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WO2016091695A1 - Processus de production d'un catalyseur de synthèse fischer-tropsch à activation réductrice, et processus de production d'hydrocarbures utilisant celui-ci - Google Patents

Processus de production d'un catalyseur de synthèse fischer-tropsch à activation réductrice, et processus de production d'hydrocarbures utilisant celui-ci Download PDF

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Publication number
WO2016091695A1
WO2016091695A1 PCT/EP2015/078419 EP2015078419W WO2016091695A1 WO 2016091695 A1 WO2016091695 A1 WO 2016091695A1 EP 2015078419 W EP2015078419 W EP 2015078419W WO 2016091695 A1 WO2016091695 A1 WO 2016091695A1
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carbon monoxide
hydrogen
cobalt
reduction step
process according
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Ewen Ferguson
Manuel OJEDA PINEDA
Alexander Paterson
Matthew James WELLS
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BP PLC
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BP PLC
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/18—Treating with free oxygen-containing gas with subsequent reactive gas treating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4031—Start up or shut down operations

Definitions

  • This invention relates to a process for activating a Fischer-Tropsch synthesis catalyst.
  • the invention relates to a process comprising a carbon monoxide reduction step followed thereafter by a separate low temperature hydrogen reduction step for producing an activated Fischer-Tropsch synthesis catalyst which exhibits improved selectivity for C 5+ hydrocarbons in subsequent Fischer-Tropsch reactions.
  • metals for example cobalt, nickel, iron, molybdenum, tungsten, thorium, ruthenium, rhenium and platinum are known to be catalytically active, either alone or in combination, in the conversion of synthesis gas into hydrocarbons and oxygenated derivatives thereof.
  • cobalt, nickel and iron have been studied most extensively.
  • the metals are used in combination with a support material, of which the most common are alumina, silica and carbon.
  • a solid support is typically impregnated with a cobalt-containing compound, which may for instance be an organometallic or inorganic compound (e.g. Co(N0 3 ) 2 .6H 2 0), by contacting with a solution of the compound.
  • a cobalt-containing compound which may for instance be an organometallic or inorganic compound (e.g. Co(N0 3 ) 2 .6H 2 0), by contacting with a solution of the compound.
  • the particular form of cobalt-containing compound is generally selected for its ability to form a cobalt oxide (for instance, CoO, Co 2 0 3 or Co 3 0 4 ) following a subsequent calcination/oxidation step.
  • a reduction step is necessary in order to form the pure cobalt metal as the active catalytic species.
  • the reduction step is also commonly referred to as an activation step.
  • WO 03/035257 and WO 06/075216 disclose a two-step reduction of a Fischer-Tropsch catalyst precursor with hydrogen, wherein the final reduction stage is conducted with pure hydrogen gas at a temperature of from 300 °C to 600 °C.
  • US 4,626,552 also proposes a pretreatment of the catalyst with hydrogen gas mixed with a minor proportion of carbon monoxide.
  • DE 977498 describes the pretreatment of a catalyst comprising a Group VIII metal, preferably iron, with a carbon monoxide containing gas.
  • US 8,557,879 describes a process for producing an activated Fischer-Tropsch synthesis catalyst having improved initial catalyst activity comprising a hydrogen reduction step at a temperature of from 300 °C to 600 °C, preferably followed by a separate carbon monoxide reduction step at a temperature of from 200 °C to 400 °C.
  • US 5,585,316 describes a method for the pretreatment of a cobalt-containing catalyst with a gas containing carbon monoxide and less than 30 vol.% hydrogen, preferably no hydrogen. This method is reported to afford improvements in selectivity for C 5+ hydrocarbons in subsequent Fischer-Tropsch reactions over conventional pretreatment processes employing a hydrogen reduction at elevated temperatures of, for instance, 320 °C (Comparative Example 2).
  • a reductively activated cobalt-containing Fischer-Tropsch catalyst exhibiting improved selectivity for C 5+ hydrocarbons, as well as improved catalytic activity in at least some embodiments, in subsequent Fischer-Tropsch reactions may be prepared by a process comprising two distinct reduction steps.
  • the activation process comprises a first carbon monoxide reduction of a cobalt- containing Fischer-Tropsch catalyst precursor, followed by a separate hydrogen reduction step conducted at a temperature of from 200 °C to 280 °C.
  • the present invention thus provides a process for the production of a reductively activated cobalt-containing Fischer-Tropsch catalyst, said process comprising i) a carbon monoxide reduction step comprising contacting a cobalt-containing Fischer-Tropsch catalyst with a gaseous stream comprising carbon monoxide and less than 10 vol.% hydrogen based on the volume of carbon monoxide; followed by ii) a hydrogen reduction step comprising contacting the product of the carbon monoxide reduction step i) with a gaseous stream comprising hydrogen and less than 10 vol.% carbon monoxide based on the volume of hydrogen at a temperature of from 200 °C to 280 °C.
  • both the order of the reduction steps and the temperature of the hydrogen reduction reaction have been found to be key to the present invention.
  • a subsequent, separate hydrogen reduction step generally improves selectivity for C 5+ hydrocarbons in subsequent Fischer-Tropsch reactions, beyond that which is achievable by either a carbon monoxide reduction or hydrogen reduction alone.
  • the catalytic activity of the reductively activated cobalt-containing catalyst prepared in accordance with the process of the invention is also improved over those processes comprising either a carbon monoxide reduction or hydrogen reduction alone.
  • temperatures may refer to feed temperatures, applied temperatures and/or catalyst bed temperatures.
  • the carbon monoxide reduction step i) of the process of the present invention comprises contacting a cobalt-containing Fischer-Tropsch catalyst with a gaseous stream comprising carbon monoxide and less than 10 vol.% hydrogen based on the volume of carbon monoxide.
  • the gaseous stream comprising carbon monoxide used in step i) of the process of the invention may, in addition to carbon monoxide, comprise inert diluent gases such as argon, helium, nitrogen, hydrocarbons such as methane, and/or water vapour.
  • the upper limit of hydrogen which may be present in the carbon monoxide-containing gaseous stream as reported herein is relative only to the volume of carbon monoxide in the gaseous stream, and not relative to the combined volume of carbon monoxide and any inert diluents.
  • the carbon monoxide containing gaseous stream comprises from 5 to 50 vol.% of carbon monoxide with the balance comprising inert diluents, more preferably the carbon monoxide containing gaseous stream comprises from 15 to 35 vol.% of carbon monoxide, and the balance comprising inert diluents. Still more preferably, the carbon monoxide containing gaseous stream comprises from 20 to 30 vol.% carbon monoxide, and the balance comprising inert diluents. In other embodiments, the carbon monoxide containing gaseous stream comprises up to 80 vol.%, up to 90 vol.% or even up to 95 vol.% carbon monoxide.
  • the carbon monoxide-containing gaseous stream comprises less than 5 vol.%) hydrogen based on the volume of carbon monoxide, more preferably less than 2 vol.%, yet more preferably less than 1 vol.%>. Most preferably, the carbon monoxide- containing gaseous stream comprises substantially no hydrogen.
  • the temperature at which the carbon monoxide reduction is performed is from 100 °C to 500 °C, preferably 200 °C to 350 °C.
  • the temperature at which the carbon monoxide reduction is performed may be from 120 °C to 350 °C, from 150 °C to 280 °C, from 160 °C to 240 °C or from 170 °C to 200 °C.
  • the carbon monoxide reduction step may be carried out at any desired pressure, for instance from 10 to 5500 kPa, preferably from 20 to 3000 kPa, more preferably from 50 to 1000 kPa, and even more preferably from 100 to 800 kPa. More preferably, the carbon monoxide reduction step is performed at atmospheric pressure.
  • other pressures may be desirable for this reduction step, such as from 1 to 10 barg (0.1 to 1 MPa), 5 to 10 barg (0.5 to 1 MPa) or 6 to 8 barg (0.6 to 0.8 MPa).
  • Other examples may include at least 2 barg (0.2 MPa), at least 4 barg (0.4 MPa), at least 5 barg (0.5 MPa) or at least 6 barg (0.6 MPa).
  • the carbon monoxide-containing gas is suitably passed over the catalyst bed at a gas hourly space velocity (GHSV) in the range from 100 to 10000 h “1 (gas volumes converted to standard temperature and pressure), preferably from 250 to 5000 h “1 , such as from 250 to 3000 h “1 and more preferably from 250 to 2000 h "1 , for example 1000 h "1 .
  • GHSV gas hourly space velocity
  • the carbon monoxide reduction step is conducted over a period of at least 30 minutes, preferably over a period of from 1 to 24 hours, more preferably over a period of from 2 to 18 hours, most preferably over a period of from 3 to 12 hours.
  • the carbon monoxide reduction step in addition to leading to at least partial reduction of the oxidic cobalt of the catalyst precursor, is thought to lead to the formation of coke deposits on the catalyst, thus potentially blocking active sites thereby affecting catalyst selectivity and activity. However, this coking may be removed upon a subsequent treatment with hydrogen.
  • step ii) of the reductive activation process of the present invention the product of the carbon monoxide reduction step i) is subjected to a hydrogen reduction comprising contacting with a gaseous stream comprising hydrogen and less than 10 vol.% carbon monoxide based on the volume of hydrogen at a temperature of from 200 °C to 280 °C.
  • hydrogen referred to herein as a component of the hydrogen containing gaseous stream corresponds to molecular hydrogen (H 2 gas).
  • the gaseous stream comprising hydrogen used in step ii) of the process of the invention may, in addition to hydrogen, comprise inert diluent gases such as argon, helium, nitrogen and/or water vapour.
  • inert diluent gases such as argon, helium, nitrogen and/or water vapour.
  • the hydrogen containing gaseous stream comprises from 5 to 60 vol.% of hydrogen with the balance comprising inert diluents, more preferably the hydrogen containing gaseous stream comprises from 15 to 50 vol.% of hydrogen, and the balance comprising inert diluents. Still more preferably, the hydrogen containing gaseous stream comprises from 25 to 40 vol.% hydrogen, and the balance comprising inert diluents. In other embodiments, the hydrogen containing gaseous stream comprises up to 80 vol.%, up to 90 vol.% or even up to 95 vol.% hydrogen. In some embodiments, the hydrogen containing gaseous stream consists essentially of hydrogen in the absence of diluents.
  • the hydrogen-containing gaseous stream comprises less than 5 vol.% carbon monoxide based on the volume of hydrogen, more preferably less than 2 vol.%, yet more preferably less than 1 vol.%. Most preferably, the hydrogen-containing gaseous stream comprises substantially no carbon monoxide.
  • the hydrogen reduction step is carried out at a temperature of from 200 °C to 280 °C, preferably 220 °C to 270 °C, most preferably 240 °C to 260 °C, for example 250 °C.
  • the hydrogen reduction step may be carried out at any desired pressure, for instance from from 10 to 5500 kPa, preferably from 20 to 3000 kPa, more preferably from 50 to 1000 kPa, and even more preferably from 100 to 800 kPa. More preferably, the hydrogen reduction step is carried out at atmospheric pressure.
  • other pressures may be desirable for this reduction step, such as from 1 to 10 barg (0.1 to 1 MPa), 5 to 10 barg (0.5 to 1 MPa) or 6 to 8 barg (0.6 to 0.8 MPa).
  • Other examples may include at least 2 barg (0.2 MPa), at least 4 barg (0.4 MPa), at least 5 barg (0.5 MPa) or at least 6 barg (0.6 MPa).
  • These other pressures may be in addition to, or alternative to, the corresponding pressures for the carbon monoxide reduction step.
  • the hydrogen-containing gas is suitably passed over the catalyst bed at a gas hourly space velocity (GHSV) in the range from 100 to 10000 h “1 (gas volumes converted to standard temperature and pressure), preferably from 250 to 5000 h “1 , such as from 250 to 3000 h “1 and more preferably from 250 to 2000 h “1 , for example 1000 h "1 .
  • GHSV gas hourly space velocity
  • the hydrogen reduction step is conducted over a period of at least 30 minutes, preferably over a period of from 1 to 48 hours, more preferably over a period of from 6 to 36 hours, most preferably over a period of from 8 to 18 hours.
  • the two stage reduction may lead to the formation of an enhanced level of available active cobalt metal, or otherwise favourable distribution of available active cobalt metal over the catalyst surface, giving rise to the superior C 5+ hydrocarbon selectivity in subsequent Fischer- Tropsch reactions.
  • the level of reduction and/or distribution of active cobalt metal species is also believed to be dictated largely by the temperature of the subsequent hydrogen reduction step, which is from 200 °C to 280 °C, indicating that the temperature of this reduction influences the nature of the surface reactions favorably.
  • hydrogen only reductions conducted outside the above range of temperature gave inferior results in terms of C 5+ hydrocarbon selectivity in subsequent Fischer- Tropsch reactions.
  • the cobalt-containing catalyst referred to herein comprises a reducible cobalt species which may upon reduction be converted to cobalt metal, i.e. the predominant catalytic species.
  • the cobalt-containing catalyst preferably at least partially comprises cobalt in the form of an oxide, for example CoO, Co 2 0 3 and/or Co 3 0 4 , at least prior to reductive activation.
  • the cobalt-containing catalyst for reductive activation in accordance with the method of the invention may be a freshly prepared catalyst material.
  • the cobalt-containing catalyst may be obtained from a cobalt-containing material which has previously been used for catalyzing a Fischer-Tropsch reaction. If necessary, the cobalt- containing material which has previously been used for catalyzing a Fischer-Tropsch reaction is subjected to a passivation step, so as to convert at least a part of the cobalt contained in the material into the oxide form.
  • Fischer-Tropsch reaction may be passivated by treating at elevated temperature with a gas containing molecular oxygen, such as air, prior to reductive activation in accordance with the present invention.
  • a gas containing molecular oxygen such as air
  • Such passivation desirably increases the proportion of oxidic cobalt in the cobalt-containing material which has been previously used in a Fischer-Tropsch reaction.
  • the elevated temperature for this passivation is usually in the range of from 100 °C to 500 °C, preferably 120 °C to 250 °C.
  • the treatment may be carried out at any desired pressure, atmospheric pressure being preferred.
  • the optimum treatment time will depend upon the history of the cobalt- containing material, on the oxygen content of the gas used and on the treatment conditions.
  • the treatment time should in general be of sufficient length to remove any carbonaceous residues present on the cobalt containing material, and is thus especially useful with a cobalt-containing material which has previously been used in Fischer-Tropsch reactions. Treatment times of at least 30 minutes, preferably from 1 to 48 hours, are preferred.
  • the reductive activation process according to the present invention may therefore be used as an activation for a fresh cobalt-containing catalyst, or it can be used as part of a regeneration sequence for a cobalt-containing material which has already been used in a Fischer-Tropsch reaction. In either case, the treatment leads to improved performance in subsequent Fischer-Tropsch reactions. Such an improvement is not seen with conventional activation or regeneration treatments such as a single reduction step with hydrogen at elevated temperature, or a single reduction step with carbon monoxide.
  • the present invention also provides a use of a cobalt- containing Fischer-Tropsch catalyst prepared by a process described herein for increasing selectivity towards C 5 + hydrocarbons, and preferably also catalytic activity, in a Fischer- Tropsch reaction.
  • the present invention also provides a reductively activated cobalt-containing Fischer-Tropsch catalyst prepared by a process as described herein.
  • this use and this catalyst relate are associated with the process for the production of a reductively activated cobalt-containing Fischer-Tropsch catalyst as herein described, any features of the process for the production of a reductively activated cobalt- containing Fischer-Tropsch catalyst are applicable to these aspects, either individually or in any combination..
  • the cobalt-containing Fischer-Tropsch catalyst may be unsupported or preferably supported on a conventional refractory support material, for example a support material comprising silica, alumina, silica/alumina, ceria, zirconia, titania (titanium dioxide), magnesia or the like including mixtures thereof, preferably titania.
  • the support material may be a silica, alumina, silica/alumina, ceria, zirconia or titania support material (including mixtures thereof), or may consist of silica, alumina, silica/alumina, ceria, zirconia, titania or mixtures thereof.
  • the support material may be a titania support material, or may consist of titania.
  • the cobalt-containing Fischer-Tropsch catalyst may be prepared by any suitable method of which the skilled person is aware. For example, it may be prepared by impregnation, precipitation or gelation. A suitable Fischer-Tropsch catalyst may also be prepared by mulling or kneading alumina, silica, titania or zirconia with either of a soluble or insoluble cobalt compound, before extruding, drying and calcining the product.
  • a suitable impregnation method for example, comprises impregnating a support material with a compound of cobalt which is thermally decomposable to the oxide form.
  • Any suitable impregnation technique including the incipient wetness technique or the excess solution technique, both of which are well-known in the art, may be employed.
  • the incipient wetness technique is so-called because it requires that the volume of
  • impregnating solution be predetermined so as to provide the minimum volume of solution necessary to just wet the entire surface of the support, with no excess liquid.
  • the excess solution technique as the name implies requires an excess of the impregnating solution, the solvent being thereafter removed, usually by evaporation.
  • the impregnation solution may suitably be either an aqueous solution or a non- aqueous, organic solution of the thermally decomposable cobalt compound.
  • Suitable nonaqueous organic solvents include, for example, alcohols, ketones, liquid paraffinic hydrocarbons and ethers.
  • aqueous organic solutions, for example an aqueous alcoholic solution, of the thermally decomposable cobalt compound may be employed.
  • Suitable soluble compounds include for example the nitrate, acetate or
  • acetylacetonate preferably the nitrate, of cobalt. It is preferred to avoid the use of the halides because these have been found to be detrimental.
  • Impregnation may be conducted with a support material which is in a powder, granular or pelletized form. Alternatively, impregnation may be conducted with a support material which is in the form of a shaped extrudate.
  • a suitable precipitation method for producing the cobalt-containing catalyst comprises, for example, the steps of: (1) precipitating at a temperature in the range from 0 °C to 100 °C cobalt in the form of an insoluble thermally decomposable compound thereof using a precipitant comprising ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, a tetraalkylammonium hydroxide or an organic amine, and (2) recovering the precipitate obtained in step (1).
  • any soluble salt of cobalt may be employed.
  • Suitable salts include, for example, carboxylates, chlorides and nitrates. It is preferred to use aqueous solutions of the cobalt salt(s), although aqueous alcoholic solutions for example may be employed if desired.
  • tetraalkylammonium hydroxides and organic amines may also be used.
  • the alkyl group of the tetraalkylammonium hydroxide may suitably be a C to C 4 alkyl group.
  • a suitable organic amine is cyclohexylamine.
  • compositions free from alkali metal may suitably be produced using as the precipitant either ammonium carbonate or ammonium bicarbonate, even more preferably ammonium bicarbonate.
  • Ammonium carbonate may suitably be used in a commercially available form, which comprises a mixture of ammonium bicarbonate and ammonium carbamate. Instead of using a pre-formed carbonate or bicarbonate it is possible to use the precursors of these salts, for example a soluble salt and carbon dioxide.
  • Calcination may be used to afford a catalyst comprising cobalt in the oxide form by, for instance, causing thermal-decomposition of a thermally decomposable compound of cobalt formed previously. Calcination may be performed by any method known to those of skill in the art, for instance in a fluidized bed or rotary kiln at a temperature suitably in the range from 200 °C to 700 °C. In some embodiments, calcination may be conducted as part of an integrated process also comprising the reductive activation and performed in the same reactor.
  • the amount of cobalt compound present in the cobalt-containing catalyst is not particularly limited. According to some embodiments of the present invention, the catalyst comprises from 5% to 40%, preferably from 5% to 35%, more preferably from 10% to 30% and more preferably from 15% to 25%, cobalt, or cobalt compound, by weight of the catalyst. Alternatively, the amount of cobalt compound present in the cobalt-containing catalyst may be from 5% to 30%, preferably from 5% to 25% and more preferably from 10%) to 20% cobalt, or cobalt compound, by weight of the catalyst.
  • the cobalt-containing catalyst may additionally comprise one or more promoters, which may promote reduction of an oxide of cobalt to cobalt metal, preferably at lower temperatures.
  • the one or more promoters is selected from the list consisting of ruthenium, palladium, platinum, rhodium, rhenium, manganese, chromium, nickel, iron, molybdenum, boron tungsten, zirconium, gallium, thorium, lanthanum, cerium and mixtures thereof.
  • the promoter is typically used in a cobalt to promoter atomic ratio of up to 250:1 and more preferably up to 125:1, still more preferably up to 25: 1, and most preferably 10: 1.
  • a promoted catalyst may be prepared by a variety of methods including
  • the promoter may be added at one or more of the catalyst preparation stages including: during precipitation as a soluble compound; precipitation by incipient wetness impregnation; or following calcination of the cobalt comprising precipitate.
  • the cobalt-containing catalyst may also be a composition additionally comprising titania, as described, for instance, in US7851404. Such a composition is preferably made by the preferred process described therein.
  • the reductive activation process of the present invention is preferably carried out batch wise in a fixed bed reactor. In at least some embodiments, the reductive activation process of the present invention is conducted in the same reactor as the subsequent Fischer- Tropsch synthesis reaction.
  • the carbon monoxide-containing gaseous stream and/or the hydrogen-containing gaseous stream may be separately fed into the reactor in the gas-phase, or alternatively as a condensed phase which vaporizes within the reactor so that it contacts the solid catalyst in the gas-phase.
  • the process of the present invention may optionally comprise a plurality of reactors arranged in series, such that any composition removed from the first reactor is fed to a second reactor, and composition removed from the second reactor is fed to a third reactor and so on.
  • the cobalt-containing catalyst may be contacted with the carbon monoxide gaseous stream in one reactor before the product of that reduction is transferred to a second reactor for contacting with the hydrogen gaseous stream.
  • both reduction steps i) and ii) according to the process of the present invention are conducted in the same reactor.
  • the reductively activated cobalt-containing catalyst formed following the process according to the present invention is useful in the heterogeneously catalysed production of hydrocarbons from syngas by Fischer-Tropsch synthesis, for example in the production of a diesel or aviation fuel or precursor thereof.
  • Fischer-Tropsch synthesis of hydrocarbons from syngas may be represented by Equation 1 : mCO + (2m+ i ) H 2 ⁇ m H 2 0 + C m H 2m+2 Equation 1
  • Equation 1 mCO + (2m+ i ) H 2 ⁇ m H 2 0 + C m H 2m+2 Equation 1
  • the process comprises an additional step iii) of performing a Fischer-Tropsch synthesis reaction for forming hydrocarbons, said additional step comprising contacting the reductively activated cobalt- containing Fischer-Tropsch catalyst obtained in step ii) with a mixture of carbon monoxide and hydrogen gases, preferably in the form of a synthesis gas mixture (syngas).
  • a mixture of carbon monoxide and hydrogen gases preferably in the form of a synthesis gas mixture (syngas).
  • the reductively activated cobalt-containing Fischer-Tropsch catalyst obtained in step ii) may be transferred to a different reactor for contacting with a mixture of carbon monoxide and hydrogen gases as part of the Fischer-Tropsch reaction according to step iii).
  • steps ii) and iii) may be conducted in the same reactor.
  • the present invention also provides a process for the conversion of a mixture of hydrogen and carbon monoxide, preferably in the form of a synthesis gas mixture, to hydrocarbons, which process comprises contacting a mixture of hydrogen and carbon monoxide with a reductively activated catalyst composition as hereinbefore described, or produced as hereinbefore described.
  • the present invention also provides a product (preferably a fuel) comprising hydrocarbons obtained from a process as
  • reductively activated cobalt-containing Fischer-Tropsch catalyst are applicable these aspects, either individually or in any combination.
  • the volume ratio of hydrogen to carbon monoxide (H 2 :CO) in the gaseous reactant mixture is preferably in the range of from 0.5 : 1 to 5 : 1, more preferably from 1 : 1 to 3 : 1, and most preferably 1.6 : 1 to 2.2 : 1.
  • the gaseous reactant stream may also comprise other gaseous components, such as nitrogen, carbon dioxide, water, methane and other saturated and or unsaturated light hydrocarbons, each preferably being present at a concentration of less than 30% by volume.
  • the temperature of the Fischer-Tropsch reaction is preferably in the range from 100 to 400 °C, more preferably from 150 to 350 °C, and most preferably from 150 to 250 °C.
  • the pressure is preferably in the range from 1 to 100 bar (from 0.1 to 10 MPa), more preferably from 5 to 75 bar (from 0.5 to 7.5 MPa), and most preferably from 10 to 50 bar (from 1.0 to 5.0 MPa).
  • the gaseous reactants for the Fischer-Tropsch reaction may be fed into the reactor either separately or pre-mixed (e.g. as in the case of syngas). They may initially all contact the solid catalyst at the same portion of the solid catalyst, or they may be added at different positions of the solid catalyst.
  • the initial point of contact of the one or more reactants with the solid catalyst is the point at which all the reactants initially contact each other in the gas-phase and in the presence of the solid catalyst.
  • the one or more gaseous reactants flow co-currently over the solid catalyst.
  • the gaseous reactant mixture used for the Fischer-Tropsch reaction may also comprise recycled materials extracted from elsewhere in the process, such as unreacted reactants separated from reduction steps i) and ii) according to the process of the invention.
  • the mixture of hydrogen and carbon monoxide is suitably passed over the catalyst bed at a gas hourly space velocity (GHSV) in the range from 100 to 10000 h “1 (gas volumes converted to standard temperature and pressure), preferably from 250 to 5000 h "1 , such as from 250 to 3000 h "1 and more preferably from 250 to 2000 h "1 .
  • GHSV gas hourly space velocity
  • synthesis gas which is preferably used for the Fischer- Tropsch reaction, principally comprises carbon monoxide and hydrogen and possibly also minor amounts of carbon dioxide, nitrogen and other inert gases depending upon its origin and degree of purity.
  • Methods of preparing synthesis gas are established in the art and usually involve the partial oxidation of a carbonaceous substance, e.g. coal.
  • synthesis gas may be prepared, for example by the catalytic steam reforming of methane.
  • the ratio of carbon monoxide to hydrogen present in the synthesis gas may be altered appropriately by the addition of either carbon monoxide or hydrogen, or may be adjusted by the so-called shift reaction well known to those skilled in the art.
  • the Fischer-Tropsch reaction is preferably carried out continuously in a fixed bed, fluidised bed or slurry phase reactor.
  • the particle size should be of such shape and dimension that an acceptable pressure drop over the catalyst bed is achieved.
  • a person skilled in the art is able to determine the particle dimension optimal for use in such fixed bed reactors. Particles of the desired shape and dimension may be obtained by extrusion of a slurry to which optionally extrusion aids and/or binders may be added.
  • CO conversion is defined as moles of CO used/moles of CO fed x 100 and carbon selectivity as moles of CO attributed to a particular product/moles of CO converted x 100.
  • temperatures referred to in the Examples are applied temperatures and not catalyst/bed temperatures.
  • Cobalt oxide supported on titanium dioxide was manufactured as a catalyst by impregnating titanium dioxide powder with an aqueous solution of cobalt nitrate hexahydrate, followed by extrusion of the formed paste, and then drying and calcining to yield catalyst extrudates with a cobalt loading of 10% by weight of catalyst and a manganese loading of 1% by weight of catalyst.
  • the treated catalysts from Examples 2 to 4 are each exposed to Fischer-Tropsch reaction conditions in the same microreactor where respective pre -treatments are conducted.
  • the same start-up procedure is used for each of the pre-treated catalysts.
  • Temperature is then increased from 150 °C to 160 °C at 60 °C. h "1 and maintained for 15 minutes.
  • Temperature is then increased to 180 °C at 10 °C. h "1 and maintained for 15 minutes.
  • Temperature is then increased to 190 °C at 5 °C.

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Abstract

La présente invention concerne un processus pour la production d'un catalyseur Fischer-Tropsch contenant du cobalt à activation réductrice non supporté ou supporté sur un matériau de support comprenant de la silice, de l'alumine, de la silice/alumine, de l'oxyde de cérium, de l'oxyde de titane, de la magnésie et/ou des mélanges de ceux-ci, ledit processus comprenant i) une étape de réduction de monoxyde de carbone comprenant la mise en contact d'un catalyseur Fischer-Tropsch contenant du cobalt avec un flux gazeux comprenant du monoxyde de carbone et moins de 10 % en volume d'hydrogène sur la base du volume de monoxyde de carbone ; suivie ii) d'une étape de réduction d'hydrogène comprenant la mise en contact du produit de l'étape de réduction de monoxyde de carbone i) avec un flux gazeux comprenant de l'hydrogène et moins de 10 % en volume de monoxyde de carbone sur la base du volume d'hydrogène à une température de 200 °C à 280 °C.
PCT/EP2015/078419 2014-12-12 2015-12-02 Processus de production d'un catalyseur de synthèse fischer-tropsch à activation réductrice, et processus de production d'hydrocarbures utilisant celui-ci Ceased WO2016091695A1 (fr)

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EP4202018A1 (fr) * 2021-12-23 2023-06-28 Bp P.L.C. Démarrage de synthèse fischer-tropsch
EP4379022A1 (fr) * 2022-12-02 2024-06-05 Bp P.L.C. Activation d'un catalyseur fischer-tropsch
EP4379026A1 (fr) * 2022-12-02 2024-06-05 Bp P.L.C. Activation d'un catalyseur fischer-tropsch
WO2024116152A1 (fr) * 2022-12-02 2024-06-06 Bp P.L.C. Traitement in situ d'un catalyseur fischer-tropsch

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4202018A1 (fr) * 2021-12-23 2023-06-28 Bp P.L.C. Démarrage de synthèse fischer-tropsch
WO2023119234A1 (fr) * 2021-12-23 2023-06-29 Bp P.L.C. Démarrage de synthèse de fischer-tropsch
EP4379022A1 (fr) * 2022-12-02 2024-06-05 Bp P.L.C. Activation d'un catalyseur fischer-tropsch
EP4379026A1 (fr) * 2022-12-02 2024-06-05 Bp P.L.C. Activation d'un catalyseur fischer-tropsch
WO2024116146A1 (fr) * 2022-12-02 2024-06-06 Bp P.L.C. Activation de catalyseur de fischer-tropsch
WO2024116152A1 (fr) * 2022-12-02 2024-06-06 Bp P.L.C. Traitement in situ d'un catalyseur fischer-tropsch
WO2024116149A1 (fr) * 2022-12-02 2024-06-06 Bp P.L.C. Activation de catalyseur de fischer-tropsch
WO2024116151A1 (fr) * 2022-12-02 2024-06-06 Bp P.L.C. Traitement in situ d'un catalyseur fischer-tropsch

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