixing.
  • the absence of gas recycle improves plug flow behavior.
  • the process may include withdrawing a tail gas comprising residual unreacted reactants and any reaction products that are formed, from the second reaction stage.
  • the tail gas which is withdrawn from the second reaction stage may be subjected to hydrogen recovery, such as by means of pressure swing absorption ('PSA'), or membrane separation known in the art.
  • This hydrogen can then be used as part of the hydrogen component with which the H 2 /CO ratio of the tail gas feedstream to the second reaction stage is increased.
  • the tail gas from the first reaction stage may pass through a hydrogen recovery stage, with the hydrogen rich stream from this stage then passing to the second reactor stage.
  • synthesis gas produced by the autothermal reformers synthesis gas produced by the autothermal reformers with decreased CO 2 recycle or in the absence of CO 2 recycle - a synthesis gas produced by the well known steam reforming process a hydrogen rich stream produced by separation from any of the above synthesis gas streams by means known in the art, for example, membranes subjecting a synthesis gas stream to the water gas shift reaction followed by separation of a hydrogen rich stream by means known in the art.
  • the tail gas from the second reaction stage may be subjected to further cooling to below ambient temperatures to separate additional light hydrocarbons and reaction water.
  • the various liquid hydrocarbons and reaction water produced are subjected to various fractionation and optionally hydroprocessing steps to produce a range of useful products. These products include a fuel for a compression ignition engine and a naphtha that is suitable for cracking to lower olefins comprising mainly ethylene and propylene.
  • a process for synthesising hydrocarbons which process includes feeding a gaseous feedstock comprising hydrogen and carbon monoxide, into a first Fischer-Tropsch reaction stage which is a three-phase low temperature Fischer- Tropsch reaction stage employing non-shifting Fischer-Tropsch catalyst; allowing the hydrogen and carbon monoxide partially to react catalytically in the first reaction stage to form hydrocarbons; enriching with hydrogen at least a portion of a tail gas, comprising unreacted hydrogen and carbon monoxide obtained from the first reaction stage to provide a feed gas with an increased H 2 /CO molar ratio; feeding the feed gas with the increased H 2 /CO molar ratio into a second Fischer-
  • Tropsch reaction stage which is a three phase low temperature Fischer-Tropsch reaction stage employing non-shifting Fischer-Tropsch catalyst; and allowing the hydrogen and carbon monoxide at least partially to react catalytically in the second reaction stage to form hydrocarbons.
  • the gaseous feedstock to the first reaction stage may be a synthesis gas stream comprising mainly the hydrogen and the carbon monoxide, the molar ratio of hydrogen to carbon monoxide in the synthesis gas (the H 2 /CO molar ratio) being between 1.8 and 2.0.
  • Tail gas recycle from the first reaction stage may be used to further decrease the H 2 /CO molar ratio of the gas stream to the first reaction stage.
  • the non-shifting Fischer-Tropsch catalyst of the first reaction stage may be a cobalt-based Fischer-Tropsch catalyst containing no selectivity-only enhancing promoters, thereby reducing the cost of the catalyst.
  • the cobalt catalyst is a supported cobalt catalyst which contains a reduction promoter.
  • the hydrogen to carbon monoxide (H 2 /CO) molar ratio in the gaseous feedstock entering the first reaction stage may be between 1.4 and 2.0.
  • the H 2 /CO molar ratio in the gaseous feedstock entering the first reaction stage is between 1.5 and 1.7.
  • At least 80% of the reactants in the gaseous feedstock may be converted in the first reaction stage.
  • the non-shifting Fischer-Tropsch catalyst of the second reaction stage may be a cobalt based Fischer-Tropsch catalyst.
  • the non-shifting Fischer-Tropsch catalyst of the second reaction stage is a supported cobalt catalyst which includes a selectivity enhancing promoter to enhance selectivity performance at low CO partial pressures.
  • the H 2 /CO molar ratio in the feed gas to the second Fischer-Tropsch reaction stage may be at least 2.0.
  • Both the first reaction stage and the second reaction stage may operate at a temperature of between 160 °C and 280 °C. Typically, both the first reaction stage and the second reaction stage operate at a temperature of between 220 °C and 260 °C.
  • the second reaction stage operates in a once through mode, with the conversion of the carbon monoxide and hydrogen reactants present in the feed gas to the second reaction stage exceeding 60 %.
  • At least a portion of the hydrocarbons synthesised may be upgraded by one or more hydroconversion processes.
  • hydroconversion processes are hydroisomerisation, hydrocracking, hydrodewaxing, hydrorefining and hydrotreating.
  • At least a portion of the synthesised hydrocarbons may be upgraded to a product selected from the group of products consisting of synthetic crude oil, gasoline, diesel fuel, jet fuel, olefins, solvents, lubricating oil, industrial oil, medicinal oil and waxy hydrocarbons.
  • FIGURE 1 shows a simplified flow diagram of a process for synthesizing hydrocarbons, according to a first embodiment of the invention
  • FIGURE 2 shows a simplified flow diagram of a process for synthesizing hydrocarbons, according to a second embodiment of the invention.
  • FIGURE 3 shows a simplified flow diagram of a process for synthesizing hydrocarbons, according to a third embodiment of the invention.
  • reference numeral 10 generally indicates a process for synthesizing hydrocarbons, according to a first embodiment of the invention.
  • the process 10 includes a slurry phase reactor 12. Typically, a plurality, e.g. four, such slurry phase reactors, arranged in parallel, will be provided. However, only one of the reactors is shown.
  • the reactor 12 contains a slurry bed of a solid particulate non-shifting Fischer-Tropsch cobalt catalyst, optionally promoted with platinum, palladium, ruthenium or rhenium, suspended in liquid hydrocarbon product, which acts as a carrier medium.
  • a feed line 14 leads into the bottom of the reactor 12, with a liquid hydrocarbon product withdrawal line 16 also leading from any suitable point on the reactor.
  • a gas/vapour withdrawal line 18 leads from the top of the reactor 12, through a cooler 20, into a separator vessel or drum 22.
  • a tail gas line 28 leads from the separator drum 22, passes through a compressor 27, and then splits into a tail gas recycle line 30 which leads to the feed line 14, and a tail gas line 29.
  • a hydrogen rich gas line 56 joins the line 29, to form a line 31.
  • the process 10 also includes a fixed bed reactor 32 into which the line 31 leads.
  • the reactor 32 contains a fixed bed of solid particulate non-shifting Fischer-Tropsch cobalt catalyst, promoted with a promoter such as zirconia or other suitable promoters.
  • a promoter such as zirconia or other suitable promoters.
  • a liquid hydrocarbon product withdrawal line 34 leads from the bottom of the reactor 32, and a gas/vapour withdrawal line 36 also leads from the bottom of the reactor 32.
  • the line 36 leads through a cooler 38 into a separator vessel or drum 40.
  • a tail gas withdrawal line 46 also leads from the separator drum 40.
  • the slurry bed reactor 12 is typically maintained at an inlet operating pressure of about 25 bar, and at an operating temperature between 160°C and 280°C, typically about 230°C to 240°C.
  • a synthesis gas comprising mainly carbon monoxide and hydrogen, is fed, along the line 14, into the bottom of the slurry bed.
  • the reactants i.e. the carbon monoxide and hydrogen
  • liquid hydrocarbon products are formed by means of catalyzed Fischer-Tropsch reaction of the reactants.
  • the liquid hydrocarbon products are withdrawn through the line 16.
  • the reactor 12 is also provided with internal or external separation means (not shown) for separating catalyst particles from the liquid hydrocarbon products that are withdrawn.
  • the H 2 /CO ratio of the feedstock to the reactor 12 (the combined streams along lines 14 and 30) is between 1.5 and 1.7. 80% to 90% of the carbon monoxide and hydrogen reactants present in the stream in line 14 are converted in the reactor 12.
  • a tail gas is withdrawn from the separator drum 22 along the line 28. Some of this tail gas is recycled to the feedstock to the reactor 12, along the line 30.
  • the reactor 32 will operate with an inlet pressure between 25 bar and 50 bar, and the temperature in the catalyst containing tubes is typically within the range from 160°C to 280°C.
  • reference numeral 100 generally indicates a process for synthesizing hydrocarbons, according to a second embodiment of the invention.
  • the process 100 includes a reformer 102 for generating the synthesis gas.
  • a natural gas feed line 104 leads into the reformer 102, with the synthesis gas line 14 leading from the reformer 102.
  • the process 100 includes a heavy ends recovery unit or section 106, with the line 50 leading into the unit 106.
  • a condensate or heavy ends recovery ('HER') withdrawal line 108 leads from the unit 106, as does a gas withdrawal line 110.
  • the line 46 leads into a pressure swing adsorption stage 48 (or other unit capable of separating a hydrogen rich gas), with a residual tail gas withdrawal line 50 leading from the stage 48.
  • a hydrogen rich gas line 52 leads from the stage 48 and is joined by a line 54, which leads from an external source (not shown) of hydrogen, to form the hydrogen rich gas line 56.
  • a compressor 57 is provided in the line 56.
  • reference numeral 150 generally indicates a process for synthesizing hydrocarbons, according to a third embodiment of the invention.
  • the pressure swing adsorption stage 48 is positioned between the reactor 12 and the reactor 32, with the tail gas line 29 feeding into the stage 48 and the line 52 leading from the stage 48 and joining line 54 to give line 31 entering the reactor 32.
  • the compressor 57 of the processes 100 is dispensed with, and the reactor 32 of the process 150 can operate at a slightly lower pressure than the reactor 32 of the processes 10, 100.
  • the stage 48 preferentially separates mainly H 2 as well as some CO from the tail gas entering it through the line 29.
  • the gas stream exiting the stage 48 of the process 150 along the line 52 will be richer in H 2 and CO than is the case for line 29 in the processes 10, 100, with a H 2 /CO ratio that is higher than that of the stream in the line 29.
  • the residual tail gas that is withdrawn along the line 50 in the process 150 will be richer in CO 2 and CH 4 , with a H 2 /CO molar ratio that is lower than that of the tail gas stream passing along the line 29 in the processes 10, 100.
  • Example 1 the catalysts in the primary reactors 12 and the secondary reactor 32 are the same.
  • the catalyst in the secondary reactor 32 is different to that in the primary reactor 12, and produces the same product spectrum as the primary reactors 12.
  • the reactors 12, 32 are all slurry bed reactors.
  • Table 2 Stream compositions for the Base Case example (mol%).
  • Reactor 12 reaction water formed (stream 24) 97.0 (t/h)
  • Reactor 32 reaction water formed (stream 42) 8.2 (t/h)
  • a further advantage of the process of the invention is that when the option where a fixed bed is used as the reactor 32, is used, it is protected from any poisons that may be present in the feedstock to the slurry bed 12. This protection, together with the relatively mild operating conditions in the fixed bed reactor 32, should result in a long catalyst life for the fixed bed reactor 32. This is important since it is difficult and time consuming to change the catalyst in a fixed bed reactor.
  • the feedstocks to such reactors are manipulated so that the carbon monoxide partial pressure is kept sufficiently high.
  • the result is that the tail gas leaving the slurry phase reactor, after condensing of primary liquid products, contains an excess of unconverted carbon monoxide, which results in wastage or higher cost recycle schemes.
  • the process of the invention avoids this problem with excessive methane formation by limiting the higher methane selectivity to the reactants converted in the second stage reactor only or by the appropriate catalyst selection for the second stage reactor so that the higher cost for the selected catalyst is less significant to the overall process cost.

Landscapes

  • 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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour synthétiser des hydrocarbures. Le procédé consiste à introduire une charge d'alimentation gazeuse comprenant de l'hydrogène et du monoxyde de carbone dans une première cellule de réaction contenant un lit en suspension d'un catalyseur Fischer-Tropsch constant de particules solides, en suspension dans un liquide vecteur, ladite charge d'alimentation pénétrant dans le lit en suspension avec un débit lent. Le procédé consiste ensuite à laisser l'hydrogène et le monoxyde de carbone réagir catalytiquement pendant leur ascension au travers du lit en suspension, pour former des produits hydrocarbonés liquides et, éventuellement, des produits gazeux, lesdits produits hydrocarbonés liquides constituant ainsi le liquide vecteur du lit en suspension. Les produits hydrocarbonés liquides sont retirés de la première cellule de réaction, et les gaz et vapeurs quittant le lit en suspension sont refroidis de façon à condenser les hydrocarbures liquides et l'eau de réaction qu'il contient. Les hydrocarbures liquides et l'eau de réaction sont recueillis dans une cuve de séparation puis évacués de celle-ci. Un gaz résiduaire de la première cellule est retiré de la cuve de séparation, et comprend de l'hydrogène inaltéré, du monoxyde de carbone inaltéré et d'éventuels produits gazeux formés à partir de la première cellule de réaction. Le procédé consiste également à: combiner au moins une partie du gaz résiduaire avec un flux gazeux contenant de l'hydrogène; alimenter le flux gazeux combiné résultant dans une seconde cellule de réaction contenant un lit de catalyseur de Fischer-Tropsch constant de particules solides; et laisser l'hydrogène et le monoxyde de carbone présents dans le gaz résiduaire réagir catalytiquement dans la seconde cellule de réaction pour former des produits hydrocarbonés liquides et, éventuellement, des produits gazeux; retirer les produits hydrocarbonés liquides de la seconde cellule de réaction; et refroidir les gaz et les vapeurs quittant le lit catalytique de la seconde cellule de réaction pour condenser les hydrocarbures liquides et l'eau de réaction qu'il contient, les hydrocarbures liquides et l'eau de réaction étant recueillis dans une cuve de séparation puis évacués de celle-ci.
PCT/IB2003/003937 2002-09-19 2003-09-15 Synthese d'hydrocarbures Ceased WO2004026994A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003260828A AU2003260828A1 (en) 2002-09-19 2003-09-15 Hydrocarbon synthesis

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA2002/7531 2002-09-19
ZA200207531 2002-09-19

Publications (1)

Publication Number Publication Date
WO2004026994A1 true WO2004026994A1 (fr) 2004-04-01

Family

ID=32031275

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2003/003937 Ceased WO2004026994A1 (fr) 2002-09-19 2003-09-15 Synthese d'hydrocarbures

Country Status (2)

Country Link
AU (1) AU2003260828A1 (fr)
WO (1) WO2004026994A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1746143A1 (fr) * 2005-07-20 2007-01-24 Shell Internationale Research Maatschappij B.V. Procédé Fischer-Tropsch
WO2007009952A1 (fr) 2005-07-20 2007-01-25 Shell Internationale Research Maatschappij B.V. Synthese fischer-tropsch a plusieurs niveaux
WO2007065904A1 (fr) * 2005-12-09 2007-06-14 Shell Internationale Research Maatschappij B.V. Procede de lancement d'un procede de production d'hydrocarbures a partir de gaz de synthese
WO2008000784A1 (fr) * 2006-06-30 2008-01-03 Shell Internationale Research Maatschappij B.V. Procédé pour l'optimisation d'un procédé de fischer-tropsch en plusieurs étapes
WO2008062208A3 (fr) * 2006-11-23 2009-04-30 Gtl F1 Ag Installations de transformation de gaz en liquides, équipées de réacteurs de type fischer-tropsch montés en série avec apport d'hydrogène
CN100529023C (zh) * 2007-02-07 2009-08-19 中国科学院山西煤炭化学研究所 一种合成气合成汽油联产芳烃的工艺
US7705060B2 (en) 2005-12-09 2010-04-27 Shell Oil Company Method to start a process for producing hydrocarbons from synthesis gas
US7855236B2 (en) 2005-12-09 2010-12-21 Shell Oil Company Method to start a process for producing hydrocarbons from synthesis gas
WO2011131928A1 (fr) * 2010-04-19 2011-10-27 Gtl.F1 Ag Appareillage et procédé pour conduire une réaction de synthèse de fischer-tropsch
US20140135410A1 (en) * 2011-03-30 2014-05-15 Japan Oil, Gas And Metals National Corporation Hydrocarbon synthesis reaction apparatus, start-up process thereof, and hydrocarbon synthesis reaction system
US8980201B2 (en) 2009-06-26 2015-03-17 Gtl.Fi Ag Apparatus and process for three-phase reaction
US9039980B2 (en) 2008-11-18 2015-05-26 Gtl.Fi Ag Slurry bubble column reactor
US9278891B2 (en) 2008-12-22 2016-03-08 Gtl.F1 Ag Apparatus and method for conducting a fischer-tropsch synthesis reaction

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB454948A (en) * 1934-04-25 1936-10-12 Studien Und Verwertungsgesells Method of increasing yield in the catalytic synthesis of aliphatic hydrocarbons
US4443561A (en) * 1981-07-17 1984-04-17 Shell Oil Company Process for the preparation of organic compounds
WO2002020439A1 (fr) * 2000-09-01 2002-03-14 Exxonmobil Research And Engineering Company Processus de fischer tropsch

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB454948A (en) * 1934-04-25 1936-10-12 Studien Und Verwertungsgesells Method of increasing yield in the catalytic synthesis of aliphatic hydrocarbons
US4443561A (en) * 1981-07-17 1984-04-17 Shell Oil Company Process for the preparation of organic compounds
WO2002020439A1 (fr) * 2000-09-01 2002-03-14 Exxonmobil Research And Engineering Company Processus de fischer tropsch

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2006271760B2 (en) * 2005-07-20 2009-06-25 Shell Internationale Research Maatschappij B.V. Multi stage Fischer-Tropsch process
WO2007009952A1 (fr) 2005-07-20 2007-01-25 Shell Internationale Research Maatschappij B.V. Synthese fischer-tropsch a plusieurs niveaux
RU2409608C2 (ru) * 2005-07-20 2011-01-20 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Многостадийный способ фишера-тропша
US7795318B2 (en) 2005-07-20 2010-09-14 Shell Oil Company Multi stage Fischer-Tropsch process
EP1746143A1 (fr) * 2005-07-20 2007-01-24 Shell Internationale Research Maatschappij B.V. Procédé Fischer-Tropsch
US7855235B2 (en) 2005-12-09 2010-12-21 Shell Oil Company Method to start a process for producing hydrocarbons from synthesis gas
AU2006323998B2 (en) * 2005-12-09 2009-10-29 Shell Internationale Research Maatschappij B.V. Method to start a process for producing hydrocarbons from synthesis gas
US7705060B2 (en) 2005-12-09 2010-04-27 Shell Oil Company Method to start a process for producing hydrocarbons from synthesis gas
US7855236B2 (en) 2005-12-09 2010-12-21 Shell Oil Company Method to start a process for producing hydrocarbons from synthesis gas
WO2007065904A1 (fr) * 2005-12-09 2007-06-14 Shell Internationale Research Maatschappij B.V. Procede de lancement d'un procede de production d'hydrocarbures a partir de gaz de synthese
RU2414445C2 (ru) * 2005-12-09 2011-03-20 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ пуска процесса получения углеводородов из синтез-газа
CN101351529B (zh) * 2005-12-09 2013-01-02 国际壳牌研究有限公司 起动由合成气制备烃的工艺的方法
WO2008000784A1 (fr) * 2006-06-30 2008-01-03 Shell Internationale Research Maatschappij B.V. Procédé pour l'optimisation d'un procédé de fischer-tropsch en plusieurs étapes
WO2008062208A3 (fr) * 2006-11-23 2009-04-30 Gtl F1 Ag Installations de transformation de gaz en liquides, équipées de réacteurs de type fischer-tropsch montés en série avec apport d'hydrogène
US20100137458A1 (en) * 2006-11-23 2010-06-03 Gtl.F1 Ag Gas to liquids plant with consecutive fischer-tropsch reactors and hydrogen make-up
GB2444055B (en) * 2006-11-23 2011-11-23 Gtl F1 Ag Gas to liquids plant with consecutive Fischer-Tropsch reactors and hydrogen make-up
CN100529023C (zh) * 2007-02-07 2009-08-19 中国科学院山西煤炭化学研究所 一种合成气合成汽油联产芳烃的工艺
US9039980B2 (en) 2008-11-18 2015-05-26 Gtl.Fi Ag Slurry bubble column reactor
US9278891B2 (en) 2008-12-22 2016-03-08 Gtl.F1 Ag Apparatus and method for conducting a fischer-tropsch synthesis reaction
US8980201B2 (en) 2009-06-26 2015-03-17 Gtl.Fi Ag Apparatus and process for three-phase reaction
WO2011131928A1 (fr) * 2010-04-19 2011-10-27 Gtl.F1 Ag Appareillage et procédé pour conduire une réaction de synthèse de fischer-tropsch
CN102892865A (zh) * 2010-04-19 2013-01-23 Gtl.F1公司 用于进行费-托合成反应的装置和方法
CN102892865B (zh) * 2010-04-19 2014-12-24 Gtl.F1公司 用于进行费-托合成反应的装置和方法
US20140135410A1 (en) * 2011-03-30 2014-05-15 Japan Oil, Gas And Metals National Corporation Hydrocarbon synthesis reaction apparatus, start-up process thereof, and hydrocarbon synthesis reaction system
US9434657B2 (en) * 2011-03-30 2016-09-06 Japan Oil, Gas And Metals National Corporation Hydrocarbon synthesis reaction apparatus, start-up process thereof, and hydrocarbon synthesis reaction system

Also Published As

Publication number Publication date
AU2003260828A1 (en) 2004-04-08

Similar Documents

Publication Publication Date Title
NL1027594C2 (nl) Regeling van de CO2-emissies van een Fischer-Tropsch-installatie door toepassing van tweevoudig functionele syngas-omzetting.
EP1054850B1 (fr) Transformation de gaz au moyen d'hydrogene de gaz de synthese et d'hydrogene de gaz residuaires d'hydrotransformation
EP1054851B9 (fr) Conversion au gaz utilisant de l'hydrogene produit a partir d'un gaz de synthese pour le rajeunissement catalytique et la conversion d'hydrocarbures
GB2444055A (en) Multi reactor Fischer Tropsch process
CN109135798B (zh) 在gtl环境中用于制备烃类燃料的增强的费-托法
WO2000063141B1 (fr) Systeme a reacteurs multiples et procede fischer-tropsch de synthese
SA99200195B1 (ar) تحويل غاز باستخدام هيدروجين ناتج من غاز تخليق لإزالة الكبريت من سوائل هيدروكربونية لبئر غاز
CN104508091B (zh) 在gtl环境中用于烃燃料配制的费希尔-特罗普希工艺的增强
WO2004026994A1 (fr) Synthese d'hydrocarbures
CN101223259A (zh) 多阶段费-托方法
US9074148B2 (en) Hydrogen and carbon utilization in synthetic fuels production plants
AU2002362693B2 (en) System for power generation in a process producing hydrocarbons
EP1887072A1 (fr) Procédé de traitement de gaz résiduaires de Fischer-Tropsch
AU2003274689B2 (en) Process for the production of hydrocarbons from gaseous hydrocarbonaceous feed
EP0212758B1 (fr) Procédé de préparation de gaz de synthèse à partir d'une alimentation hydrocarbonée
CA2748216C (fr) Procede fischer-tropsch basse pression
US11104852B2 (en) Fluidized bed processes and catalyst systems for Fischer-Tropsch conversion

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP