WO2014140973A1 - Procédé de synthèse d'hydrocarbures - Google Patents

Procédé de synthèse d'hydrocarbures Download PDF

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Publication number
WO2014140973A1
WO2014140973A1 PCT/IB2014/059259 IB2014059259W WO2014140973A1 WO 2014140973 A1 WO2014140973 A1 WO 2014140973A1 IB 2014059259 W IB2014059259 W IB 2014059259W WO 2014140973 A1 WO2014140973 A1 WO 2014140973A1
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Prior art keywords
cobalt
catalyst
silicon carbide
support
slurry bed
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PCT/IB2014/059259
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English (en)
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Peter Jacobus Van Berge
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Sasol Technology (Pty) Limited
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Publication of WO2014140973A1 publication Critical patent/WO2014140973A1/fr

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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • 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
    • B01J37/0205—Impregnation in several steps
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g

Definitions

  • This invention relates to a process for producing hydrocarbons, and more particularly to such a process which includes the use of a cobalt-based silicon carbide supported catalyst.
  • Fischer-Tropsch synthesis Hydrocarbon synthesis from synthesis gas (or syngas) including a mixture of hydrogen and carbon monoxide in the presence of a Fischer-Tropsch (FT) catalyst is commonly known as Fischer-Tropsch synthesis (FTS).
  • FTS forms part of gas-to-liquids, coal-to-liquids, and biomass-to-liquids processes in which natural gas, coal, and biomass respectively are usually converted by means of a three step process into liquid hydrocarbons.
  • the three process steps are normally (i) production of synthesis gas (or syngas) comprising a mixture of hydrogen and carbon monoxide from natural gas, coal, or biomass, (ii) conversion of the syngas into a waxy syncrude by means of FTS, and (iii) a hydrocracking or hydrotreating step to convert the waxy syncrude into liquid transportation fuels such as diesel, petrol, jet fuel, as well as naphtha.
  • synthesis gas or syngas
  • conversion of the syngas into a waxy syncrude by means of FTS and
  • a hydrocracking or hydrotreating step to convert the waxy syncrude into liquid transportation fuels such as diesel, petrol, jet fuel, as well as naphtha.
  • FTS catalysts in the form of cobalt supported on alumina deactivate much faster at higher water partial pressures of around 1000 kPa than at a water partial pressure of around 450 kPa, as illustrated in Table 1. Due to this high deactivation rate at a high P H 2o > the FTS either has to be carried out at a low P H 2o resulting in a lower syngas conversion, or the average catalyst activity will be lower, requiring mitigating actions such as replacing the catalyst more frequently, loading more catalyst into the reactor, etc., that is, a less economical process is obtained. Accordingly, it is desirable to have a FTS catalyst that is resistant to deactivation under high P H2 o during FTS.
  • High P H 2o is more problematic in slurry bed reactors compared to fixed bed reactors, since there is a substantial extent of back-mixing in slurry bed reactors so that a comparatively large part of the slurry bed is exposed to high P H 2o-
  • the catalyst particles in a slurry bed reactor circulate continuously through the whole slurry bed, so that all particles frequently pass through zones of high P H 2o-
  • the catalyst particles are stationary and the P H 2o increases from the reactor inlet to the outlet; accordingly, a much smaller part of the catalyst bed is exposed to the higher P H2 o-
  • silicon carbide As a support for catalysts.
  • silicon carbide has been identified as a support for catalysts in Ledoux et a/., J Catal. 114 (1988) 176-188; Philippe et al., Catal Today 147S (2009) S305-S312; De la Osa er a/., Catalysis Today 176 (2011) 298-302; Nguyen et al., Appl. Catal. 391 (2011) 443-454; Lacroix et al., Appl. Catal. 397 (2011 ) 62-72; US Patent No. 7,393,877; International Application No. WO 2007/000506; US Patent No.
  • Silicon carbide is also known for its chemical inertness (see, for example, De la Osa, Fuel 95 (2012) 587, page 587, second column, last 4 lines to page 588, first column, first 4 lines) and although it has been used as a catalyst support on an experimental basis, it would be expected that the interaction of the cobalt with the silicon carbide support would be low due to the chemical inertness of this support. Low interaction with the supported cobalt would be expected to cause sintering of the cobalt and result in deactivation during FTS at a high P H 2 O . especially for FTS carried out in a slurry bed FTS reactor.
  • a process for producing hydrocarbons and, optionally, oxygenates of hydrocarbons including:
  • syngas which includes a mixture of hydrogen and carbon monoxide
  • a cobalt-based supported catalyst in a slurry bed of a slurry bed reactor at a temperature above 180°C in the slurry bed, a pressure of at least 10 bar(a) (1000 kPa(a)) in the slurry bed and a water partial pressure ( ⁇ ⁇ 2 ⁇ ) reaching at least 5 bar(a) (500 kPa(a)) in the slurry bed;
  • the cobalt-based supported catalyst has been prepared by
  • the particulate silicon carbide catalyst support may be any suitable silicon carbide support for supporting cobalt or a cobalt compound thereon, provided that the silicon carbide catalyst support is suitable for use as a support in a catalyst for producing hydrocarbons and, optionally, oxygenates of hydrocarbons from at least hydrogen and carbon monoxide.
  • the catalyst is a Fischer-Tropsch (FT) synthesis catalyst to be used in a three phase slurry bed FT synthesis process.
  • FT Fischer-Tropsch
  • the silicon carbide catalyst support contains more than 50% by weight silicon carbide, preferably more than 90% by weight silicon carbide. More preferably, the support (excluding promoters and dopants) consists of substantially 100% by weight silicon carbide.
  • the silicon carbide in the support includes more than 50% by weight beta-SiC, preferably above 90% by weight beta-SiC, and preferably substantially 100% by weight beta- SiC.
  • the silicon carbide catalyst support includes an outer layer of Si0 2 . The outer layer may be formed by treating the silicon carbide of the silicon carbide support in air.
  • the silicon carbide catalyst support may be a beta-SiC support supplied by Sicat Sari.
  • the particulate silicon carbide catalyst support is usually porous.
  • the incipient wetness support pore volume may be between 0.1 and 1ml/g catalyst support, and in one embodiment of the invention it may be 0.19 ml/g catalyst support, or even above 0.3 ml/g catalyst support.
  • the incipient wetness support pore volume is defined as the pore volume as determined by adding water to the support until external wetting is observed.
  • the catalyst support may have a support surface above 20 m 2 /g catalyst support, and in one embodiment of the invention it may be 28 m 2 /g catalyst support, or even about 40 m 2 /g catalyst support.
  • the catalyst support may be pre-shaped.
  • the catalyst support may be in the form of crushed and sieved particles.
  • the particulate support may have an average particle size of between 1 and 500 micrometers, preferably between 10 and 250 micrometers, more preferably between 38 and 150 micrometers.
  • the cobalt loaded silicon carbide catalyst support is prepared by introducing a cobalt compound onto and/or into the particulate silicon carbide catalyst support.
  • the cobalt compound may be an organic cobalt compound, but preferably it is an inorganic cobalt compound.
  • the cobalt compound may be a cobalt salt, preferably an inorganic cobalt salt.
  • the inorganic cobalt salt may be cobalt nitrate, preferably Co(N0 3 ) 2 .6H 2 0.
  • the cobalt compound may be introduced onto and/or into the catalyst support by any suitable manner, but preferably it is by means of impregnation.
  • the catalyst support is impregnated by the cobalt compound by forming a mixture of the cobalt compound; a liquid carrier for the cobalt compound; and the catalyst support.
  • the liquid carrier may comprise a solvent for the cobalt compound and preferably the cobalt compound is dissolved in the liquid carrier.
  • the liquid carrier may be water.
  • the impregnation may be effected by any suitable impregnation method, including incipient wetness impregnation or slurry phase impregnation. Slurry phase impregnation is preferred.
  • the cobalt compound is dissolved in the liquid carrier in order that the volume of the solution is greater than xy litre, which solution is then mixed with the catalyst support, and wherein x is the BET pore volume of the catalyst support in ml/g support, and y is the mass of catalyst support to be impregnated in kg.
  • the volume of the solution is greater than 1.5 xy litre, and preferably it is about 2 xy litre.
  • the impregnation may be carried out at sub-atmospheric pressure, preferably below 85 kPa(a), preferably at 20kPa(a) and lower.
  • the impregnation is also carried out at a temperature above 25°C.
  • the temperature is above 40°C, preferably above 60°C, but preferably not above 95°C.
  • the impregnation may be followed by partial drying of the impregnated support, preferably at a temperature above 25°C.
  • the temperature is above 40°C, preferably above 60°C, but preferably not above 95°C.
  • the partial drying may be effected at sub- atmospheric conditions, preferably below 85kPa(a), preferably at 20kPa(a) and lower.
  • the impregnation and partial drying may be carried out in a procedure which includes a first step wherein the catalyst support is impregnated (preferably slurry impregnated) with the cobalt compound at a temperature above 25°C, and at sub-atmospheric pressure, and the resultant product is dried; and at least one subsequent step wherein the resulting partially dried impregnated catalyst support of the first step is subjected to treatment at a temperature above 25°C, and sub-atmospheric pressure such that the temperature of the subsequent step exceeds that in the first step and/or the sub- atmospheric pressure in the subsequent step is lower than that in the first step.
  • This two step impregnation may be the process as described in WO 00/20116, which is incorporated herein by reference.
  • a dopant capable of enhancing the reducibility of the cobalt in the cobalt compound may also be introduced onto and/or into the catalyst support.
  • the dopant may be introduced during or after the introduction of the cobalt compound onto and/or into the catalyst support.
  • the dopant may be introduced as a dopant compound which is a compound of a metal selected from the group including palladium (Pd), platinum (Pt), ruthenium (Ru), rhenium (Re) and a mixture of one or more thereof.
  • the dopant compound is an inorganic salt, and preferably it is soluble in water.
  • the dopant may be introduced to be present at mass proportion of the metal of the dopant to cobalt at 1 :300 to 1 :3000.
  • the catalyst precursor is formed by calcining the cobalt loaded silicon carbide catalyst support under non-reducing conditions at a temperature above 400°C.
  • the calcination is carried out after partial drying of the impregnated support, as described above.
  • the calcination may be effected to form one or more cobalt oxide compounds, preferably by decomposing the cobalt compound and/or causing the cobalt compound to react with oxygen.
  • cobalt nitrate may be converted into a compound selected from CoO, CoO(OH), C03O4, Co 2 0 3 or a mixture of one or more thereof.
  • the calcination may be carried out in an inert atmosphere, but preferably it is carried out under oxidation conditions, preferably in an oxygen containing atmosphere, preferably in air.
  • the calcination may be carried out in any suitable manner such as in a rotary kiln, but preferably it is carried out in a fluidised bed reactor.
  • the calcination is carried out at a temperature of at least 450°C, preferably of at least 500°C, and preferably at about 550°C and even above 550°C, but preferably not above 750°C, preferably not above 650°C.
  • the calcination may be carried out by using a heating rate and an air space velocity that complies with the following criteria:
  • the impregnation, the partial drying and calcination may be repeated to achieve higher loadings of the catalyst precursor compound on the catalyst support.
  • the cobalt-based supported catalyst is formed by reducing the catalyst precursor at an elevated temperature, preferably of at least 200°C, more preferably at least 300°C, and most preferably at least 400°C, to activate the catalyst precursor.
  • the temperature during reduction is preferably at least 450°C, more preferably at least 500°C, most preferably about 550°C and even above.
  • cobalt metal is formed.
  • the catalyst precursor is preferably treated with a reducing gas to activate the catalyst precursor.
  • the reducing gas is hydrogen or a hydrogen containing gas.
  • the hydrogen containing gas may consist of hydrogen and one or more inert gases which are inert in respect of the active catalyst.
  • the hydrogen containing gas preferably contains at least 90 volume % hydrogen.
  • the reducing gas may also be a carbon monoxide containing gas.
  • the catalyst may also be activated by treating it with different types of reducing gases in subsequent stages of the activation procedure.
  • the reducing gas may be contacted with the catalyst precursor in any suitable manner.
  • the catalyst precursor is provided in the form of a bed of particles with the reducing gas being caused to flow through the bed of particles.
  • the bed of particles may be a fixed bed, but preferably it is a fluidised bed and preferably the reducing gas acts as the fluidising medium for the bed of catalyst precursor particles.
  • the reduction may be carried out at a pressure from 0.6 to 1.5 bar(a) (60 to 150 kPa(a)), preferably from 0.8 to 1.3 bar(a) (80 to 130 kPa(a)).
  • the pressure may be from 1.5 to 20 bar(a) (150 to 2000 kPa(a)).
  • the pressure is at about atmospheric pressure.
  • the temperature may be varied, and preferably it is increased to a maximum temperature as set out above.
  • the flow of the reducing gas through the catalyst bed is preferably controlled to ensure that contaminants produced during reduction are maintained at a sufficiently low level.
  • the reducing gas may be recycled, and preferably the recycled reducing gas is treated to remove one or more contaminants produced during reduction.
  • the contaminants may comprise one or more of water and ammonia.
  • the activation may be carried out in two or more steps during which one or more of the heating rate, the space velocity of the reducing gas and the reducing gas composition is varied.
  • the cobalt-based supported catalyst may include a cobalt loading in an amount of more than 12 g Co/100g catalyst support. Preferably, the cobalt loading is more than 15 g Co/100g catalyst support.
  • the catalyst may be coated by a coating medium (preferably a wax), preferably by introducing a mixture of the catalyst particles and a coating medium, in the form of a molten organic substance (preferably a wax), which is at a temperature T ⁇ and which sets or congeals at a lower temperature T 2 so that T 2 ⁇ T 1 , into at least one mould; and at least partly submerging the mould in a cooling liquid, so as to cool the organic substance down to a temperature T 3 , where T 3 ⁇ T 2 .
  • a coating medium preferably a wax
  • the hydrocarbon synthesis process is a three phase slurry bed Fischer-Tropsch process for producing hydrocarbons and, optionally oxygenates of hydrocarbons.
  • the hydrocarbon synthesis may be carried out in any suitable slurry bed reactor comprising a reactor vessel containing the cobalt-based supported catalyst in a liquid medium (preferably an organic substance, preferably a wax).
  • a reactor vessel containing the cobalt-based supported catalyst in a liquid medium (preferably an organic substance, preferably a wax).
  • a liquid medium preferably an organic substance, preferably a wax.
  • Such reactors which are also called slurry phase reactors, slurry bubble column reactors or the like, are provided in the art, e.g. FT Technology, Stud. Surf. Sci. Cat. Vol. 152, Chapter 2.
  • the slurry bed may be in a churn-turbulent flow regime, and preferably the slurry bed reactor has a diameter of more than 1m.
  • the slurry bed temperature during the hydrocarbon synthesis process is at least 180°C, preferably at least 200°C, preferably at least 220°C, and more preferably about 230°C. Preferably, the temperature is below 250°C.
  • the pressure in the slurry bed during hydrocarbon synthesis is preferably at least 20 bar(a) (2000 kPa(a)), preferably about 30 bar(a) (3000 kPa(a)). Preferably, the pressure is below 70 bar(a) (7000 kPa(a)).
  • the water partial pressure (P H 2 O ) reached in the slurry bed is above 7 bar(a) (700kPa(a)) and most preferably it is above 9 bar(a) (900 kPa(a)).
  • the said P H 2o is also reached in the gas leaving the slurry bed.
  • P H2 o can be achieved in various ways, including by increasing the catalyst activity, increasing the temperature, increasing the total pressure, increasing the amount of catalyst loaded, decreasing the space velocity, and combinations hereof.
  • a process for producing hydrocarbons and, optionally, oxygenates of hydrocarbons including:
  • the process may also include a hydroprocessing step for converting the hydrocarbons and, optionally, oxygenates thereof to liquid fuels and/or chemicals.
  • a cobalt-based supported catalyst in a process for producing hydrocarbons by contacting syngas, which includes a mixture of hydrogen and carbon monoxide, with the cobalt-based supported catalyst in a slurry bed of a slurry bed reactor at a temperature above 180°C in the slurry bed, a pressure of at least 10 bar(a) (1000 kPa(a)) in the slurry bed and a water partial pressure (P H 2o) reaching at least 5 bar(a) (500 kPa(a)) in the slurry bed;
  • the cobalt-based supported catalyst has been prepared by
  • hydrocarbon synthesis products produced by the processes as described above.
  • a standard crushed and sieved (that is, particulate) beta-SiC catalyst support was supplied by the company Sicat Sari.
  • the particle size distribution of this material ranged from a diameter of 38 pm to 150 pm, the incipient wetness pore volume was 0.19 ml/g.
  • the surface area was 28 m 2 /g, as analysed by the technique of N 2 Sorptometry.
  • the SiC support includes a Si0 2 outer layer of a few nanometers.
  • Example 1 The support material of Example 1 was impregnated with a cobalt compound, by applying a slurry phase impregnation method with an aqueous cobalt nitrate solution followed by vacuum drying using the following procedure:
  • the intermediate material (the cobalt loaded silicon carbide catalyst support) was calcined in air at 250°C in a fluidised bed reactor, using a heating rate of 1°C/min and a space velocity of 1.0 Nm 3 /(kg Co(N0 3 ) 2 .6H 2 0.hr) (as also described in US 6,806,226). Three subsequent impregnation and calcination steps were executed to obtain a catalyst precursor with the targeted cobalt loading. The cobalt content of this catalyst precursor was 13 mass%, i.e. [15.9g Co/100g ⁇ -SiC].
  • the calcined catalyst precursor was activated (i.e. reduced in a dynamic environment of pure H 2 ) at atmospheric pressure during which the temperature was increased from 25°C to 550°C at a rate of 1.0°C/minute at a pure H 2 flow of 23 ml n /(minute . g catalyst) whereafter it was kept isothermally at 550°C for 4 hours at a pure H 2 flow of 23 ml n /(minute . g catalyst) to provide a cobalt-based supported catalyst. Subsequently, the catalyst was cooled down in hydrogen to room temperature and loaded under an argon blanket in molten Fischer- Tropsch wax, ensuring proper protection of the cobalt-based supported catalyst from the atmosphere.
  • This catalyst was prepared according to the procedures of Example 2, except that the calcination was executed at a temperature of 450°C.
  • This catalyst was prepared according to the procedures of Example 2, except that the calcination was executed at a temperature of 550°C.
  • This catalyst was prepared according to the procedures of Example 2, except that the calcination was executed at a temperature of 650°C.
  • This catalyst was prepared according to the procedures of Example 2, except that the calcination was executed at a temperature of 750°C.
  • Example 2 A standard Sasol Germany Puralox 2/150 gamma alumina support was impregnated with cobalt and platinum, a slurry impregnation method as per Example 2 was applied, followed by calcination and reduction as per Example 2.
  • the activated and wax protected catalysts of Examples 2 to 7 were tested for their slurry phase FTS performance in a laboratory micro slurry CSTR of about 700 ml volume at a reactor temperature of 230°C and a reactor pressure of 30 bar during which a pure H 2 and CO and Ar feed gas mixture was utilised with a 10 volume% Ar content and a molar H 2 /CO ratio of 2.1.
  • the gas space velocity was changed to such an extent that the catalyst performance was determined first at P H 2o of 500 kPa(a) and thereafter at P H 2o of 1000 kPa(a).
  • the P H 2o is measured at the outlet of the laboratory CSTR, but due to the nature of a CSTR the complete catalyst inventory is exposed to this P 2 at all times during the experiment.
  • the alumina-based catalyst lost a significant amount of its activity when operated at conditions of high water partial pressures.
  • the beta-SiC based catalysts are however very stable at high water partial pressures.
  • the catalyst calcined at 550°C even shows an increase in catalyst activity when subjected to high water partial pressures.
  • the FT activity of the SiC based catalysts (Examples 2 to 6) is shown in Table 2, and it can be seen that calcination of the impregnated and dried catalyst intermediate should be done in excess of 250°C to obtain catalysts with a high activity. Excellent methane selectivity is obtained for Examples 3, 4, 5 and 6, i.e. the catalysts calcined in excess of 250°C.
  • Example 7 The activated and wax protected catalyst of Example 7 was tested in a similar manner as in Example 8, but for a longer period of time.
  • the activity of this comparative catalyst decreases about 50% over a 4 day period (from day 4 to day 8) at a P H 2o of between about 600-900kPa(a).
  • Example 4 The activated and wax protected catalyst of Example 4 was tested in a similar manner as in Example 8, but for a longer period of time.
  • the activity of this inventive catalyst decreases only about 10% over a 60 day period at a P H2 o of about 1 000 kPa(a).
  • Comparing Figures 1 and 2 clearly shows that the inventive catalyst is much more stable for a long period of time at high ⁇ ⁇ 2 ⁇ (>500 kPa(a)) than the comparative catalyst.

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Abstract

La présente invention porte sur un procédé pour la production d'hydrocarbures et, plus particulièrement, sur un tel procédé qui comprend l'utilisation d'un catalyseur à base de cobalt supporté sur du carbure de silicium. Selon l'invention, le procédé pour la production d'hydrocarbures et, éventuellement, de composés oxygénés d'hydrocarbures, comprend : la mise en contact de gaz de synthèse, qui comprend un mélange d'hydrogène et de monoxyde de carbone, avec un catalyseur à base de cobalt supporté dans un lit de suspension épaisse d'un réacteur à lit de suspension épaisse à une température au-dessus de 180°C dans le lit de suspension épaisse, une pression d'au moins 10 bar(a) (1000 kPa(a)) dans le lit de suspension épaisse et une pression partielle d'eau (PH2O) atteignant au moins 5 bar(a) (500 kPa(a)) dans le lit de suspension épaisse, le catalyseur à base de cobalt supporté ayant été préparé par (i) introduction d'un composé du cobalt sur et/ou dans un support de catalyseur en carbure de silicium particulaire pour produire un support de catalyseur en carbure de silicium chargé de cobalt ; (ii) calcination du support de catalyseur en carbure de silicium chargé de cobalt dans des conditions non réductrices à une température au-dessus de 400°C pour produire un précurseur de catalyseur ; et (iii) réduction du précurseur de catalyseur pour activer le précurseur de catalyseur et ainsi produire un catalyseur à base de cobalt supporté.
PCT/IB2014/059259 2013-03-14 2014-02-26 Procédé de synthèse d'hydrocarbures WO2014140973A1 (fr)

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Cited By (5)

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JP2016002527A (ja) * 2014-06-18 2016-01-12 株式会社Ihi 触媒の製造方法
US11213806B1 (en) * 2018-06-21 2022-01-04 Mid-Atlantic Technology, Research & Innovation Center, Inc. Catalyst supports—composition and process of manufacture
CN114618542A (zh) * 2020-12-14 2022-06-14 中国科学院大连化学物理研究所 一种低剂量过渡金属促进的钴基费托合成催化剂及其制备方法
US11396007B2 (en) 2018-06-21 2022-07-26 Mid-Atlantic Technology, Research & Innovation Center Catalyst supports—composition and process of manufacture
WO2024056416A1 (fr) 2022-09-15 2024-03-21 IFP Energies Nouvelles Procede de preparation d'un catalyseur a base de carbure de silicium pour la deshydration d'acide hydroxypropanoïque et ses derives

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Publication number Priority date Publication date Assignee Title
JP2016002527A (ja) * 2014-06-18 2016-01-12 株式会社Ihi 触媒の製造方法
US11213806B1 (en) * 2018-06-21 2022-01-04 Mid-Atlantic Technology, Research & Innovation Center, Inc. Catalyst supports—composition and process of manufacture
US11396007B2 (en) 2018-06-21 2022-07-26 Mid-Atlantic Technology, Research & Innovation Center Catalyst supports—composition and process of manufacture
US11547985B2 (en) 2018-06-21 2023-01-10 Mid-Atlantic Technology, Research Innovation Center, Inc. Catalyst supports—composition and process of manufacture
US11772082B1 (en) 2018-06-21 2023-10-03 Avn Corporation Catalyst supports—composition and process of manufacture
CN114618542A (zh) * 2020-12-14 2022-06-14 中国科学院大连化学物理研究所 一种低剂量过渡金属促进的钴基费托合成催化剂及其制备方法
WO2024056416A1 (fr) 2022-09-15 2024-03-21 IFP Energies Nouvelles Procede de preparation d'un catalyseur a base de carbure de silicium pour la deshydration d'acide hydroxypropanoïque et ses derives
FR3139733A1 (fr) 2022-09-15 2024-03-22 IFP Energies Nouvelles Procede de preparation d’un catalyseur a base de carbure de silicium pour la deshydration d’acide hydroxypropanoïque et ses derives

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