EP0979258B1 - Slurrykohlenwasserstoffsyntheseverfahren miet verlängerter lebensdauer - Google Patents

Slurrykohlenwasserstoffsyntheseverfahren miet verlängerter lebensdauer Download PDF

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Publication number
EP0979258B1
EP0979258B1 EP98920021A EP98920021A EP0979258B1 EP 0979258 B1 EP0979258 B1 EP 0979258B1 EP 98920021 A EP98920021 A EP 98920021A EP 98920021 A EP98920021 A EP 98920021A EP 0979258 B1 EP0979258 B1 EP 0979258B1
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EP
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Prior art keywords
catalyst
slurry
process according
hcn
hydrocarbons
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EP98920021A
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English (en)
French (fr)
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EP0979258A1 (de
Inventor
Stephen C. Leviness
Charles J. Mart
William C. Behrmann
Stephen J. Hsia
Daniel R. Neskora
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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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

Definitions

  • the invention relates to a hydrocarbon synthesis process with increased catalyst life. More particularly, the invention relates to a slurry catalytic hydrocarbon synthesis process employing a supported cobalt metal catalyst in which catalyst half life is increased by using a syngas feed containing less than fifty parts per billion of nitrogenous, catalyst deactivating species.
  • HCS Slurry hydrocarbon synthesis
  • a synthesis gas comprising a mixture of H 2 and CO is bubbled up as a third phase through a slurry in a reactor in which the slurry liquid comprises hydrocarbon products of the synthesis reaction and the dispersed, suspended solids comprise a suitable Fischer-Tropsch type hydrocarbon synthesis catalyst.
  • Reactors which contain such a three phase slurry are sometimes referred to as "bubble columns", as is disclosed in U.S. Patent 5,348,982.
  • the mixing conditions in the slurry will typically be somewhere between the two theoretical conditions of plug flow and back mixed. It is also known that Fischer-Tropsch type catalysts useful for forming hydrocarbons from a syngas are rapidly, but reversibly deactivated by certain nitrogenous species in the syngas feed, particularly HCN and NH 3 .
  • Syngas made from hydrocarbon feedstocks which contain nitrogen (i.e., natural gas) or nitrogen containing compounds (i.e., resids, coal, shale, coke, tar sands, etc.) invariably contains HCN and NH 3 which contaminate the reactive slurry and deactivate the catalyst.
  • Certain oxygenates and carbonaceous compounds which are formed in the slurry as byproducts of the HCS reaction are also believed to cause rapid deactivation.
  • Deactivation of such catalysts by HCN and NH 3 may be reversed and catalytic activity restored (rejuvenated) by contacting the deactivated catalyst with hydrogen or a hydrogen containing gas (rejuvenating gas).
  • Deactivation of such catalysts by these species is reversible and catalytic activity is restored (the catalyst rejuvenated) by contacting the deactivated catalyst with hydrogen either continuously or intermittently as is disclosed, for example, in U.S. Patents 5,260,239; 5,268,344 and 5,283,216.
  • the present invention relates to a slurry hydrocarbon synthesis (HCS) process employing a supported cobalt metal catalyst in which the short term catalyst half life is at least 10 days, preferably at least 30 and more preferably at least 40 or more days.
  • short term half life is meant that the catalytic activity caused by reversible deactivation of the catalyst is 50% that of fresh catalyst and that this loss is substantially restored (the catalyst rejuvenated) by contacting the deactivated catalyst with a rejuvenating gas comprising H 2 .
  • Catalyst activity is defined in terms of the CO conversion to hydrocarbons.
  • the catalyst half life is realized when the conversion drops to 40%, as a result of contact with the reversibly deactivating nitrogenous species in the synthesis gas (syngas) feed.
  • reversibly deactivating nitrogenous species is meant HCN, NH 3 and mixture thereof.
  • the catalyst will have a long term half life of at least 100 days and preferably at least 200 days. It has been found that there is also an unrejuvenable catalyst activity loss which occurs over time, which cannot be restored by contacting the catalyst with H 2 , but which can be restored by regeneration.
  • the catalyst has to be separated from the slurry and regenerated by processes that include oxidation or burning, rereduction of the catalytic metal(s) and, optionally, passivation in CO and/or syngas.
  • long term loss of catalyst activity in the context of the invention is regenerable, but not rejuvenable with H 2 .
  • regenerable activity loss is different from irreversible catalyst activity loss due to, for example, sulfur poisoning, which requires catalyst replacement.
  • a slurry HCS catalyst useful in the practice of the invention comprises a catalytically active cobalt component dispersed and supported on a particulate inorganic refractory oxide carrier or support, and preferably as a thin catalytically active surface layer, ranging in thickness from about 5-200 microns.
  • the catalyst have a productivity of at least 150 hr -1 at 200°C, preferably at least 500 hr -1 and more preferably at least 1000 hr -1 .
  • productivity is meant the standard volume of CO converted per volume of catalyst per hour.
  • the catalyst employed in the process of the invention will have a methane selectivity of less than 10 mole % and preferably less than 5 mole %. This means that less than 10% of the CO converted is converted to methane.
  • the catalyst comprises catalytically effective amounts of Co and one or more of Re, Ru, Fe, Ni, Th, Zr, Hf, U, Mg and La on a suitable inorganic support material, and preferably one which comprises one or more refractory metal oxides.
  • Preferred supports for Co containing catalysts comprise titania and titania-silica composites, particularly when employing a slurry HCS process in which higher molecular weight, primarily paraffinic liquid hydrocarbon products are desired.
  • Useful catalysts and their preparation are known and illustrative, but nonlimiting examples may be found, for example, in U.S. Patents 4,568,663; 4,663,305; 4,542,122; 4,621,072 and 5,545,674, with those disclosed in U.S. 5,545,674 being particularly preferred.
  • An HCS slurry process of the invention comprises reacting a syngas which contains HCN, HN 3 or mixture thereof in the presence of a solid, particulate HCS catalyst in a slurry which comprises the catalyst and gas bubbles in a hydrocarbon slurry liquid, at reaction conditions effective to produce hydrocarbons from the syngas, wherein the total amount of HCN, HN 3 or mixture thereof in the syngas is less than 50 vppb, preferably less than 20 vppb and more preferably less that 10 vppb to achieve a short term catalyst half life greater than 10 days, preferably greater than 30 days and more preferably greater than 40 days, and with a long term catalyst half life greater than 100 and preferably greater than 200 days.
  • the process of the invention has been demonstrated with a slurry HCS process in which the syngas is bubbled up through a three phase HCS slurry comprising the particulate catalyst and gas bubbles in a hydrocarbon slurry liquid, and in which the catalyst comprised a catalytically active cobalt component dispersed and supported on a particulate inorganic refractory oxide carrier or support, as a thin catalytically active surface layer which met the above requirements for productivity and methane make.
  • This catalyst was of the type disclosed and claimed in the '674 patent referred to above.
  • a number of methods have been found to achieve the low concentration of the HCN to NH 3 in the syngas useful in the practice of the invention. These include catalytic hydrolysis of the HCN to NH 3 , followed by scrubbing with water to dissolve out the NH 3 and, optionally, the use of guard beds containing one or more solid adsorbents, preferably acidic, to adsorb any HCN and NH 3 that may break through. This process is disclosed in copending US application Serial No. 08/797,368 referred to above.
  • Another method comprises cryogenic separation of nitrogen from natural gas used as a syngas feed, so that not enough nitrogen is present in the natural gas to produce the catalyst deactivating species in the syngas generating unit.
  • solid adsorbent beds will be placed between the syngas generation and the HCS reactor(s), in the event of a nitrogen break through upstream of the syngas generating unit and result in increasing the concentration of the catalyst deactivating species in the syngas.
  • the invention comprises reacting a synthesis gas comprising a mixture of H 2 and CO and containing HCN, NH 3 or mixture thereof, in the presence of a hydrocarbon synthesis catalyst in a slurry comprising said catalyst and gas bubbles in a hydrocarbon slurry liquid, under reaction conditions effective to form hydrocarbons from said syngas, said catalyst comprising a catalytically active cobalt component dispersed and supported on a particulate inorganic refractory oxide carrier or support, as a thin catalytically active surface layer, said catalyst having a productivity of at least 150 hr -1 and less than 5 mole % methane make from said synthesis gas, and wherein the amount of said HCN, NH 3 or mixture thereof present in said gas is less than 50 vppb so as to achieve a short term catalyst half life of at least 10 days.
  • the hydrocarbon slurry liquid comprises hydrocarbon products of the HCS reaction which are liquid at the reaction conditions and a portion is continuously or intermittently withdrawn from the slurry HCS reactor as long as the hydrocarbons are being produced.
  • the hydrocarbon liquid withdrawn from the reactor comprises C 5+ , primarily paraffinic hydrocarbons and is typically upgraded into more valuable products by one or more conversion operations, or sold neat.
  • the catalyst loses activity due to the presence of the HCN, NH 3 or mixture thereof in the syngas and must be either continuously or intermittently rejuvenated by bubbling H 2 or an H 2 containing gas up through the slurry in which it contacts the catalyst and at least partially, and preferably substantially completely, restores the catalytic activity, as is disclosed in the prior art referred to above and more preferably after all or at least a portion of the CO has been removed from the slurry.
  • a syngas comprising a mixture of H 2 and CO is bubbled up into a reactive slurry in which it is catalytically converted into hydrocarbons and preferably liquid hydrocarbons.
  • the mole ratio of the hydrogen to the carbon monoxide may broadly range from about 0.5 to 4, but which is more typically within the range of from about 0.7 to 2.75 and preferably from about 0.7 to 2.5.
  • the stoichiometric mole ratio for a Fischer-Tropsch HCS reaction is 2.0, but there are many reasons for using other than a stoichiometric ratio as those skilled in the art know and a discussion of which is beyond the scope of the present invention.
  • a slurry HCS process the mole ratio of the H 2 to CO is typically about 2.1/1.
  • Slurry HCS process conditions vary somewhat depending on the catalyst and desired products. Typical conditions effective to form hydrocarbons comprising mostly C 5+ paraffins, and preferably C 10+ paraffins (e.g., C 5+ -C 200 ), in a slurry HCS process employing a catalyst comprising a supported cobalt component include, for example, temperatures, pressures and hourly gas space velocities in the range of from about 320-600°F, 80-600 psi and 100-40,000 V/hr/V, expressed as standard volumes of the gaseous CO and H 2 mixture (0°C, 1 atm) per hour per volume of catalyst, respectively.
  • Slurry catalyst rejuvenation conditions of temperature and pressure are similar to those for hydrocarbon synthesis and are disclosed in the prior art.
  • the syngas may be formed by various means, including contacting a hot carbonaceous material such as coke or coal, with steam, or from a feed comprising methane.
  • a feed comprising methane is preferred for convenience, cleanliness and because it does not leave large quantities of ash to be handled and disposed of.
  • the methane containing gas feed is obtained from natural gas or by burning coal, tar, liquid hydrocarbons and the like and is fed into a syngas generator.
  • the production of syngas from methane by either partial oxidation, steam reforming or a combination thereof is well known as is disclosed, for example, in U.S. Patent 4,888,131.
  • FBSG fluid bed syngas generating unit
  • nitrogen or nitrogen containing compounds are present in the methane containing gas fed into the syngas generator, some of which are converted into NH 3 and HCN during the syngas formation.
  • a Fischer-Tropsch HCS catalyst particularly those comprising Co as the catalytic metal.
  • deactivation by these species is reversible and the catalyst can be rejuvenated by contacting it with hydrogen.
  • catalyst rejuvenation This restoration of the catalytic activity of a reversibly deactivated catalyst is referred to as catalyst rejuvenation and is disclosed, for example, in the 5,260,239; 5,268,344 and 5,283,216 patents referred to above. It has also been found that both the short term and long term catalyst half life of a Co containing slurry HCS catalyst are unacceptably short unless the combined amount of the HCN and NH 3 present in the syngas being fed into an HCS reactor is less than 50 vppb, preferably less than 20 vppb and more preferably less than 10 vppb, so that the short term or H 2 rejuvenable catalyst half life will be at least 10 days, preferably at least 30 days and more preferably at least 40 days and for the long term catalyst half life to be at least 100 days and preferably at least 200 days.
  • the reactor in cyclic or batchwise rejuvenation, the reactor is taken off-line for one-quarter of each day to maintain the activity level at no less than about 90%, during which time the catalyst in the reactor is rejuvenated with hydrogen.
  • the reactor is off-line more than one-quarter of each day, due to the time it takes to purge out the syngas, pass in the hydrogen or hydrogen containing catalyst rejuvenating gas and then restart the HCS reaction. This results in a continuous average 25% loss of hydrocarbon production from the reactor, even with rejuvenation.
  • the conversion level drops resulting in a decrease in liquid hydrocarbon make and a small increase in methane make.
  • conversion can be held relatively constant despite the catalyst deactivation, by increasing the reactor temperature, but this results in a relatively large increase in methane make and consequent decrease in liquid product make.
  • the catalyst half life is 20 days. This means that about every fourth day the catalyst has to be rejuvenated, using the same amount of time and hydrogenation for the rejuvenation as for the case above, yielding an average production loss of only about 6%. At about 40-50 vppb, it is about 15%.
  • the catalyst half life is about 40 days and the catalyst has to be rejuvenated for one-quarter of a day only every 8 days, yielding a productivity loss of only about 3%.
  • the catalyst half life is about 30 days when the combined amounts of HCN and NH 3 is about 13-17 vppb.
  • the catalyst in the slurry can be either continuously rejuvenated with the reactor remaining on-line using the methods disclosed in U.S. Patents 5,260,239 and 5,268,344. Nevertheless, the case of a catalyst half life of only 4 days will still consume five times more hydrogen rejuvenation gas than if the half life were 20 days, and ten times the amount required for a 40 day half life.
  • HCN is not soluble enough in water to be able to remove it down to the low levels of less than 50 vppb, preferably less than 20 vppb and more preferably less than 10 vppb required to achieve reasonable levels of catalyst half life.
  • Chemical scrubbing processes are not selective enough to remove the HCN down to these levels.
  • Some prior art catalytic conversion processes have employed relatively low activity catalysts which require excessive catalyst volume and/or high processing temperatures.
  • Other processes have employed sulfided catalysts which will leak out sulfur and irreversibly deactivate an HCS catalyst downstream.
  • liquid and gaseous hydrocarbon products are formed by contacting a syngas comprising a mixture of H 2 and CO with a Fischer-Tropsch type of HCS catalyst, under shifting or non-shifting conditions and preferably under non-shifting conditions in which little or no water gas shift reaction occurs, particularly when the catalytic metal comprises Co, Ru or mixture thereof.
  • Suitable Fischer-Tropsch reaction types of catalyst comprise, for example, one or more Group VIII catalytic metals such as Fe, Ni, Co, Ru and Re.
  • the catalytic metal comprises a catalytically active cobalt component dispersed and supported on a particulate inorganic refractory oxide carrier or support, with the total thickness of the catalytically active layer in the range of from about 5-200 microns.
  • the metal will be impregnated as a thin surface layer no thicker than this range.
  • the catalytic metal may be either uniformly impregnated throughout the particles or deposited as a thin(ner) surface layer.
  • Paraffinic, C 5+ hydrocarbon products are preferred and preferably more than 50% of the C 5+ hydrocarbons will be paraffins.
  • the catalyst will have a productivity in excess of 150 hr -1 at 200°C and exhibit a methane selectivity of less than 10%.
  • the catalyst comprises catalytically effective amounts of Co and one or more of Re, Ru, Fe, Ni, Th, Zr, Hf, U, Mg and La on a suitable inorganic support material, and preferably one which comprises one or more refractory metal oxides.
  • Preferred supports for Co containing catalysts comprise titania and titania-silica composites, particularly when employing a slurry HCS process in which higher molecular weight, primarily C 5+ paraffinic liquid hydrocarbon products are desired.
  • the hydrocarbons produced by an HCS process according to the invention are typically upgraded to more valuable products, by subjecting all or a portion of the C 5+ hydrocarbons to fractionation and/or conversion.
  • conversion is meant one or more operations in which the molecular structure of at least a portion of the hydrocarbon is changed and includes both noncatalytic processing (e.g., steam cracking), and catalytic processing (e.g., catalytic cracking) in which a fraction is contacted with a suitable catalyst.
  • hydroconversion processes are typically referred to as hydroconversion and include, for example, hydroisomerization, hydrocracking, hydrodewaxing, hydrorefining and the more severe hydrorefining referred to as hydrotreating, all conducted at conditions well known in the literature for hydroconversion of hydrocarbon feeds, including hydrocarbon feeds rich in paraffins.
  • More valuable products formed by conversion include one or more of a synthetic crude oil, liquid fuel, olefins, solvents, lubricating, industrial or medicinal oil, waxy hydrocarbons, nitrogen and oxygen containing compounds, and the like.
  • Liquid fuel includes one or more of motor gasoline, diesel fuel, jet fuel, and kerosene
  • lubricating oil includes, for example, automotive, jet, turbine and metal working oils.
  • Industrial oil includes well drilling fluids, agricultural oils, heat transfer fluids and the like.

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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)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (10)

  1. Suspensions-Kohlenwasserstoffsyntheseverfahren zur Herstellung flüssiger Kohlenwasserstoffe aus einer H2 und CO umfassenden Synthesegasmischung, die HCN, NH3 oder Mischungen davon enthält, bei dem das Gas in Gegenwart eines Kohlenwasserstoffsynthesekatalysators in einer Suspension, die den Katalysator und Gasblasen in einer Kohlenwasserstoffsuspensionsflüssigkeit umfasst, unter Reaktionsbedingungen umgesetzt wird, die geeignet sind, Kohlenwasserstoffe aus dem Synthesegas zu bilden, von denen unter den Reaktionsbedingungen zumindest ein Teil flüssig ist, wobei die Suspensionsflüssigkeit die flüssigen Kohlenwasserstoffe umfasst, der Katalysator eine Produktivität von wenigstens 150 h-1 aufweist und eine katalytisch aktive Kobaltkomponente auf einem teilchenförmigen, anorganischen, feuerfesten Oxidträger umfasst und wobei die Gesamtmenge an HCN, NH3 und Mischungen davon, die in dem Synthesegas vorhanden sind, geringer als 50 Vol.ppb ist.
  2. Verfahren nach Anspruch 1, bei dem die durch die Reaktion hergestellte Kohlenwasserstoffflüssigkeit C5+ Kohlenwasserstoffe umfasst.
  3. Verfahren nach Anspruch 2, bei dem die C5+ Kohlenwasserstoffe hauptsächlich Paraffine umfassen.
  4. Verfahren nach Anspruch 2 oder Anspruch 3, bei dem zumindest ein Teil der C5+ Kohlenwasserstoffe durch eine oder mehrere Umwandlungsschritte zu wertvolleren Produkten veredelt wird.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem die katalytisch aktive Kobaltkomponente des Katalysators auf einem anorganischen feuerfesten Oxidträger dispergiert und geträgert ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem die katalytisch aktive Kobaltkomponente auf dem Träger als Schicht mit einer Dicke von 2 bis 200µm vorliegt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem der Katalysator eine Methanselektivität von weniger als 5 Mol.% hat.
  8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem die Gesamtmenge an HCN, NH3 oder Mischungen davon, die in Synthesegas vorliegen, weniger als 20 Vol.ppb beträgt.
  9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem die Gesamtmenge an HCN, NH3 oder Mischungen davon, die in dem Gas vorliegen, geringer als 10 Vol.ppb ist, um eine kurzfristige Katalysatorhalbwertszeit von wenigstens 40 Tagen zu erreichen.
  10. Verfahren nach einem der Ansprüche 1 bis 9, bei dem der Katalysator eine langfristige Halbwertszeit von wenigstens 100 Tagen und eine kurzfristige Halbwertszeit von wenigstens 30 Tagen besitzt.
EP98920021A 1997-05-02 1998-04-29 Slurrykohlenwasserstoffsyntheseverfahren miet verlängerter lebensdauer Expired - Lifetime EP0979258B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US85035597A 1997-05-02 1997-05-02
US850355 1997-05-02
PCT/US1998/008687 WO1998050487A1 (en) 1997-05-02 1998-04-29 Slurry hydrocarbon synthesis process with increased catalyst life

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EP0979258A1 EP0979258A1 (de) 2000-02-16
EP0979258B1 true EP0979258B1 (de) 2003-01-08

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EP (1) EP0979258B1 (de)
JP (1) JP4126100B2 (de)
AU (1) AU731227B2 (de)
BR (1) BR9809786A (de)
CA (1) CA2286347C (de)
DE (1) DE69810607T2 (de)
NO (1) NO995331L (de)
WO (1) WO1998050487A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6900151B2 (en) * 2001-11-13 2005-05-31 Exxonmobil Research And Engineering Company In situ catalyst regeneration/activation process

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2231581A (en) * 1989-05-15 1990-11-21 Shell Int Research Process for the preparation of hydrocarbons
US5348982A (en) * 1990-04-04 1994-09-20 Exxon Research & Engineering Co. Slurry bubble column (C-2391)
DE69607423T2 (de) * 1995-08-08 2000-08-03 Exxon Research And Engineering Co., Florham Park Verfahren zur Beseitigung von Cyanwasserstoff aus Synthesegas
DE69713622T2 (de) * 1996-04-23 2002-10-31 Exxonmobil Research And Engineering Co., Annandale Verfahren zur entfernung von cyanwasserstoff aus synthesegas

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Publication number Publication date
EP0979258A1 (de) 2000-02-16
JP4126100B2 (ja) 2008-07-30
CA2286347C (en) 2005-04-19
AU731227B2 (en) 2001-03-29
DE69810607D1 (de) 2003-02-13
NO995331L (no) 1999-12-29
AU7267998A (en) 1998-11-27
NO995331D0 (no) 1999-11-01
DE69810607T2 (de) 2003-08-07
BR9809786A (pt) 2000-06-20
WO1998050487A1 (en) 1998-11-12
JP2002512650A (ja) 2002-04-23
CA2286347A1 (en) 1998-11-12

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