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WO1994004476A1 - Production d'un produit de melange d'essence - Google Patents

Production d'un produit de melange d'essence Download PDF

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Publication number
WO1994004476A1
WO1994004476A1 PCT/AU1993/000433 AU9300433W WO9404476A1 WO 1994004476 A1 WO1994004476 A1 WO 1994004476A1 AU 9300433 W AU9300433 W AU 9300433W WO 9404476 A1 WO9404476 A1 WO 9404476A1
Authority
WO
WIPO (PCT)
Prior art keywords
paraffins
normal paraffins
catalyst
stream
naphtha
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/AU1993/000433
Other languages
English (en)
Inventor
Sandra Bessell
Peter John Jackson
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.)
Broken Hill Proprietary Company Pty Ltd
Original Assignee
Broken Hill Proprietary Company 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 Broken Hill Proprietary Company Pty Ltd filed Critical Broken Hill Proprietary Company Pty Ltd
Priority to AU49339/93A priority Critical patent/AU4933993A/en
Publication of WO1994004476A1 publication Critical patent/WO1994004476A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen

Definitions

  • the invention relates to an improved reformulated gasoline blendstock obtained from synthesis gas, and a process for producing this blendstock.
  • RVP Reid Vapour Pressure
  • Benzene is undesirable because of its effect on human health as it is a known carcinogen. So despite its high octane value, it will be limited to less than 1 vol %. Other aromatics are also undesirable because of the toxicity of the emissions they cause and so will have to be limited to meet the targeted emission reductions. This will probably mean a ceiling of the order of 25% aromatics. Other undesirable hydrocarbons in gasoline are those which cause emissions of ozone-forming volatile organic compounds. Heavy aromatics also fall into this group, as well as olefins, which have a high photochemical reactivity. A high endpoint of the gasoline (which is measured by the T90 ASTM distillation procedure) has also been found to contribute to these emissions, and so will be targeted for reduction in reformulated gasolines.
  • a minimum oxygen content of 2% has been targeted. This will promote complete combustion to carbon dioxide rather than carbon monoxide. This may be achieved by the addition of significant quantities of MTBE (11%) or other ethers such as ETBE (ethyl tertiary butyl ether) or TAME (tertiary amyl methyl ether) . These are high octane additives, and would compensate for octane losses due to reduction in aromatics and olefin content.
  • ETBE ethyl tertiary butyl ether
  • TAME tertiary amyl methyl ether
  • Methanol and ethanol although oxygenates of high octane, are not as favourable as additives as the ethers because of their high blending vapour pressures and lack of water tolerance.
  • a more suitable reformulated gasoline blendstock could, however, be obtained via the Fischer-Tropsch process.
  • the naphthas produced from this process are generally straight chain, paraffinic and non-aromatic. Depending on the catalyst composition used and the operating conditions selected, variations in the characteristics of the product can be obtained.
  • the most common catalyst compositions used for the Fischer- Tropsch process consist of iron or cobalt, supported or unsupported, containing optional promoters or additives. If, however, the process is being used to convert a synthesis gas derived from natural gas, cobalt based catalyst formulations are preferred to iron based catalysts because of their greater carbon efficiency.
  • the "classic" cobalt, thoria, magnesia on kieselguhr catalyst is useful for distillate production producing considerable amounts of hydrocarbons boiling in both distillate and wax fractions.
  • the wax can then be hydrocracked to increase the amount of distillate produced.
  • the hydrocarbons are also essentially linear paraffins which give a high quality, high cetane rated distillate. Similar products result from silica, alumina and silica- alumina supported cobalt catalysts.
  • bifunctional catalyst systems In order to produce hydrocarbons suitable for use as gasoline, bifunctional catalyst systems have been introduced, in which the Fischer-Tropsch active metal is supported on a zeolite, so as to utilise the shape selective and acidic properties of the zeolite to limit the chain length of the product and produce a gasoline fraction of enhanced octane number by increasing the levels of branching and/or aromatics in the product.
  • Zeolites such as Zeolite Y and ZSM-5 have been used as such supports.
  • US Patent 4 086 262 (Mobil Oil Corporation) describes the use of zeolites such as ZSM-5 as supports for Fischer- Tropsch metals including iron, cobalt, nickel, ruthenium, thorium and osmium, to produce an aromatic rich product from synthesis gas.
  • Australian Patent Application AU 34883/84 (Union Carbide Corporation) describes the use of catalyst compositions consisting of steam-stabilised Zeolite Y as a support for conventional Fischer-Tropsch metals such as iron or cobalt. These compositions enhanced the amount of product boiling in the liquid fuel range as well as branching and aromatisation in the products.
  • Australian Patent Application AU 88929/82 (U.S. Department of Energy) describes a catalyst composition of cobalt, promoted with thoria, on a ZSM-5 type zeolite support which is used to produce high octane liquid hydrocarbon products containing branched aliphatic hydrocarbons rather then aromatics to impart high octane numbers.
  • This catalyst when operated at approximately 280°C produced a liquid hydrocarbon product which contained only approximately 3% aromatics.
  • the present invention provides a process for producing gasoline blendstock which process comprises contacting synthesis gas comprising carbon monoxide and hydrogen with a catalyst comprising cobalt supported on a ZSM-5 type zeolite at a temperature in the range from 220°C to 280°C to produce a naphtha, fractionating the naphtha to remove butanes and hydrocarbons boiling at a temperature in excess of 174°C and isomerising normal paraffins contained in the fractionated naphtha to produce a gasoline blendstock.
  • Fischer-Tropsch naphthas for use in this invention consist predominantly of hydrocarbons in the gasoline range have high levels of branching and contain little or no detectable quantities of aromatics.
  • the synthesis gas comprises substantial proportions of carbon monoxide and hydrogen, but may also contain carbon dioxide, water, methane and nitrogen.
  • the synthesis gas may be obtained from carbonaceous sources such as natural gas, coal, oil shale and petroleum hydrocarbons by known processes such as partial oxidation, gasification and steam reforming.
  • the relative concentrations of the gaseous components depend on the source of the synthesis gas and the process by which it is obtained. Hydrogen to carbon monoxide molar ratios of synthesis gases for use in the present invention may lie in the range from 0.2 to 6.
  • cobalt is the Fischer-Tropsch active metal used in the Fischer- Tropsch catalyst formulations to produce these naphthas, and is preferably present in an amount of 1 to 50 weight percent based on the total weight of the catalyst composition.
  • a shape selective, acidic zeolite is required as the catalyst support. Zeolites of reasonably high silica to alumina ratios, i.e. 10 or higher, fulfil this requirement. These zeolites are exemplified by the ZSM-5 type zeolites which include ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38 and other similar materials.
  • ZSM-5 type zeolites As described in our Australian Patent 613 813, in which ZSM-5 type zeolites of 5 ⁇ m or less, or more preferably l ⁇ or less, are used as supports to produce a highly branched, and hence high octane, liquid hydrocarbon product.
  • the ZSM-5 type zeolite is preferably present in the formulation in an amount of from 10 to 98 weight percent.
  • thoria and/or other materials such as magnesia, beryllium oxide, alumina, uranium oxides and manganese can be used as promoters for cobalt Fisher-Tropsch catalysts in order to improve catalyst activity and selectivity.
  • Other additives or promoters such as chromium, scandium and praseodymium have also been shown to be beneficial in these compositions in Australian Patent Application Serial No. 638741 and our co- pending International patent applications PCT/AU92/00457 and PCT/AU93/00067, Australian patent applications AU 62238/90, PK7995 and PL0941. Presence of these promoter materials is optional, but preferred.
  • Thoria and/or other promoters/additives can be present in an amount of from 0.01 to 25 weight percent, more preferably from 0.05 to 5 weight percent.
  • the cobalt, promoter and other additives may be loaded onto the support by any of the methods known to those skilled in the art. These methods include: (i) mixing the appropriate oxides and support,
  • the catalyst Before use in synthesis gas conversion, the catalyst is reduced or activated.
  • hydrogen, synthesis gas or another reductant may be used for this reduction step under conditions of elevated temperature and pressures of from atmospheric to the pressures used in the synthesis.
  • Typical reduction temperatures are of the order of 250-350°C, with typical pressures of from atmospheric to 3.5 MPa.
  • the Fischer-Tropsch process can be performed over a wide range of temperatures, pressures and space velocities.
  • temperature range used if the required product is to be obtained.
  • the system In order for the zeolite to be effective in producing branched hydrocarbons the system must be at a temperature at which isomerisation reactions can occur on the zeolite. This places a lower limit of 200°C on the reaction. As the temperature is increased to 280°C aromatics formation begins. As the temperature is further increased other undesirable side reactions begin to occur, including cracking, methanation, carbon deposition and the water gas shift.
  • the reaction temperature is maintained in the range from 220 to 280°C, and most preferably in the range from 220 to 270°C.
  • Typical pressures used in the synthesis are of the order of from 0 to 5 MPa, usually from 1 to 3.5 MPa, whilst typical space velocities are at GHSV's (Gas Hourly Space Velocities) of the order of from 10 to 10000 hr- 1 , usually from 50 to 5000 hr- 1 .
  • the first step in the treatment of the Fischer-Tropsch naphtha is fractionation.
  • the Fischer-Tropsch naphthas used in the invention generally contain of the order of 1- 2% C 4 hydrocarbons. However, any C 4 's removed can be converted to isobutylenes for MTBE production.
  • the endpoint of the gasoline will also have to be controlled to avoid emissions of volatile organic compounds.
  • the endpoint is usually 216°C (412°F) or higher. This corresponds to a C 12 cut ⁇ off.
  • the endpoints of the Fischer-Tropsch naphthas used in this invention vary with the catalyst and process conditions used, but generally 60-99% of the liquid hydrocarbon product boils under 216°C. In fact, generally 50-98% of the product boils under 174°C (345°F), or the C 10 cut-off. Due to emission reductions which can be achieved by dropping the endpoint to C 10 , the product boiling above 174°C is separated. This separated fraction can be used as a distillate blendstock or be selectively cracked for inclusion into the gasoline pool.
  • the fractionated Fischer-Tropsch naphtha now consists of iso-paraffins, normal paraffins, iso-olefins and normal olefins boiling between C 5 and C 10 .
  • This naphtha may contain of the order of 10-60% normal paraffins, 1-30% normal olefins and 50-80% iso-paraffins and iso-olefins, with preferred naphthas typically containing 15-25% normal paraffins, 1-10% normal olefins and 65-75% iso-paraffins and iso-olefins.
  • This process can be reactor-lead, where the fresh feed and any recycle are fed to the isomerisation reactor before separation of non-normals, or adsorber- lead, where the fresh feed is fed to the adsorber before isomerisation.
  • the feed to be isomerised is normally of low normal paraffin content, it is preferable to first extract these by adsorption, thus requiring a smaller isomerisation unit.
  • TIP Total Isomerisation Process
  • UOP formerly Union Carbide Corporation
  • Handbook of Petroleum Refining Processes edited by R.A. Meyers (McGraw-Hill, New York, 1986)
  • IsoSiv UOP's separation technology
  • Shell's Hysomer isomerisation process In IsoSiv normal paraffins are separated from a hydrocarbon mixture by selective adsorption on a zeolite molecular sieve. This material has uniform pores of such a size as to allow the normal paraffins to pass through the pore openings into the zeolite cavities where they are adsorbed.
  • This process operates in the vapour phase at temperatures of 200 to 370°C, and pressures of 1.4 to 3.4 MPa.
  • the product from this isomerisation process is a high octane, highly isomerised naphtha, excellent as a reformulated gasoline blendstock. Its other properties include low volatility, very little or no detectable aromaticity, and because of its low endpoint and low aromaticity it causes minimum emissions of organic compounds.
  • oxygen containing compounds such as MTBE or other ethers or alcohols will have to be added to this blendstock so as to bring the oxygen content up to a minimum of 2%. This would have the effect of further increasing the octane rating of the product.
  • the butanes removed in the fractionation step could be used in MTBE production.
  • a synthesis gas stream 1 comprising substantially hydrogen and carbon monoxide with a preferred H 2 to CO molar ratio in the range from 1 - 3 is passed to a Fischer-Tropsch reactor 2 containing an activated cobalt on ZSM-5 type zeolite catalyst, preferably a promoted, activated cobalt on small crystal ZSM-5 type zeolite catalyst at 220-280°C, 0-5MPa with a GHSV of 10 - 10,000 hr- 1 , preferably at 220-270°C, l-3.5MPa with a GHSV of 50 - 5,000-t ⁇ r- 1 .
  • an activated cobalt on ZSM-5 type zeolite catalyst preferably a promoted, activated cobalt on small crystal ZSM-5 type zeolite catalyst at 220-280°C, 0-5MPa with a GHSV of 10 - 10,000 hr- 1 , preferably at 220-270°C, l-3.5MPa with a GHSV of 50 - 5,000-t
  • the Fischer-Tropsch naphtha 3 exiting from this reactor is then passed to a fractionator 4 for removal of C 4 hydrocarbons 5 and all hydrocarbons with a boiling point above 174°C 6.
  • the C 4 hydrocarbons removed can be used to produce MTBE for incorporation into reformulated gasoline, while the higher hydrocarbons can be used as a distillate blendstock or be selectively cracked for inclusion into the gasoline pool.
  • the fractionated Fischer-Tropsch naphtha 7 may then be passed to a hydrotreating unit 8 along with additional hydrogen 9 in order to reduce its olefin content.
  • This optionally hydrotreated feed 10 is then isomerised, most preferably in an adsorber-lead isomerisation process with recycle, whereby the feed 10 is passed to an adsorption bed 11 where the normal paraffins are adsorbed, whilst the iso-paraffins 12 pass through for collection. Desorption of the normal paraffins is effected by stripping with hydrogen (make up hydrogen 13 and recycle hydrogen 16).
  • the normal paraffins in the hydrogen stream 14 are then passed to the isomerisation reactor 15 where the normal paraffins are partially isomerised to iso-paraffins and the effluent stream 16 containing iso-paraffins, normal paraffins and recycle hydrogen is recycled to the adsorption bed 11 to separate the iso-paraffins formed and to further isomerise the normal paraffins in the isomerisation reactor 15.
  • the isomerisation and adsorption steps are operated at 200 to 370°C and 1.4 to 3.4 MPa.
  • the product obtained is a highly isomerised, non-aromatic naphtha, with a low endpoint and volatility. It's RON is of the order of 90.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'un produit de mélange d'essence. On produit un naphta (3) en mettant en contact du gaz de synthèse (1) avec un catalyseur (2) comprenant du cobalt supporté sur une zéolithe du type ZSM-5, à une température comprise entre 220 °C et 280 °C. Le naphta est fractionné (4) pour en séparer le butane (5) et les hydrocarbures ayant un point d'ébullition supérieur à 174 °C (6). Les paraffines normales contenues dans le naphta fractionné (7) sont isomérisées (8) pour obtenir un produit de mélange d'essence. Un procédé d'isomérisation décrit consiste à séparer les paraffines normales des isoparaffines (12) contenues dans le naphta fractionné par absorption sélective des paraffines normales sur un tamis moléculaire à zéolithe (11), désorption des paraffines normales à l'aide d'hydrogène (13) et passage du flux d'hydrogène et de paraffines normales ainsi formé (14) sur un tamis moléculaire acide (15) chargé de métal.
PCT/AU1993/000433 1992-08-25 1993-08-25 Production d'un produit de melange d'essence Ceased WO1994004476A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49339/93A AU4933993A (en) 1992-08-25 1993-08-25 Producing blendstock

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPL4281 1992-08-25
AUPL428192 1992-08-25

Publications (1)

Publication Number Publication Date
WO1994004476A1 true WO1994004476A1 (fr) 1994-03-03

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999000190A1 (fr) * 1997-06-26 1999-01-07 Agip Petroli S.P.A. Procede pour la preparation d'un catalyseur a base de cobalt et de scandium
US6703429B2 (en) 2001-08-23 2004-03-09 Chevron U.S.A. Inc. Process for converting synthesis gas into hydrocarbonaceous products
WO2009083466A1 (fr) * 2008-01-02 2009-07-09 Shell Internationale Research Maatschappij B.V. Compositions de carburant liquide
US7973086B1 (en) 2010-10-28 2011-07-05 Chevron U.S.A. Inc. Process of synthesis gas conversion to liquid hydrocarbon mixtures using alternating layers of synthesis gas conversion catalyst and hydrocracking catalyst
US7973087B2 (en) 2009-11-18 2011-07-05 Chevron U.S.A. Inc. Process of synthesis gas conversion to liquid fuels using mixture of synthesis gas conversion catalyst and dual functionality catalyst
US8461220B2 (en) 2010-06-10 2013-06-11 Chevron U.S.A. Inc. Process and system for reducing the olefin content of a fischer-tropsch product stream
US8481601B2 (en) 2010-11-23 2013-07-09 Chevron U.S.A. Inc. Process of synthesis gas conversion to liquid hydrocarbon mixtures using a catalyst system containing ruthenium and an acidic component
US8519011B2 (en) 2010-10-28 2013-08-27 Chevron U.S.A. Inc. Process of synthesis gas conversion to liquid hydrocarbon mixtures using alternating layers of synthesis gas conversion catalyst, hydrocracking and hydroisomerization catalyst
WO2022223332A1 (fr) * 2021-04-21 2022-10-27 Clariant International Ltd Système et procédé d'isomérisation de naphta léger

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4659743A (en) * 1981-10-09 1987-04-21 The United States Of America As Represented By The United States Department Of Energy Process and catalyst for converting synthesis gas to liquid hydrocarbon mixture
AU6223890A (en) * 1989-09-11 1991-03-14 Broken Hill Proprietary Company Limited, The Catalyst for conversion of synthesis gas into hydrocarbons
AU1604092A (en) * 1991-05-07 1992-11-12 Shell Internationale Research Maatschappij B.V. A process for the production of isoparaffins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4659743A (en) * 1981-10-09 1987-04-21 The United States Of America As Represented By The United States Department Of Energy Process and catalyst for converting synthesis gas to liquid hydrocarbon mixture
AU6223890A (en) * 1989-09-11 1991-03-14 Broken Hill Proprietary Company Limited, The Catalyst for conversion of synthesis gas into hydrocarbons
AU1604092A (en) * 1991-05-07 1992-11-12 Shell Internationale Research Maatschappij B.V. A process for the production of isoparaffins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
INDUSTRIAL & ENGINEERING CHEMISTRY PRODUCT RESEARCH AND DEVELOPMENT, Volume 23, No. 4, (1984), SHAMSL A. et al., "Zeolite-Supported Cobalt Catalysts for the Conversion of Synthesis Gas to Hydrocarbon Products", pages 513-514. *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6096790A (en) * 1997-06-26 2000-08-01 Agip Petroli S.P.A. Process for the preparation of a catalyst based on cobalt and scandium
CN1128012C (zh) * 1997-06-26 2003-11-19 阿吉佩罗里股份公司 以钴和钪为基的催化剂的制备方法
WO1999000190A1 (fr) * 1997-06-26 1999-01-07 Agip Petroli S.P.A. Procede pour la preparation d'un catalyseur a base de cobalt et de scandium
US6703429B2 (en) 2001-08-23 2004-03-09 Chevron U.S.A. Inc. Process for converting synthesis gas into hydrocarbonaceous products
AU2008342650B2 (en) * 2008-01-02 2012-09-27 Shell Internationale Research Maatschappij B.V. Liquid fuel compositions
WO2009083466A1 (fr) * 2008-01-02 2009-07-09 Shell Internationale Research Maatschappij B.V. Compositions de carburant liquide
US8974552B2 (en) 2008-01-02 2015-03-10 Shell Oil Company Liquid fuel compositions
US7973087B2 (en) 2009-11-18 2011-07-05 Chevron U.S.A. Inc. Process of synthesis gas conversion to liquid fuels using mixture of synthesis gas conversion catalyst and dual functionality catalyst
US8461220B2 (en) 2010-06-10 2013-06-11 Chevron U.S.A. Inc. Process and system for reducing the olefin content of a fischer-tropsch product stream
US8519011B2 (en) 2010-10-28 2013-08-27 Chevron U.S.A. Inc. Process of synthesis gas conversion to liquid hydrocarbon mixtures using alternating layers of synthesis gas conversion catalyst, hydrocracking and hydroisomerization catalyst
US7973086B1 (en) 2010-10-28 2011-07-05 Chevron U.S.A. Inc. Process of synthesis gas conversion to liquid hydrocarbon mixtures using alternating layers of synthesis gas conversion catalyst and hydrocracking catalyst
US8481601B2 (en) 2010-11-23 2013-07-09 Chevron U.S.A. Inc. Process of synthesis gas conversion to liquid hydrocarbon mixtures using a catalyst system containing ruthenium and an acidic component
WO2022223332A1 (fr) * 2021-04-21 2022-10-27 Clariant International Ltd Système et procédé d'isomérisation de naphta léger

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