WO1998050487A1 - Procede de synthese de boues d'hydrocarbures, a duree de vie prolongee du catalyseur - Google Patents

Procede de synthese de boues d'hydrocarbures, a duree de vie prolongee du catalyseur Download PDF

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Publication number
WO1998050487A1
WO1998050487A1 PCT/US1998/008687 US9808687W WO9850487A1 WO 1998050487 A1 WO1998050487 A1 WO 1998050487A1 US 9808687 W US9808687 W US 9808687W WO 9850487 A1 WO9850487 A1 WO 9850487A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
slurry
process according
hcn
days
Prior art date
Application number
PCT/US1998/008687
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English (en)
Inventor
Stephen C. Leviness
Charles J. Mart
William C. Behrmann
Stephen J. Hsia
Daniel R. Neskora
Original Assignee
Exxon Research And Engineering Company
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 Exxon Research And Engineering Company filed Critical Exxon Research And Engineering Company
Priority to JP54819598A priority Critical patent/JP4126100B2/ja
Priority to AU72679/98A priority patent/AU731227B2/en
Priority to DE69810607T priority patent/DE69810607T2/de
Priority to EP98920021A priority patent/EP0979258B1/fr
Priority to BR9809786-5A priority patent/BR9809786A/pt
Priority to CA002286347A priority patent/CA2286347C/fr
Publication of WO1998050487A1 publication Critical patent/WO1998050487A1/fr
Priority to NO995331A priority patent/NO995331L/no

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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 by-products 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 slu ⁇ y 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 paraff ⁇ nic 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 earner 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 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 stoichiomerric mole ratio for a Fischer-Tropsch HCS reaction is 2.0, but there are many reasons for using other than a stoichiomerric ratio as those skilled in the ait 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 ⁇ o+ paraffins (e.g., C 5+ -C 20 o), 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 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 offline 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 hydrogena- tion 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+ hydrocaibons 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 hydrocaibons 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.
  • conver- sion 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)

Abstract

L'invention concerne un procédé de synthèse catalytique de boues d'hydrocarbures selon lequel on utilise un catalyseur comprenant un constituant cobalt sur support. On parvient à une demi-vie supérieure à dix jours du catalyseur à court terme, à l'aide d'une charge de gaz de synthèse qui contient moins de 55 parties par milliard d'une quantité totale combinée de HCN et de NH3.
PCT/US1998/008687 1997-05-02 1998-04-29 Procede de synthese de boues d'hydrocarbures, a duree de vie prolongee du catalyseur WO1998050487A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP54819598A JP4126100B2 (ja) 1997-05-02 1998-04-29 触媒寿命が延長されたスラリー炭化水素合成方法
AU72679/98A AU731227B2 (en) 1997-05-02 1998-04-29 Slurry hydrocarbon synthesis process with increased catalyst life
DE69810607T DE69810607T2 (de) 1997-05-02 1998-04-29 Slurrykohlenwasserstoffsyntheseverfahren miet verlängerter lebensdauer
EP98920021A EP0979258B1 (fr) 1997-05-02 1998-04-29 Procede de synthese d'hydrocarbures, a duree de vie prolongee du catalyseur
BR9809786-5A BR9809786A (pt) 1997-05-02 1998-04-29 Processo de pasta fluida de sìntese de hidrocarboneto
CA002286347A CA2286347C (fr) 1997-05-02 1998-04-29 Procede de synthese de boues d'hydrocarbures, a duree de vie prolongee du catalyseur
NO995331A NO995331L (no) 1997-05-02 1999-11-01 Oppslemmings-hydrokarbonsyntese prosess med forlenget katalysatorlevetid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US85035597A 1997-05-02 1997-05-02
US08/850,355 1997-05-02

Publications (1)

Publication Number Publication Date
WO1998050487A1 true WO1998050487A1 (fr) 1998-11-12

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PCT/US1998/008687 WO1998050487A1 (fr) 1997-05-02 1998-04-29 Procede de synthese de boues d'hydrocarbures, a duree de vie prolongee du catalyseur

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010174248A (ja) * 2001-11-13 2010-08-12 Exxonmobil Research & Engineering Co 原位置触媒再生／活性化法および炭化水素合成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5068254A (en) * 1989-05-15 1991-11-26 Shell Oil Company Process for the preparation of hydrocarbons
EP0757969A1 (fr) * 1995-08-08 1997-02-12 Exxon Research And Engineering Company Procédé d'élimination d'acide cyanhydrique de gaz de synthèse
WO1997039979A1 (fr) * 1996-04-23 1997-10-30 Exxon Research And Engineering Company Procede d'extraction de cyanure d'hydrogene d'un gaz de synthese

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5348982A (en) * 1990-04-04 1994-09-20 Exxon Research & Engineering Co. Slurry bubble column (C-2391)

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5068254A (en) * 1989-05-15 1991-11-26 Shell Oil Company Process for the preparation of hydrocarbons
EP0757969A1 (fr) * 1995-08-08 1997-02-12 Exxon Research And Engineering Company Procédé d'élimination d'acide cyanhydrique de gaz de synthèse
WO1997039979A1 (fr) * 1996-04-23 1997-10-30 Exxon Research And Engineering Company Procede d'extraction de cyanure d'hydrogene d'un gaz de synthese

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010174248A (ja) * 2001-11-13 2010-08-12 Exxonmobil Research & Engineering Co 原位置触媒再生／活性化法および炭化水素合成方法

Also Published As

Publication number Publication date
NO995331D0 (no) 1999-11-01
DE69810607D1 (de) 2003-02-13
DE69810607T2 (de) 2003-08-07
JP4126100B2 (ja) 2008-07-30
EP0979258A1 (fr) 2000-02-16
CA2286347A1 (fr) 1998-11-12
NO995331L (no) 1999-12-29
BR9809786A (pt) 2000-06-20
JP2002512650A (ja) 2002-04-23
EP0979258B1 (fr) 2003-01-08
CA2286347C (fr) 2005-04-19
AU7267998A (en) 1998-11-27
AU731227B2 (en) 2001-03-29

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