WO1998019979A1 - Procede de conversion de gaz utilisant un reacteur limitant la formation de composes a chaines longues - Google Patents

Procede de conversion de gaz utilisant un reacteur limitant la formation de composes a chaines longues Download PDF

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Publication number
WO1998019979A1
WO1998019979A1 PCT/US1997/019722 US9719722W WO9819979A1 WO 1998019979 A1 WO1998019979 A1 WO 1998019979A1 US 9719722 W US9719722 W US 9719722W WO 9819979 A1 WO9819979 A1 WO 9819979A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
chain
reactor
hydrocarbon product
product
Prior art date
Application number
PCT/US1997/019722
Other languages
English (en)
Inventor
Gary L. Beer
Original Assignee
Syntroleum Corporation
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 Syntroleum Corporation filed Critical Syntroleum Corporation
Priority to AU52418/98A priority Critical patent/AU5241898A/en
Publication of WO1998019979A1 publication Critical patent/WO1998019979A1/fr

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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
    • 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
    • C10G2/344—Apparatus, reactors with moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0455—Reaction conditions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0485—Set-up of reactors or accessories; Multi-step processes
    • C07C1/049—Coupling of the reaction and regeneration of the catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for converting gases to liquids and in one of its aspects relates to a process for converting "syngas” (e.g. hydrogen and carbon monoxide) to a hydrocarbon liquid (e.g. gasoline, distillates, etc.) by passing the syngas in contact with a catalyst in a chain-limiting reactor wherein the catalyst is removed from the reactor and replaced with "clean" catalyst before undesirable, long-chain hydrocarbons are formed within the reactor.
  • syngas e.g. hydrogen and carbon monoxide
  • hydrocarbon liquid e.g. gasoline, distillates, etc.
  • Fischer-Tropsch (“F-T”) synthesis proceeds by adding one carbon atom at a time to a growing chain which, in turn, is adsorbed onto an active metal catalytic site.
  • the chain length of the product is a function of the probability of the chain continuing to grow versus the probability of the product desorbing from the catalyst without further growth.
  • Different catalyst formulations have various probabilities for growth, leading to differing chain lengths being produced by each catalyst. Operating conditions can also affect the probability of growth and thereby dictate chain length.
  • the present invention provides a Fischer-Tropsch process for converting syngas to a desired hydrocarbon product wherein the product has a desired chain length, e.g. diesel.
  • the process involves passing the syngas through a bed of catalyst to convert the syngas to the desired product until at least a portion of the catalyst reaches a saturated state with "saturated state" being defined as when the hydrocarbon which is being absorbed on said catalyst reaches a chain length which is substantially equal to the chain length of the desired product .
  • the saturated portion of the catalyst is removed and replaced with fresh or unsaturated catalyst .
  • the saturated catalyst is then "regenerated” by passing a fluid e.g. steam, over the catalyst to thereby remove the absorded hydrocarbon therefrom.
  • the saturated catalyst is replaced with unsaturated catalyst at a rate substantially equal to the rate at which said saturated catalyst is removed.
  • the present invention is directed to a Fischer-Tropsch process for converting syngas to a desired hydrocarbon product having a desired chain length wherein the process is carried out in a chain-limiting reactor.
  • the syngas is passed through a fluidized bed of catalyst in the chain-limiting reactor.
  • Fresh or unsaturated catalyst is carried by the syngas into the bottom of the reactor where it forces the catalyst in the fluidized bed upward therein.
  • the catalyst remains in contact with the syngas as it rises within the reactor and the length of the chain of the hydrocarbon being absorbed on the catalyst continues to grow.
  • the saturated portion of the catalyst exits the reactor and is transferred to a regeneration vessel where a regenerating fluid, e.g. stripping gas, steam, etc., is passed over the catalyst to remove the hydrocarbon product therefrom.
  • a regenerating fluid e.g. stripping gas, steam, etc.
  • the regenerated or now unsaturated catalyst can then be recycled to the reactor.
  • the chain-limiting reactor is of the type known as "a fluidized-bed” reactor or a "circulating fluidized-bed” reactor.
  • the chain- limiting reactor is operated at a temperature and pressure at which said hydrocarbon product remains a vapor while in said reactor. This vaporized hydrocarbon product is removed from the reactor and can easily be condensed to the desired liquid product, e.g. diesel.
  • FIGURE 1 is a schematic representation of a fluidized- bed, chain-limiting reactor system for carrying out a process in accordance with the present invention
  • FIGURE 2 is a graph showing the probability of the growth of hydrocarbon chains verses the selectivity of a desired product to be formed during an F-T process
  • FIGURE 3 is a schematic representation of another embodiment of a chain-limiting reactor which can be used in carrying out the present invention.
  • FIGURE 1 discloses a schematic diagram of a fluidized bed system S which can be used in carrying out a gas-to-liquid conversion process in accordance with the present invention.
  • System S is comprised of a reactor vessel 1 of a type commonly used in certain, standard fluidized-bed reactor-type operations, e.g. fluid catalytic cracking refinery processes. It should be recognized that vessel 1 can take other configurations without departing from the present invention.
  • a feed gas (“syngas”, i.e. a gas comprised of carbon monoxide (CO) and hydrogen (H 2 ) ) is fed through supply line 2 into the bottom of vessel 1 and flows upward through fluidized bed which is comprised of a Fischer-Tropsch synthesis catalyst.
  • syngas i.e. a gas comprised of carbon monoxide (CO) and hydrogen (H 2 )
  • synthesis catalyst is any appropriate catalytic material which will convert the particular feed gas flowing into vessel 1 into a particular desired product. That is, the particular catalyst will depend on the feed gas and the particular product to be formed.
  • a typical synthesis catalyst can be copper on alumina, e.g. BASR copper catalyst type S3 -85.
  • cobalt-based Fischer-Tropsch catalyst can be used e.g., see U.S. Patents 4,579,985; 4,579,986; 4,587,008; and 4,640,766.
  • Synthesis catalyst is in the form of loose, unconsolidated granular particles of various diameters, e.g. less than 1 micron to 2.5 inches, whereby the catalyst particles comprise a "fluidized-bed" as used and understood in the art.
  • Catalyst bed 4 as shown in FIGURE 1 is an example of a fluidized bed.
  • CHEMICAL ENGINEERS' HANDBOOK J.H. Perry, 4th Edition, McGraw-Hill Book Co., pps 20-42 to 20-53.
  • the feed gas e.g. syngas
  • the feed gas flows upward through catalyst bed 4 at a superficial velocity.
  • Superficial velocity is understood in this art and is based on the flow of gas through reactor vessel 1 when the vessel is empty and is that velocity at which the upflowing gases will enlarge the spaces between the particles in catalyst bed 4 to a point where no stable arrangements between individual particles can exist and the particles will vibrate or circulate in a semi-stable arrangement; hence the velocity at which catalyst bed 4 becomes a "fluidized- bed” .
  • Exothermic heat which is generated by the catalytic reaction is extracted from the reaction zone (i.e. catalyst bed 4) to control the operating temperature within reactor 1.
  • a heat exchanger 5 which has a plurality of vertical tubes 5a is positioned within and extends substantially through catalyst bed 4.
  • a heat-conducting fluid e.g. water
  • the heated fluid e.g. steam
  • pipe 7 for disposal, e.g. power generation, recycling, etc.
  • the feedgas e.g. syngas
  • product e.g. diesel
  • operating conditions i.e. temperature and pressure
  • the actual operating temperatures and pressures during any particular conversion operation will depend upon the composition of the feed gas, desired product, the particular catalyst used, etc..
  • the temperature in the reactor will likely be from about 350°F. to about 550° F.
  • the pressure can range from about 15 to 600 psia depending on the composition of the feed gas, the particular catalyst used, etc.
  • the reason that it is desirable to maintain the desired product in its vapor phase while in the reactor is that the presence of any substantial amount of liquids within reactor 1 will adversely affect the integrity of the fluidized catalyst bed 4, possibly to the point of making the process inoperable.
  • the Fischer-Tropsch process within reactor 1 converts the feed gas ("syngas", i.e. a gas comprised of carbon monoxide
  • This phenomena significantly affects the ability a catalyst to form substantially only one product during a particular Fischer-Tropsch process. That is, where a particular catalyst is used to form a desired product such as diesel, large amounts of undesirable (i.e. less valuable) light-hydrocarbon gases (e.g. methane) are also inherently formed during the process which have to be handled or otherwise disposed of. Likewise, in a F-T process where a different catalyst is used to form a heavier, distillate product a large fraction of heavy waxes will also be produced along with the desired distillates.
  • undesirable light-hydrocarbon gases e.g. methane
  • the residence time of each catalyst particle within reactor 1 is controlled so as to limit the growth of the hydrocarbon chain which is adsorbed onto the surface of each catalyst particle to correspond substantially with the length of the hydrocarbon chain of the desired product. That is, catalyst particles remain in reactor 1 until the particles become “saturated", i.e. the length of the hydrocarbon chain being absorbed onto the surface of the particles is substantially equal to the length of the chain of the desired hydrocarbon product. At this point, the "saturated" catalyst particles are removed from reactor 1 and "regenerate” by removing the adsorbed hydrocarbons therefrom.
  • limiting the chain length of the hydrocarbon product produced by F-T synthesis may be accomplished by continuously supplying "fresh" catalyst into the bottom of reactor 1 and removing "saturated” catalyst at the top of catalyst bed 4.
  • the fresh catalyst is mixed with and is carried into the reactor 1 by the feed gas which enters through inlet 2.
  • the catalyst forces the catalyst already in catalyst bed 4 upward in the reactor so that the top of catalyst bed 4 effectively remains at a level adjacent catalyst outlet 9. Since the catalyst is withdrawn from the reactor at basically the same rate as catalyst is being added, the depth of catalyst bed 4 remains substantially constant .
  • the hydrocarbon chain formed on the catalyst will be substantially at its maximum length when the catalyst particles reach the top of catalyst bed 4. Therefore, by timing the arrival of the catalyst particles at outlet 9 to coincide with the desired maximum growth of the hydrocarbon chain absorbed thereon, the length of the chain on the catalyst particles exiting from reactor 1 will always be substantially equal to or less than the length of the chain of the hydrocarbon product which is desired to be formed during the process. This allows the majority, if not substantially all, of the hydrocarbon product being formed during the operation to be that which is desired.
  • the catalyst particles are withdrawn through outlet 9 and supplied to column 15 where they are treated to "regenerate” the catalyst particles by removing the hydrocarbons which have been adsorbed thereon. This can be done by passing a regenerating fluid or sweep gas (e.g. steam, feed gas) into the column 15 through pipe 20.
  • the sweep gas passes over the catalyst particles to desorb the hydrocarbons which, in turn, are then carried by the sweep gas out of the top of column 15 through outlet 16.
  • Any fines or particles of catalyst which are carried out of column 15 in the sweep gas/desorbed hydrocarbon stream preferably flows through hydrocyclone 17 or the like from which the separated catalyst is returned to column 15 though line 19 and passes the gas/hydrocarbons onto storage or other use through line 18.
  • the hydrocarbons desorbed from the catalyst in column 15 will have basically the same chain length as the desired hydrocarbon product so that the stream in line 18 can be processed and used accordingly.
  • the "regenerated" catalyst is removed from the bottom of column 15 and is passed through valve 21 to storage hopper 22 from which it is then fed through valve 23 back into feed gas inlet line 2 to again be used in the process.
  • the actual retention time which each catalyst particle will remain in reactor 1 will obviously depend on the particular catalyst being used, the design of the reactor, the operating conditions within the reactor, the hydrocarbon product to be formed, etc., all of which can be determined experimentally once all of the process parameters and the configuration of the reactor are known.
  • FIGURE 3 illustrates a slightly different, circulating fluidized-bed, chain-limiting reactor system S a which can be used in carrying out the present invention.
  • System S a is similar to system S of FIGURE 1 except the catalyst is continuously circulated through reactor vessel la at a rate whereby the length of the hydrocarbon chain on the catalyst reaches it maximum growth as the catalyst exits reactor la through outlet conduct 10a.
  • Reactor vessel la has a heat exchanger 5a therein to control the temperature of the reaction as described above.
  • the feed gas (e.g. syngas) flows through inlet 2a and through the catalyst bed 4a within reactor la. Further, the feed gas picks up "regenerated” catalyst from line 24a and carries it into reactor la where the catalyst forces the existing catalyst in bed 4a upward whereby the catalyst at the top of the bed is carried through conduit 10a along with the desired product. Again, the catalyst is replaced at the bottom of reactor la at substantially the same rate as that at which the catalyst at the top of reactor la is being removed.
  • the "residence time" which the catalyst remains active in reactor la is timed so that the hydrocarbon chain on the catalyst will substantially reach its maximum length (i.e. length of desired product) as it exits from reactor la.
  • the produced hydrocarbon gas (i.e. converted feed gas) carries the "saturated" catalyst through conduit 10a and into column 15a.
  • the produced hydrocarbon gas e.g. vaporized gasoline
  • the catalyst separate or disengage within the wide upper section of column 15a.
  • the hydrocarbon product flows through product outlet 16a which includes hydrocyclones 17a or the like which separate any fines or particles of catalyst from the hydrocarbon product and return them back into column 15a.
  • a "regenerating fluid” e.g. sweep gas such as steam
  • the sweep gas and the desorbed hydrocarbons which are basically the same as the desired hydrocarbon product, are removed through product outlet 16a for further processing.
  • the "regenerated" catalyst falls to the bottom of column 15a where it is returned to inlet 2a through control valve 23a for reuse in the process.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention se rapporte à une synthèse de Fischer-Tropsch destinée à la conversion d'un gaz de synthèse en un hydrocarbure, qui est telle que l'hydrocarbure produit possède une longueur de chaîne désirée, et soit par exemple un carburant pour moteur diesel. Selon le procédé de l'invention, on fait passer le gaz de synthèse à travers un lit fluidisé de catalyseur dans un réacteur limitant la longueur des chaînes jusqu'à ce que la longueur de chaîne de l'hydrocarbure absorbé sur ledit catalyseur atteigne une valeur sensiblement égale à celle de la longueur de chaîne de l'hydrocarbure désiré. On retire ensuite du réacteur la fraction 'saturée' du catalyseur que l'on remplace par du catalyseur neuf. On régénère le catalyseur 'saturé' et on le réutilise dans le réacteur.
PCT/US1997/019722 1996-11-05 1997-10-30 Procede de conversion de gaz utilisant un reacteur limitant la formation de composes a chaines longues WO1998019979A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU52418/98A AU5241898A (en) 1996-11-05 1997-10-30 Gas conversion process using a chain-limiting reactor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US74403296A 1996-11-05 1996-11-05
US08/744,032 1996-11-05

Publications (1)

Publication Number Publication Date
WO1998019979A1 true WO1998019979A1 (fr) 1998-05-14

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PCT/US1997/019722 WO1998019979A1 (fr) 1996-11-05 1997-10-30 Procede de conversion de gaz utilisant un reacteur limitant la formation de composes a chaines longues

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AU (1) AU5241898A (fr)
PE (1) PE38799A1 (fr)
WO (1) WO1998019979A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE414019A (fr) *
FR922493A (fr) * 1945-04-13 1947-06-10 Standard Oil Dev Co Procédé de fabrication d'essence

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE414019A (fr) *
FR922493A (fr) * 1945-04-13 1947-06-10 Standard Oil Dev Co Procédé de fabrication d'essence

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AU5241898A (en) 1998-05-29
PE38799A1 (es) 1999-04-10

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