EP1746143A1 - Procédé Fischer-Tropsch - Google Patents

Procédé Fischer-Tropsch Download PDF

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Publication number
EP1746143A1
EP1746143A1 EP05254536A EP05254536A EP1746143A1 EP 1746143 A1 EP1746143 A1 EP 1746143A1 EP 05254536 A EP05254536 A EP 05254536A EP 05254536 A EP05254536 A EP 05254536A EP 1746143 A1 EP1746143 A1 EP 1746143A1
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EP
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Prior art keywords
ratio
stream
entry
range
hydrogen
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EP05254536A
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German (de)
English (en)
Inventor
Robert Martijn Van Hardeveld
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority to EP05254536A priority Critical patent/EP1746143A1/fr
Publication of EP1746143A1 publication Critical patent/EP1746143A1/fr
Withdrawn legal-status Critical Current

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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

Definitions

  • the present invention relates to a process for the production of hydrocarbon products from syngas, in particular a Fischer-Tropsch process.
  • the Fischer-Tropsch process can be used for the conversion of hydrocarbonaceous feed stocks into liquid and/or solid hydrocarbons.
  • the feed stock for example natural gas, associated gas, coal-bed methane, residual (crude) oil fractions or coal
  • the syngas is then converted in one or more steps over a suitable catalyst at elevated temperature and pressure into paraffinic compounds ranging from methane to high molecular weight molecules comprising up to 200 carbon atoms, or, under particular circumstances, even more.
  • the hydrocarbonacaceous feed suitably is methane, natural gas, associated gas or a mixture of C 1-4 hydrocarbons.
  • the feed comprises mainly, i.e. more than 90v/v%, especially more than 94%, C 1-4 hydrocarbons, and especially comprises at least 60 v/v percent methane, preferably at least 75%, more preferably 90%.
  • Very suitably natural gas or associated gas is used.
  • any sulphur in the feedstock is removed.
  • normally gaseous hydrocarbons normally liquid by hydrocarbons and optionally normally solid hydrocarbons are obtained. It is often preferred to obtain a large fraction of normally solid hydrocarbons. These solid hydrocarbons may be obtained up to 85 wt% based on total hydrocarbons, usually between 50 and 75 wt%.
  • the partial oxidation process looks to convert natural gas, which is mainly methane, to the carbon monoxide and hydrogen mixture known as syngas.
  • Natural gas which is mainly methane
  • hydrogen mixture known as syngas.
  • Pure methane would create a theoretical hydrogen to carbon monoxide (hereinafter termed "H 2 /CO") molar ratio of 2, but because natural gas includes other compounds such as ethane, and because sometimes excess oxygen is used to try and achieve substantial, close or near 100% conversion of the methane, the actual H 2 /CO ratio in syngas is usually less than 2, such as 1.7-1.8.
  • the Fischer-Tropsch (FT) process may be operated in a single pass mode ("once through") or in a recycle mode. In either configuration, there is a syngas entry stream system into the process reactor or reactors, and naturally it is desired to obtain an overall CO conversion level or percentage as high as possible.
  • operational constraints for the FT process One of the operational constraints for the syngas conversion is the H 2 /CO ratio in the exit stream at the reactor outlet. A too low H 2 /CO ratio results in the loss of catalyst activity, e.g. by coke formation which may be permanent.
  • the criterion for the average H 2 /CO ratio in the exit stream at the reactor outlet(s) is desired to be ⁇ 0.4.
  • the overall usage ratio is the overall reaction stoichiometry of H 2 and CO in the Fischer-Tropsch reaction, including the water gas shift reaction.
  • the present invention provides a process for the production of hydrocarbon products from syngas in one or more syngas conversion reactors, the reactor(s) having a syngas entry stream system comprising one or more entry streams into the reactor(s) having an overall hydrogen/carbon monoxide [H 2 /Co] in ratio below the syngas consumption ratio of the reactor(s), and an exit stream system comprising one or more exit streams from said reactor(s) having an overall [H 2 /CO] out ratio lower than the [H 2 /CO] in ratio, wherein a hydrogen stream is added to at least one of the entry streams to influence the H 2 /CO ratio in said stream such that the CO conversion ratio in the reactor(s) is in the range 70-95%.
  • a reaction especially when using for example a cobalt catalyst, generally follows the equation: CO + 2H 2 ⁇ (-CH 2 ) n - + H 2 O
  • the theoretical H 2 to CO ratio is 2, although generally a slight excess of hydrogen is preferred to seek greater conversion of the carbon monoxide.
  • the ratio of hydrogen to carbon monoxide actually used in the reactor by the process and calculated by analysis of the products formed is the "consumption ratio". In the present invention, the consumption ratio is generally below the above theoretical ratio of 2.
  • the overall [H 2 /CO] in ratio of all the entry streams forming the entry stream system is in the range 1.6-2.0, preferably about 1.7-1.9.
  • the overall [H 2 /CO] out ratio of all the exit streams forming the exit stream system is in the range 0.3-0.7, preferably about 0.4-0.5.
  • the actual H 2 /CO ratio of each stream of syngas as it enters a reactor is desired to be lower, generally in the range 1.0-1.4.
  • Methods of reducing the [H 2 /CO] in ratio prior to entry are well known in the art, such as mixing the syngas with other syngas having a lower H 2 /CO ratio.
  • This [H 2 /CO] in reduction could be partly achieved by the use of recycle of the product(s) from the reaction.
  • product having a [H 2 /CO] out ratio of 0.4-0.5 can be used to reduce the [H 2 /CO] in entry ratio.
  • the present invention includes adjustment of the H 2 /CO ratio of the syngas through a second hydrogen rich syngas stream which can be mixed with the entry stream syngas, thereby increasing the operational flexibility in the CO conversion level and thereby increasing the STY.
  • the hydrogen rich stream could be for example pure hydrogen or a hydrogen rich syngas, for example from a SMR process described below.
  • Adjustment of H 2 /CO may be desired for several reasons. Variations in each of the parameters in formula (I) above can be desired for different, although sometimes interrelated, reasons. For example, whilst the UR figure can vary, it is desired to keep it relatively constant. Similarly, whilst the X co conversion level naturally varies, it is desired to keep this figure “stable", or at least as constant as possible. Meanwhile the (H 2 /CO) in ratio can vary due to several factors, such as instability in the syngas supply. As mentioned above, a change in the (H 2 /CO) in ratio from 1.8 to 1.7 results in a conversion level drop of approximately 6%. Assuming it is intended to maintain the greatest possible conversion level, or at least keep the conversion level at a stable figure, it is better to seek this by increasing the (H 2 /CO) in ratio, for instance by the introduction of a hydrogen stream.
  • the hydrogen stream may be pure hydrogen, i.e. having >99% purity, and without carbon monoxide. Alternatively the hydrogen stream may only need to be sufficiently pure to provide the intended effect of the invention.
  • Sources of partially, substantially or wholly pure hydrogen are known in the art.
  • One source is a hydrogen manufacturing unit.
  • Another source is Steam Methane Reforming (SMR), which provides a high H 2 /CO ratio through the reaction: 2CH 4 + 2H 2 O ⁇ 2CO + 6H 2
  • the methane in the above reaction can be provided from natural gas, for example the same natural gas as is used to form the syngas. Whilst the above reaction gives a theoretical H 2 /CO ratio of 3, in fact secondary reactions such as the reaction between carbon monoxide and water, increase the hydrogen content, and thus increase the H 2 /CO ratio.
  • a SMR product stream is used, it is used directly as the hydrogen stream, without any further treatment, for example purification.
  • the hydrogen stream has a H 2 /CO ratio greater than 3, preferably in the range of 4 to 8, more preferably 5 to 7.
  • the Xco conversion level is greater than 80%, and more preferably greater than 85%.
  • the present invention could involve a multi-stage conversion process which may involve, two, three, or more conversion stages, generally two. Generally, the CO conversion level for each stage of a multi-stage process of the present invention is approximately the same.
  • a hydrogen stream could be added to at least one entry streams for one, more than one, or each stage, to influence the H 2 /CO ratio in the at least one entry stream for the relevant stage(s).
  • the type and amount of hydrogen stream for each relevant stage may be the same or different to the type and amount of hydrogen stream(s) for each other stage.
  • the CO conversion level during each stage of a multi-stage conversion process is in the range 70-95%, and more preferably about 80-95%.
  • a 80% CO conversion level at each stage provides an overall approximate 96% CO conversion level.
  • the process may be carried out in one or more parallel reactors, such parallel reactors generally being provided with the same syngas entry stream, and one or more of the reactors possibly being provided by two or more entry streams.
  • One or more of the entry streams may be derived from a common source, and one or more of the exit streams may be combined.
  • exit stream system refers the combined parameters of all the exit stream(s), which may still be physically distinct.
  • exit stream system refers to the combined parameters of all the exit stream(s).
  • all the entry streams for the process are derived from a single source of syngas.
  • the present invention also provides a hydrocarbon product or products whenever formed by a process as herein described, including any products made by hydrocoversion of the hyrocarbon product(s).
  • the present invention provides products generally formed by the Fischer-Tropsch process.
  • Products of the Fischer-Tropsch synthesis may range from methane to heavy paraffinic waxes.
  • the production of methane is minimised and a substantial portion of the hydrocarbons produced have a carbon chain of at least 5 carbon atoms.
  • the amount of C 5+ hydrocarbons is at least 60% by weight of the total product, more preferably, at least 70% by weight, even more preferably, at least 80% by weight, most preferably, at least 85% by weight.
  • Fischer-Tropsch catalysts are known in the art, and typically include a Group VIII metal component, preferably cobalt, iron and/or ruthenium, more preferably cobalt.
  • the catalysts comprise a catalyst carrier.
  • the catalyst carrier is preferably porous, such as a porous inorganic refractory oxide, more preferably alumina, silica, titania, zirconia or mixtures thereof.
  • the optimum amount of catalytically active metal present on the carrier depends inter alia on the specific catalytically active metal.
  • the amount of cobalt present in the catalyst may range from 1 to 100 parts by weight per 100 parts by weight of carrier material, preferably from 10 to 50 parts by weight per 100 parts by weight of carrier material.
  • the catalyst suitably has an average diameter of 0.5-15 mm.
  • One form of catalyst is as an extrudate.
  • Such extrudates suitably have a length of 2-10mm, especially 5-6mm, and a cross section suitably of 1-6mm 2 , especially 2-3mm 2 .
  • the catalytically active metal may be present in the catalyst together with one or more metal promoters or cocatalysts.
  • the promoters may be present as metals or as the metal oxide, depending upon the particular promoter concerned. Suitable promoters include oxides of metals from Groups IIA, IIIB, IVB, VB, VIB and/or VIIB of the Periodic Table, oxides of the lanthanides and/or the actinides.
  • the catalyst comprises at least one of an element in Group IVB, VB and/or VIIB of the Periodic Table, in particular titanium, zirconium, manganese and/or vanadium.
  • the catalyst may comprise a metal promoter selected from Groups VIIB and/or VIII of the Periodic Table. Preferred metal promoters include rhenium, platinum and palladium.
  • a most suitable catalyst comprises cobalt as the catalytically active metal and manganese and/or vanadium as a promoter.
  • the promoter if present in the catalyst, is typically present in an amount of from 0.1 to 60 parts by weight per 100 parts by weight of carrier material. It will however be appreciated that the optimum amount of promoter may vary for the respective elements which act as promoter. If the catalyst comprises cobalt as the catalytically active metal and manganese and/or vanadium as promoter, the cobalt: (manganese + vanadium) atomic ratio is advantageously at least 12:1.
  • the Fischer-Tropsch synthesis is preferably carried out at a temperature in the range from 125°C to 350°C, more preferably 175°C to 275°C, most preferably 200°C to 260°C.
  • the pressure preferably ranges from 5 to 150 bar abs., more preferably from 5 to 80 bar abs.
  • the gaseous hourly space velocity may vary within wide ranges and is typically in the range from 500 to 10,000 N1/1/h, preferably in the range from 1000 to 4,000 N1/1/h.
  • the present invention provides the use of a hydrogen stream to influence the H 2 /CO ratio in a syngas entry stream into a Fischer-Tropsch reactor.
  • the hydrogen may not be pure hydrogen, and can be provided by various processes, such as the SMR process described above.
  • SMR process provides a further benefit to the present invention. It provides an integrated process for syngas production and conversion of carbonaceous feedstocks to hydrocarbonaceous products (including for example light and heavy paraffins, methanol and the like).
  • One of the advantages of such an integrated process is the ability to help balance the energy requirements/output of various steps of a Fischer-Tropsch plant overall system, and thus improve the overall efficiency (in terms of carbon efficiency and thermal efficiency) of the Fischer-Tropsch process as a whole.
  • a further advantage provided by the present invention is that in integrating the syngas production and SMR processes, there is a reduction in the overall demand for oxygen in a hydrocarbon product plant, as the oxygen required in the SMR reaction can be provided from a superheated steam of the syngas production.
  • the H 2 /CO ratio from the partial oxidation process is generally in the range 1.7-1.9, and this can be reduced to preferred ratio of 1.0-1.4 in two ways: (a) by the recycle of at least a portion of the exit stream from the reactor, and (b) introduction of a hydrogen stream.
  • the steam methane reforming process provides a high hydrogen-content stream, possibly having a H 2 /CO ratio of 5 or 6.
  • Reformed syngas can be used as a source of an enriched hydrogen stream, for example if the CO is removed by a suitable process such as pressure swing adsorption PSA.
  • the introduction of the hydrogen stream from the reforming process provides the ability to influence the H 2 /CO ratio in the Fischer-Tropsch stream, especially to seek a constant and/or stable CO conversion level.

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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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP05254536A 2005-07-20 2005-07-20 Procédé Fischer-Tropsch Withdrawn EP1746143A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05254536A EP1746143A1 (fr) 2005-07-20 2005-07-20 Procédé Fischer-Tropsch

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EP05254536A EP1746143A1 (fr) 2005-07-20 2005-07-20 Procédé Fischer-Tropsch

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013124793A1 (fr) * 2012-02-24 2013-08-29 Sasol Technology (Proprietary) Limited Synthèse de fischer-tropsch

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0178007A2 (fr) * 1984-10-10 1986-04-16 Shell Internationale Researchmaatschappij B.V. Procédé de production de gaz de synthèse
US6310108B1 (en) * 1999-02-11 2001-10-30 Institut Francais Du Petrole Process for synthesis at atmospheric distillate that comprises the use of Fischer-Tropsch technology
EP1219566A1 (fr) * 2000-12-27 2002-07-03 L'air Liquide, S.A. à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude Procédé et dispositif intégré pour la production de gaz de synthèse
US20030050348A1 (en) * 2001-03-26 2003-03-13 Kennedy Paul Edwin Hydrocarbon conversion process using a plurality of synthesis gas sources
US20040014825A1 (en) * 2000-09-28 2004-01-22 Hensman John Richard Fischer-tropsch process
WO2004026994A1 (fr) * 2002-09-19 2004-04-01 Sasol Technology (Proprietary) Limited Synthese d'hydrocarbures

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0178007A2 (fr) * 1984-10-10 1986-04-16 Shell Internationale Researchmaatschappij B.V. Procédé de production de gaz de synthèse
US6310108B1 (en) * 1999-02-11 2001-10-30 Institut Francais Du Petrole Process for synthesis at atmospheric distillate that comprises the use of Fischer-Tropsch technology
US20040014825A1 (en) * 2000-09-28 2004-01-22 Hensman John Richard Fischer-tropsch process
EP1219566A1 (fr) * 2000-12-27 2002-07-03 L'air Liquide, S.A. à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude Procédé et dispositif intégré pour la production de gaz de synthèse
US20030050348A1 (en) * 2001-03-26 2003-03-13 Kennedy Paul Edwin Hydrocarbon conversion process using a plurality of synthesis gas sources
WO2004026994A1 (fr) * 2002-09-19 2004-04-01 Sasol Technology (Proprietary) Limited Synthese d'hydrocarbures

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
OIL AND GAS JOURNAL, 6 September 1971 (1971-09-06), pages 86 - 90

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013124793A1 (fr) * 2012-02-24 2013-08-29 Sasol Technology (Proprietary) Limited Synthèse de fischer-tropsch
CN104204141A (zh) * 2012-02-24 2014-12-10 沙索技术有限公司 费托合成
US9061952B2 (en) 2012-02-24 2015-06-23 Sasol Technology (Propietary) Limited Fischer-tropsch synthesis
AP3825A (en) * 2012-02-24 2016-09-30 Sasol Tech Pty Ltd Fischer-tropsch synthesis
CN104204141B (zh) * 2012-02-24 2016-11-09 沙索技术有限公司 费托合成
AU2013223680B2 (en) * 2012-02-24 2017-03-23 Sasol Technology (Proprietary) Limited Fischer-tropsch synthesis
RU2619107C2 (ru) * 2012-02-24 2017-05-12 Сэсол Текнолоджи (Проприетери) Лимитед Синтез фишера-тропша

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