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WO2018162363A1 - Procédé série de conversion de gaz de synthèse en hydrocarbures liquides, dispositif utilisé à cet effet comprenant des catalyseurs ft et ht, catalyseur ft - Google Patents

Procédé série de conversion de gaz de synthèse en hydrocarbures liquides, dispositif utilisé à cet effet comprenant des catalyseurs ft et ht, catalyseur ft Download PDF

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Publication number
WO2018162363A1
WO2018162363A1 PCT/EP2018/055237 EP2018055237W WO2018162363A1 WO 2018162363 A1 WO2018162363 A1 WO 2018162363A1 EP 2018055237 W EP2018055237 W EP 2018055237W WO 2018162363 A1 WO2018162363 A1 WO 2018162363A1
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catalyst
range
fischer
tropsch
catalysts
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PCT/EP2018/055237
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Ferdi SCHÜTH
Gonzalo PRIETO-GONZALEZ
Nicolas DUYCKAERTS
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Studiengesellschaft Kohle Mbh
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    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
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Definitions

  • the invention relates, in a first aspect, to a process to convert a feed stream comprising carbon monoxide and hydrogen as major components (synthesis gas) into liquid hydrocarbons by means of the combination of a Fischer-Tropsch solid catalyst and a hydrotreating solid catalyst, in which the liquid hydrocarbon products display a particularly desired distribution with maximum contribution from primarily linear paraffins in the fraction corresponding to middle distillates and minimum contribution from the fraction corresponding to light tail-gas hydrocarbons (C 4- ).
  • the invention relates to a method for preparing a Fischer-Tropsch catalyst to be applied in said process.
  • Syngas is a mixture typically composed of carbon monoxide (CO), hydrogen (H 2 ) and, in certain cases, also carbon dioxide (CO 2 ) as major components.
  • This important and versatile commodity can be obtained from a large variety of carbonaceous feedstocks, e.g. via steam reforming or partial oxidation of natural gas, via gasification of coal, via gasification and/or reforming of biomass feedstocks, via hydrogenation of carbon dioxide, among other.
  • the reaction proceeds via a surface chain-growth polymerization mechanism and therefore results in primarily linear hydrocarbon products which typically obey a so-called Anderson-Schulz-Flory (ASF) chain-length distribution.
  • ASF Anderson-Schulz-Flory
  • the hydrocarbon products span a very wide range of chain-lengths, typically from Ci to C 5 o+, where the subscripts indicate the number of carbon atoms in the hydrocarbon molecule, and the selectivity to specific hydrocarbon fractions is intrinsically limited, meaning that the process leads to both desired and undesired hydrocarbon product fractions.
  • 1 -olefins are a major primary product of the Fischer-Tropsch reaction.
  • these primary products are rather reactive under the reaction conditions which are industrially relevant for this reaction, and typically undergo secondary reactions already before they egress from the Fischer-Tropsch catalyst particle were they formed.
  • Such secondary processing involves re-adsorption of the a-olefins primary products on the metal sites of the Fischer-Tropsch catalyst followed by their incorporation into growing hydrocarbon chains and/or their hydrogenation into the corresponding n-paraffins. Since n- paraffins are significantly less reactive under the standard operation conditions, they typically do not undergo any further tertiary processing.
  • hydrotreating catalyst consists typically of a metal or a metal sulphide dispersed in the form of nanoparticles on an acidic solid.
  • the acidic support is typically an amorphous S1O2-AI2O3, a zeolite (crystalline aluminosilicate) or other type of acidic zeotype.
  • the essentially linear Fischer-Tropsch hydrocarbons are subjected to reactions of skeletal isomerization and cracking resulting in hydrocarbon products of lower molecular weight.
  • the middle distillates fraction is generally the most desirable product fraction, as it can be used as precursor for high cetane-number and sulfur- free synthetic diesel and jet fuels, or directly be blended into oil-derived diesel of jet fuel fractions.
  • the hydrotreating upgrading step takes place under a high pressure atmosphere containing hydrogen and typically in the absence of carbon monoxide which might act as a poison on the metallic function of the hydrotreating catalyst and favour the production of undesired lighter hydrocarbons. Hence the separation of the unconverted syngas in between the Fischer-Tropsch and hydrotreating reaction steps is important for the ultimate product distribution.
  • the syngas feed is converted into hydrocarbons on a Fischer-Tropsch solid catalyst, and the Fischer- Tropsch hydrocarbon products can react directly on the hydrocracking catalyst were the solid waxes are cracked down to lighter hydrocarbons so that the overall hydrocarbon product comprises exclusively, or at least primarily, gas and liquid hydrocarbons. While transportable liquid hydrocarbons are the product of interest, the production of tail-gas hydrocarbons is significantly penalizing for the efficiency and economy of the process and should be ideally minimized.
  • US6410814 by Fujimoto and Tsubaki discloses a process in which a cobalt-based Fischer-Tropsch catalyst and a hydrotreating catalyst are integrated in separate an consecutive packed beds along a tubular reactor to convert syngas into liquid hydrocarbons in a single step.
  • the Fischer- Tropsch catalyst alone produces a hydrocarbon product stream which comprises essentially only n-paraffins, as customary for cobalt-based Fischer-Tropsch catalysts under standard operation conditions.
  • the Fischer-Tropsch and the hydrotreating catalyst are integrated to produce liquid hydrocarbons in a single step, the hydrocarbon products are free from waxes (C23+) but do not contain hydrocarbons in the range of middle-distillates either.
  • the contribution from tail-gas hydrocarbons to the overall hydrocarbon products exceeds 35%.
  • US201 1/0160315 by Kibby et al. discloses a process in which a cobalt-based Fischer-Tropsch catalyst and a hydrotreating catalyst are integrated in separate and consecutive packed beds along a tubular reactor to convert syngas into liquid hydrocarbons in a single step.
  • the process leads to a product hydrocarbon mixture in which the fraction of tail-gas hydrocarbons (C 4- ) contributes >20 wt% and the fraction of middle-distillates (given as C10-C22 in said document) accounts for ⁇ 35 wt%, at CO conversions in the range of 25-80%.
  • US7973086 by Saxton et al. discloses a process in which a cobalt-based Fischer- Tropsch catalyst and an acid hydrotreating catalyst are arranged in alternating packed-beds along a tubular reactor.
  • the process leads to a product hydrocarbon mixture in which the fraction of tail-gas hydrocarbons (C 4- ) contributes >34 wt% and the fraction of middle-distillates (given as C10-C21 in said document) accounts for ⁇ 35 wt%, at a CO conversion of 25- 35%.
  • the (hydro)cracking pattern of the hydrocarbons leaving the upstream bed of the Fischer-Tropsch catalyst, primarily n-paraffins, on the downstream hydrotreating catalyst under the syngas (CO-containing) atmosphere pertaining to this process is far from ideal.
  • severe hydrocarbon cracking converts not only the wax fraction but also the middle- distillates fraction of the Fischer-Tropsch products into lighter hydrocarbons, hence leading to an undesired high production of tail-gas hydrocarbons.
  • Res., 50 (201 1 ), 13732-13741 , describes a process in which the particles of a cobalt-based Fischer-Tropsch catalyst and a Ni/ZSM-5/AI 2 O3 hydrotreating catalyst are blended and packed in a single bed in a tubular reactor, therefore achieving spatial proximities of a magnitude comparable to the size of the macroscopic particles of the blended catalysts, which typically ranges from hundreds of microns to millimeters, depending on the type of catalyst particles and the reactor hydrodynamics, and it is 2 mm in this particular document.
  • the process achieved the complete de-waxing of the hydrocarbon products, for which the contribution of C21 + hydrocarbons was lower than 5% (on a molar carbon basis).
  • the process was particularly selective towards hydrocarbons in the naphtha range, achieving selectivities to hydrocarbons in the C5-C9 higher than 40 %. Nevertheless, the selectivity to the middle distillates fraction, given in the document as C10-C20, was relatively low ( ⁇ 15 %).
  • the process led to a significant production of tail-gas hydrocarbons, with selectivities to C 4- exceeding 35 %.
  • WO2014007598 by Su Ha et al. discloses a process in which a hybrid Fisher- Tropsch/hydrotreating catalyst prepared by growing a zeolite acid component within a porous cobalt oxide scaffold is employed to convert syngas to liquid hydrocarbons in a single step.
  • the process did not achieve the complete de-waxing of the hydrocarbon products, for which the C-mol contribution of C22+ hydrocarbons exceeded 17%.
  • the selectivity to tail-gas hydrocarbons (C 4- ) exceeded 25-30 %.
  • US20100160464 by Kibby et al. discloses a process in which a hybrid Fischer- Tropsch/hydrotreating catalyst is produced by impregnating a zeolite-containing extrudate using a substantially non-aqueous solution of a cobalt precursor, targeting a limited interaction of the cobalt Fischer-Tropsch active phase with the acidic zeolite component, and said hybrid catalyst is employed to convert a syngas feed to liquid hydrocarbons in a single step.
  • the inventors have considered that general limitations are associated to the integration of highly active, cobalt-based Fischer-Tropsch catalysts and acidic hydrotreating catalysts in close proximity.
  • One first limitation relates to the fact that both catalysts need to operate at a common reaction temperature, while, rather different operation temperatures are individually desired for an optimal performance of the Fischer-Tropsch catalysts, particularly the most active ones which are based on metals such as cobalt or ruthenium as the major active phase, and the hydrotreating catalysts.
  • Fisher-Tropsch catalysts provide best performances in the temperature range of 463-493 K, while hydrotreating catalysts require operation temperatures preferably in the range of 523-593K.
  • an additional important technical limitation of a close spatial intimacy of the two catalysts is the impossibility to perform pre-conditioning, rejuvenation and/or regeneration treatments individually for the Fischer-Tropsch and hydrotreating catalysts, as it would be desirable to individually optimize structural parameters such as the metal dispersion, and to adapt to the different rates of deactivation, and thereby different useful lifetimes, of the two catalysts.
  • the inventors have developed a method to perform a process which combines a Fischer-Tropsch catalyst and a hydrotreating catalyst to produce liquid hydrocarbon products in a single step, without any intermediate product separation or isolation stage, which leads to a highly desirable hydrocarbon product with an unusually high contribution of the middle distillates fraction, and an unusually low contribution of tail-gas hydrocarbons.
  • said desirable hydrocarbon product pattern can be achieved when the Fischer-Tropsch hydrocarbon products reaching the hydrotreating catalyst contain an unusually high proportion of olefins in the carbon chain-length range of C3-C10.
  • the inventors have also discovered a method to prepare Fischer-Tropsch catalysts with bespoke porosities which extend over several length scales and owing to which, under standard operation conditions, said catalysts lead to an unexpected enrichment of the Fischer-Tropsch hydrocarbon products in olefins, while they additionally display a high activity per mass of metal, high selectivity to long-chain hydrocarbons and a very low production of undesired carbon dioxide.
  • the unexpected Fischer-Tropsch product hydrocarbon distribution obtained with the inventive catalysts enables the process object of this invention as it allows the Fischer-Tropsch catalyst and the hydrotreating catalyst to operate spatially distant, in different sections of one reactor vessel or even in consecutive reactor units, at different reaction temperatures which can be adjusted individually, while the hydrocarbon stream exchanged between both catalysts corresponds to a very primary Fischer-Tropsch product, and hence resembles the case where the two catalysts are spatially very intimate. It has been discovered that such effect is responsible for a more desirable overall hydrocarbon product distribution which unites the depletion of waxes with a notably higher contribution from hydrocarbons in the middle distillate range and a notably lower contribution from hydrocarbons in the tail-gas range.
  • the present invention accordingly provides, in a first aspect, a process by means of which a syngas feedstock is converted into liquid hydrocarbons in a single step by the combination of a solid Fischer-Tropsch catalyst and a solid hydrotreating catalyst in which said catalysts are operated spatially distant, in different sections of a tubular reactor vessel or in consecutive reactors, without any intermediate product fractionation, separation or purification process step,, the Fischer-Tropsch catalyst is located upstream and the hydrotreating catalyst is located downstream of the former, the hydrocarbon stream leaving the upstream catalyst displays an unusually high content in olefins in the C3-C10 carbon chain length range and the final hydrocarbon products leaving the downstream catalyst display a desirable distribution.
  • the present invention additionally provides a method to prepare a Fischer-Tropsch catalyst with a multimodal porosity, which can be applied in said process.
  • the present invention is concerned, in a first aspect, with a process for the conversion of syngas mixtures into liquid hydrocarbons in a single step, i.e. with no intermediate product fractionation, separation or purification process step,, in which a Fischer-Tropsch catalyst displaying an unusual product selectivity is combined with an acidic hydrotreating catalyst.
  • the Fischer-Tropsch and the hydrotreating catalysts are located in different packed beds along a tubular reactor with two differentially heated zones, being the Fischer-Tropsch catalyst located upstream and the hydrotreating catalyst downstream.
  • the gas stream leaving the packed bed containing the Fischer-Tropsch catalyst i.e. the stream which contains the Fischer-Tropsch products along with unconverted syngas, flows directly to the packed bed containing the hydrotreating catalyst, without any product fractionation, isolation or purification unit operation in between.
  • the two combined catalysts are located in two different sub-units of a compact reactor or micro-reactor vessels, whose temperature can be controlled independently, being the Fischer-Tropsch catalyst located upstream and the hydrotreating catalyst located downstream, without any product fractionation, isolation or upgrading unit operation in between both subunits of the reactor vessel.
  • the two catalysts are placed in two different reactor vessels, connected in series, whose temperature can be controlled independently, and being the Fischer-Tropsch catalyst loaded into the reactor vessel located upstream and the hydrotreating catalyst loaded into the reactor vessel located downstream, without any product fractionation, isolation or purification unit operation in between both reactors.
  • the spatial compartmentalization of the Fischer-Tropsch and hydrotreating catalysts in different reactor sub-units, or different reactors allows their connection in series, during periods of time in which the syngas feed is being converted consecutively on both catalysts, but it also enables an operation in parallel, in which each catalyst compartment is set to receive a different gas feed under selected pressure and temperature conditions, in order to submit either one or the two catalysts to individually designed treatments of pre-conditioning, rejuveneation, re-generation or to carry out the partial or total renovation of one or the two catalysts.
  • the different sub-units of one reactor vessel, or the different reactor vessels, containing each of the combined catalysts can be connected back in series, under an essentially common operation pressure and individually adjusted operation temperatures, to receive the syngas stream which is thus converted into liquid hydrocarbons.
  • the spatial compartmentalization of the Fischer- Tropsch and hydrotreating catalysts in different reactor sub-units, or different reactor vessels enables to perform said individual catalyst treatments and operations in a mode which is known as "swing mode" in the art, and thus without interrupting the continuous process of conversion of the syngas feed stream into hydrocarbons.
  • the present invention comprises the following embodiments:
  • specific surface area shall be determined by nitrogen physisorption at the liquid nitrogen boiling point at atmospheric pressure (77 K) after drying the solid material (ca. 100 mg, 0.4-0.6 mm particle size) at 523 K under vacuum for 10 h.
  • the specific surface area shall be determined using the B.E.T method in the relative pressure (P/Po) regime of 0.05-0.30 of the adsorption branch of the isotherm, where Po is the vapor pressure of nitrogen at the temperature of the measurement.
  • total pore volume and pore size distributions shall be determined by mercury intrusion porosimetry after drying the sample (0.4-0.6 mm particle size) at 383 K for 72 h.
  • the intrusion-extrusion isotherms shall be recorded at room temperature in the pressure range of 6.9- 10 4 - 4.1 ⁇ 10 4 Pa with an equilibration rate of 0.1 ⁇ - g "1 s ⁇ 1 .
  • a geometrical pore model shall be considered, assuming a Hg density of 13.55 g cm "3 and a contact angle of 141 degrees. Pores shall be denoted according to their diameter following the lUPAC recommendations, i.e.
  • total macropore volume shall be defined as the cumulative pore volume corresponding to pores with diameters larger than 50 nm as determined by the method described above.
  • the range of catalyst particle size shall be defined be the opening size of standard stainless steel sieves tested according to the ISO 3310 norm, between which more than 80% of the catalyst mass is retained after a sieving procedure.
  • step b Adding an organic polymer substance to the suspension obtained in step a), which polymer is preferably a non-ionic surfactant selected from the group which comprises:
  • alkyl-polyethylene oxides also known as polyethoxilates, such as those pertaining to the family of surfactants commercialized under the name of Tergitol 15-S- with general formula R-O(EO) x H where R is a hydrophobic alkyl group with n carbon atoms, where n typically spans in the range from 1 to at least 20, EO represents an ethylene oxide building unit (OCH 2 CH 2 ) with x ranging from about 7 to 40;
  • alkyl-phenyl polyethylene oxides such as those pertaining to the family of surfactants commercialized under the name of Igepal-RC or Triton-X;
  • polyethylene oxide (PEO) -polypropylene oxide (PPO) block-copolymers such as those pertaining to the family of surfactants commercialized under the name Pluronic, having a formula (EO) m -(PO) 0 -(EO)p with m and p being independently in the range of 2-130 and o being in the range of 15-70;
  • polysorbate-type surfactants formed by the ethoxylation of sorbitan followed by the addition of lauric acid such as those pertaining to the family of surfactants commercialized under the names Polysorbate, Alkest or Tween; and combinations thereof, more preferably a non-ionic surfactant of the alkyl- polyethylene oxide type, also known as polyethoxylates, such as those pertaining to the family of surfactants commercialized under the name of Tergitol 15-S- with general formula R-O(EO) x H where R is a hydrophobic alkyl group with n carbon
  • step b) Subjecting the suspension obtained in step b) to a hydrothermal treatment under autogenous pressure in an autoclave, preferably in a temperature range from 300 K to 400 K, more preferably from 330 to 350 K, preferably over a time span from 12 h to 72, more preferably from 40 to 60 h;
  • step d Depressurizing the autoclave and drying the product obtained in step c) until the water content is below 10 wt%;
  • step d) Thermally treating the dried product of step d) at an elevated temperature up to 1000 K under oxidizing conditions, preferably under air, whereby the hydrocarbon polymer is combusted in the dried product of step d) and the product of step d) is calcined;
  • step e Impregnating the product of step e) with a solution of at least one salt of an active metal selected from Co, Ru and Fe, preferably according to the incipient wetness method, drying the impregnated product and submitting it to a preferably thermal treatment to decompose said metal salt into a metal oxide or the corresponding metallic form.
  • an active metal selected from Co, Ru and Fe
  • a device for converting a feed stream comprising carbon monoxide and hydrogen as major components (synthesis gas) into liquid hydrocarbons comprising:
  • a Hydrotreating catalyst preferably in the form of a metal or a metal sulphide dispersed in the form of nanoparticles on particles of an acidic solid, which is preferably selected from an amorphous S1O2-AI2O3, a zeolite (crystalline aluminosilicate) or an acidic zeotype,
  • the FT-catalyst and the HT-catalyst are contained in separate compartments (units) of the device which compartments are in fluid communication with each other and where the HT-compartment is positioned downstream of the FT-compartment, preferably in a spatial distance sufficient to establish a temperature difference between the two catalysts of at least 20 K.
  • a feed stream comprising carbon monoxide and hydrogen as major components (synthesis gas) with a molar H 2 /CO ratio in the range of 0.5-3, preferably in the range of 1 -2, is provided to the inlet of a device according to claim 4 and further directed to the FT-catalyst operated at a reaction temperature range selected in the range of 423-513 K, preferably in the range of 460 to 500 K,
  • the obtained gas mixture is directed to the HT-catalyst operated at a reaction temperature range selected in the range of 483-623 K, preferably in the range of 503-553 K, and
  • the obtained gaseous hydrocarbon mixture is directed to a collection vessel, whereby the operating temperature of the FT-catalyst is lower than the operating temperature of the HT-catalyst, and
  • syngas space velocity is selected to achieve a CO conversion in the range of 5-100%, preferably in the range from 20-80%.
  • the FT catalyst of the invention is suitable to achieve the beneficial technical effect of the process of the invention, which leads, under standard FT reaction conditions, to a product mixture with a minimum content of olefins in the C3-C10 hydrocarbon fraction, as mentioned several times in the spec.
  • This aspect is the foundation of the invention.
  • the distance between the two compartments can be, depending on the size of the device, just a few cm up to several hundreds of meters and all the way to km.
  • the main requirement is that the distance is sufficient so that taking into account the thermal conduction properties of the vessels (or vessel subunits) were the catalysts are operated, the temperature of the catalysts can be controlled independently.
  • the catalysts are only ca. 4 cm away from each other.
  • the catalysts could be km away from each other as long as there is no further catalytic conversion and no product fractionation, isolation or purification in between FT-catalyst and HT-catalyst.
  • the distance is to be defined in the direction of the feedstock flow.
  • the catalysts could be placed on both sides of a micrometer thick stainless steel plate in a microreactor, i.e. very close to each other physically, although without direct contact.
  • the "temperature" difference can be used to define the spatial distance. If the catalysts need to work at a temperature difference of at least e.g. 20K, this sets already a minimum requirement for their spatial distance.
  • a syngas mixture with a molar H 2 /CO ratio in the range of 0.5-3, preferably in the range of 1 -2, is used as feedstock.
  • the final product stream leaving the hydrotreating catalyst has a weight contribution from carbon dioxide lower than 3 wt%, and preferably lower than 1 wt%, on the basis of all carbon-containing reaction products.
  • the final product stream leaving the hydrotreating catalyst has a weight contribution from solid hydrocarbons, e.g. C25+ lower than 5 wt%, and preferably lower than 2 wt%, based on the total hydrocarbon products.
  • the final product stream leaving the hydrotreating catalyst has a weight contribution from the tail-gas hydrocarbons (C 4- ) lower than 25 wt%, preferably lower than 20 wt%, along with a weight contribution from hydrocarbons in the carbon number range of C10-C25 larger than 40%, preferably larger than 45 wt%, based on the total hydrocarbon products.
  • the gas stream leaving the Fischer-Tropsch catalyst constituting the feed stream to the hydrotreating catalyst located downstream, displays an unusually high content in olefin Fischer-Tropsch products, as a result of a limited secondary processing of the most primary Fischer-Tropsch products within the particles of the catalyst were they are produced.
  • composition of the hydrocarbons produced in a given Fischer-Tropsch catalyst, and therefore sent as feed onto a hydrocracking catalyst according to the process of the present invention can be adequately determined by means of catalytic tests in which the Fischer-Tropsch catalyst is tested alone, without any additional catalyst, for the conversion of a syngas feed stream under reaction conditions which are standard for the industrial operation for the Fischer-Tropsch synthesis, and the corresponding product stream analyzed, for instance by gas chromatography analytical methods, as a function of the reaction conditions and the degree of CO conversion per reactor pass.
  • the Fischer-Tropsch catalyst produces a hydrocarbon product stream with an unusually high concentration of olefins in the carbon chain length range of C3-C10.
  • the weight fraction of C 5+ hydrocarbons in the FT products is higher than 80 wt%
  • the weight ratio of alpha-olefin to n-paraffin products in the carbon chain length range of C3-C10 is higher than 0.5, and more preferably higher than 0.75, when a syngas feedstock with a H 2 /CO molar ratio of 2.0 is processed at a reaction temperature of 483 K, a reaction pressure of 20 bar and a gas space velocity leading to a CO conversion of 30 ⁇ 5 % per reactor pass.
  • the pressure can be selected in the range of 5 to 200 bar, preferably in the range of 5-50 bar.
  • the Fischer-Tropsch catalyst operates at a reaction temperature which can be selected in the range of 423-513 K, preferably in the range of 460 to 500 K .
  • the hydrotreating catalyst operates at a reaction temperature which can be selected in the range of 483-623 K, preferably in the range of 503-553 K.
  • the syngas space velocity can be selected to achieve a CO conversion in the range of 5-100%, preferably in the range from 20-80%.
  • the present invention provides also a method to prepare a Fischer-Tropsch catalyst with original physicochemical and catalytic properties which enable the process of the invention.
  • Said inventive Fischer-Tropsch catalyst should display a high specific activity under standard Fischer-Tropsch reaction conditions.
  • this activity expressed as a mass-specific rate of CO conversion, is equal or higher than 10 mmolco g ca t h ⁇ 1 , and more preferably higher than 20 mmolco g ca t h ⁇ 1 , at an operation temperature of 483 K using a syngas feed with a molar H 2 /CO ratio of 2.
  • a high specific activity is desired for process intensification.
  • the inventive Fischer-Tropsch catalyst should display a limited activity for the water-gas-shift reaction, hence the selectivity to CO2 (per reactor pass) preferably does not exceed 3 wt%, and most preferably does not exceed 1 wt%.
  • a very low per-pass production of CO2 is desirable to maximize the efficiency of the CO conversion process and avoid the need for extensive recycle streams and additional reverse-water-gas-shift unitary operations, hence contributing to process intensification, a lower overall energy requirement and a lower overall carbon footprint of the process.
  • the inventive Fischer-Tropsch catalyst should additionally display an unusually high selectivity to alpha-olefin primary products under standard Fischer-Tropsch reaction conditions.
  • the weight content of alpha-olefins products in the hydrocarbon chain length range of C3-C10 is higher than 25 wt% when a syngas feedstock with a nominal H 2 /CO molar ratio of 2.0 is processed at a reaction temperature of 483 K, a reaction pressure of 20 bar and a CO conversion of 30 ⁇ 5 % is achieved per reactor pass, which are standard reaction conditions for the Fischer-Tropsch synthesis.
  • the weight content of alpha-olefin products in the hydrocarbon chain length range of C3-C10 is higher than 45 wt% when a syngas feedstock with a nominal H 2 /CO molar ratio of 2.0 is processed at a reaction temperature of 483 K, a reaction pressure of 20 bar and a CO conversion of 30 ⁇ 5 % is achieved per reactor pass.
  • the Fischer-Tropsch catalyst is a supported metal catalyst.
  • supported metal catalyst is understood in the art as a catalyst composition comprising a catalytically active metal part, dispersed in the form of particles with an average diameter typically smaller than 100 nm (nanoparticles), which is therefore active, or can be converted into an active phase in situ prior to or during the usage of the catalyst, and a catalytically non-active part, wherein the catalytically non-active part, denoted as carrier or support material in the art, is generally porous and forms the majority of the catalyst on a mass bases.
  • the Fischer-Tropsch catalyst comprises cobalt as the major Fischer-Tropsch active part, dispersed in the form of particles on a porous carrier material which does not contribute to the Fischer-Tropsch catalytic activity.
  • the weight loading of cobalt i.e. the weight fraction of the total catalyst which corresponds to cobalt in said catalyst, is in the range of 5-50 wt%, and more preferably in the range of 10- 30 wt%.
  • the porous carrier material should be chemically stable under the severe hydrothermal reaction conditions encountered in a process of syngas conversion into hydrocarbons.
  • Said porous carrier can be an oxide selected among those oxide porous carriers which are employed as support materials for supported metal catalysts in the art, and which can comprise, but it is not limited to, AI2O3, S1O2, T1O2, or combinations thereof.
  • the support material can be based on a carbide or oxy-carbide material such as SiC, SiO x C y .
  • the support material can be based on carbon.
  • the support material can be a composite incorporating a combination of said materials.
  • the pore modality, pore diameter and pore volume of the inventive Fischer- Tropsch catalyst have been deemed particularly significant for the process of the invention.
  • the porosity of a solid material can be determined in the art by analytical methods such as nitrogen physisorption combined to suitable mathematical models for the analysis of the physisorption isotherms, thermometry combined to suitable mathematical models for the analysis of the corresponding scanning calorimetry profiles, mercury intrusion porosimetry combined to suitable mathematical models for the analysis of the intrusion isotherms or by electron microscopy methods such as transmission electron microscopy, scanning electron microscopy and their tomographic variations which allow imaging in the three directions in space, combined with suitable methods for quantification of said porosity.
  • pores are denoted micropores when their diameter is smaller to 2nm, they are denoted mesopores if their diameter is in the range of 2-50 nm and they are denoted macropores if their diameter is larger than 50 nm. Macropores can thus lay in the nanometer regime if their diameter is in the 50-1000 nm range or in the micrometer regime if their diameter exceeds 1000 nm (1 micrometer).
  • the Fischer-Tropsch catalyst according to the invention has a specific surface area ranging between 10 and 1 100 m 2 /g, preferably between 50 and 400 m 2 /g.
  • a Fischer-Tropsch catalyst according to the present invention displays at least two modes of pores: one in the mesopore regime and one in the macropore regime. Yet more preferably, the Fischer-Tropsch catalyst displays at least three modes of pores: one in the mesopore regime and two in the macropore regime, one of which consists of macropores with average diameter in the nanometer regime and the other one consists of macropores with an average diameter in the micrometer regime.
  • the multimodal porosity facilitates the evacuation of primary hydrocarbon products from the catalyst pores under standard operation conditions, preventing more effectively the secondary processing of the most primary alpha-olefin products and increasing their contribution up to unusual contents in the hydrocarbon stream produced on the Fischer-Tropsch catalyst and further processed on the hydrotreating catalyst.
  • the total pore volume of the Fischer-Tropsch catalyst is at least 0.3 cm 3 g "1 , preferably at least 0.8 cm 3 g ⁇ 1 .
  • the mesopores of the catalyst have an average diameter in the range of 5-40 nm, and most preferably in the range of 5-20 nm. Said average mesopore diameter is preferred to confine and stabilize cobalt nanoparticles of a diameter in the range of 6-12 nm, which according to what is known in the art, provide high CO conversion rates per unit mass of metal.
  • the macropores of the Fischer-Trospch catalyst account for a fraction of the total pore volume of at least 5 %, and more preferably of at least 20%.
  • the porosity of the Fischer- Tropsch catalyst becomes dictated primarily by the support material, being the contribution of the active metal component to the total porosity negligible, aside from the corresponding mass dilution effect on mass-specific porosity parameters, i.e. those expressed per unit total mass of catalyst.
  • the support material of the Fischer-Tropsch catalyst of the invention can be obtained by a method which involves:
  • the alumina source employed to prepare the suspension is preferably selected from the list of hydragillite, bayerite, pseudoboehmite, amorphous gels, transition aluminas which comprise at least one phase taken from the group comprising rho, chi, eta, gamma, kappa, theta and alpha phases. More preferably, said alumina source is a high-purity dispersible pseudoboehmite, for example Disperal® commercialized by Sasol. Preparation of the suspension is accomplished for instance by mechanical stirring or ultrasound stirring;
  • a polymer in a second step the addition of a polymer to the suspension.
  • Said polymer can be solid or liquid at ambient conditions, and is preferentially liquid at ambient conditions;
  • a thermal treatment under an oxidizing, preferably air, atmosphere to crystallize the alumina precursor and combust the organic material in the dried solid.
  • an oxidizing, preferably air, atmosphere to crystallize the alumina precursor and combust the organic material in the dried solid.
  • These methods include the use of solid combustive porogen materials in combination with peptization, extrusion or granulation methodologies, followed by selective removal of the porogen, for instance by calcination or selective dissolution, coagulation methods, methods in which an emulsion is employed as porogen agent, methods in which ice or an alternative frozen substance is employed as porogen agent and removed by freeze drying.
  • the crush strength might be increased via partial sintering of the constituents after high temperature treatments.
  • the crush strength might be increased by the incorporation of binder or reinforcement materials.
  • Supported metal catalysts can be synthesized by applying a suitable metal precursor on the support material, followed by suitable methods to decompose said precursor into the species which is responsible for the catalytic activity.
  • suitable metal precursors are inorganic and organic cobalt salts, cobalt clusters, and cobalt organometallic complexes. Representative of these compounds are cobalt nitrate, cobalt chloride, cobalt sulphate, cobalt phosphate, cobalt chloroplatinate, cobalt hydroxide, cobalt acetate, cobalt acetylacetonate, cobalt oxalate, cobalt oleate, cobalt citrate, cobalt carbonyl, and the like.
  • Cobalt precursors can provide cobalt in a zero oxidation state, II oxidation state, III oxidation state, or a combination thereof.
  • the Fischer-Tropsch catalyst is prepared using cobalt nitrate as cobalt precursor.
  • cobalt nitrate as cobalt precursor.
  • Several methods are known in the art to incorporate the active metal part on a support material. These methods comprise preparation techniques such as impregnation, deposition precipitation, ion exchange, electrochemical deposition, electrostatic adsorption, co-precipitation which are known methods in the art.
  • cobalt is incorporated on the support material by impregnation using a liquid solution of the cobalt precursor in a suitable solvent.
  • a suitable solvent is selected from the list comprising water, methanol, ethanol, ether, acetone or combinations thereof. More preferably said solvent is water.
  • supported metal catalysts comprise so-called promoters, in addition to the main active metal part and the support material.
  • a promoter is a substance that enhances the catalyst's performance in terms of any of activity, selectivity to a given product or fraction of products, stability under the operation conditions, or combinations thereof.
  • the Fischer-Tropsch catalyst comprises at least one metal promoter which assists the reduction of cobalt species and which is selected form the list of ruthenium, rhenium, platinum, palladium, silver, gold, copper, preferably form the list of ruthenium, rhenium, platinum, palladium, and more preferably from the list of ruthenium, rhenium, platinum.
  • the Fischer-Tropsch catalyst comprises at least one promoter element which adds to the stability of the support material under the hydrothermal conditions encountered in the Fischer-Tropsch synthesis reaction.
  • Said promoter element can be selected from the list of alkali metals, alkaline earth metals, lanthanides, transition metals, boron, aluminium, gallium, indium, carbon, silicon, germanium, tin, nitrogen, phosphor, arsenic, antimony, and any combination thereof. Any of these elements can be either in elementary form or in ionic form.
  • the Fischer-Tropsch catalyst comprises at least one promoter element which contributes to a higher selectivity to olefin Fischer-Tropsch products under standard reaction conditions for the Fischer-Tropsch synthesis.
  • Said promoter element can be selected from the list of alkali metals, alkaline earth metals, lanthanides, yttrium, scandium, titanium, zirconium, chromium, manganese, iron, zinc, gallium, boron, indium, germanium, tin, phosphor, sulfur, and any combination thereof. Any of these elements can be either in elementary form or in ionic form.
  • the stream leaving the Fischer-Tropsch catalyst which contains the unconverted syngas as well as the Fischer-Tropsch products, is sent on a hydrotreating solid catalyst where part of the primarily linear hydrocarbons generated on the Fischer-Tropsch catalyst are further processed by catalytic reactions which comprise oligomerization, hydride transfer, (hydro)isomerization and/or (hydro)cracking.
  • the hydrotreating catalyst comprises a metal promoter and an acidic component.
  • Said acid component can be selected from materials such as amorphous silica-alumina, tungstated zirconia, zeolites or a non-silicoaluminate zeotypes.
  • the inventors believe that one hydrotreating catalyst in which the acidic component is active for the reaction of oligomerization of short-chain olefins (C2- C 4 ) is preferred to attain a more desirable ultimate hydrocarbon product distribution, as short-chain olefin oligomerization reactions contribute a net chain- growth pathway which reduces the selectivity to tail-gas hydrocarbons.
  • the acidic component of the hydrotreating catalyst is a zeolite classified as "medium-pore” according to the IZA.
  • the statement "medium pore” as used herein means having a crystallographic free diameter in the range of from about 3.9 to about 7.1 Angstrom when the zeolitic material is in the calcined form.
  • the crystallographic free diameters of the channels of molecular sieves are published in the "Atlas of Zeolite Framework Types", Fifth Revised Edition, C H. Baerlocher, W. M. Meier, and D. H. Olson (Editors), Elsevier, Amsterdam, 2001 .
  • said zeolite component is selected from the list of zeolite topologies comprising MFI, FER, MWW, TON, MTT, MTW, MEL, EMT, IMF, TUN. More preferably the zeolite has a MFI topology (trade name ZSM-5).
  • MFI topology trade name ZSM-5.
  • Si/AI Si to Al
  • the zeolite component of the hydrotreating catalyst is relatively hydrophobic as it displays a Si/AI atomic ratio greater than 20, and more preferably greater than 30.
  • microporous domains refers to those regions within the zeolite crystals which comprise exclusively pores in the micropore size regime, i.e. ⁇ 2 nm in diameter.
  • microporous domains are delimited by larger pores in the mesopore or macropore regimes in the case that the zeolite crystals display multiple pore modes, or by the outer boundary of the individual zeolite crystals in the case of zeolites which are entirely microporous and hence do not display intra-crystal meso- or macropores.
  • the average size of the microporous domains in the zeolite acid component of the hydrotreating catalyst is smaller than 500 nm, and more preferably smaller than 100 nm.
  • the hydrotreating catalyst incorporates a metal component dispersed in the form of nanoparticles on the acidic component.
  • these components are usually added as a metal precursor salt by methods which are known in the art, such for instance impregnation, deposition precipitation, ion exchange, electrochemical deposition, electrostatic adsorption, co-precipitation.
  • the metal promoter is typically a metal or combination of metals selected from Group VIII noble and non-noble metals, Group 1 B coinage metals, and Group VIB metals.
  • Noble and coinage metals which can be used include platinum, palladium, rhodium, ruthenium, osmium, silver, gold and iridium, or any combination thereof.
  • the nature of the metal component is selected to bind carbon monoxide strongly under the typical operation conditions of the hydrotreating catalyst in the process of the invention.
  • the inventors believe that partial inhibition of the hydrogenation catalytic activity of the metal component in the hydrotreating catalyst by strong adsorption of carbon monoxide from the syngas unconverted on the upstream Fischer-Tropsch catalyst contributes to the preservation of an unusually high partial pressure of olefins in the reaction medium, hence enabling their beneficial technical effect on the ultimate hydrocarbon product distribution.
  • said metal component is selected from the list of platinum and platinum-containing multimetallics.
  • the catalysts may be present within the reactor as pellets, spheres, extrudates, irregular shaped granules, coated monoliths, etc, of various possible sizes, depending of the type of reactor and the fluid-solid dynamics experienced in said reactor.
  • the Fischer-Trospch catalyst is present as particles in the size range of 50-1000 micrometers, and more preferably in the size range of 50-500 micrometers, a size which is suitable for compact tubular milli-reactors.
  • the Fischer-Tropsch catalyst is present as a layer coated on the outer surface of a monolithic substrate or a micro-reactor module.
  • the catalysts Prior to their use in catalysis, the catalysts might be subjected to thermal treatments in the presence of hydrogen or an alternative reducing agent to render their metal components into the metallic state.
  • said reduction treatment takes place at a temperature in the range of 473-873K, and more preferably in the range of 573-773K.
  • Said reduction treatment can be performed in situ, i.e. once the catalysts have been loaded into the reactor.
  • Drawing 1 Pore size distribution as determined by mercury intrusion porosimetry for a gamma-AI 2 O3 porous support material for the synthesis of a Fischer-Tropsch catalyst according to one embodiment of the present invention.
  • Drawing 2. Pore size distribution as determined by mercury intrusion porosimetry for a commercial gamma-AI 2 O3 porous support material representative of those employed for the synthesis of Fischer-Tropsch catalysts according to state of the art procedures.
  • Macropore and mesopore size distributions, as well as total macropore volumes were determined by means of mercury intrusion porosimetry in a Micromeritics AutoPore IV 951 apparatus.
  • 80-150 mg of sample (0.4-0.6 mm) were dried at 383 K for 72 h before the measurement.
  • the intrusion-extrusion isotherms were recorded at room temperature in the pressure range of 6.9 ⁇ 10 4 - 4.1 ⁇ 10 4 Pa with an equilibration rate of 0.1 ⁇ _ g "1 s ⁇ 1 .
  • pore diameter and volume For the determination of pore diameter and volume, a geometrical pore model was considered, with a Hg density of 13.55 g cm "3 and a contact angle of 141 °.
  • Micropore volume, mesopore volume and specific surface area were determined by means of nitrogen physisorption. Nitrogen physisorption isotherms were recorded at 77K using a Micromeritics ASAP instrument after degassing the sample (ca. 100 mg, 0.4-0.6 mm particle size) at 523 K under vacuum for 10 h. Surface areas were derived using the B.E.T method in the relative pressure (P/Po) regime of 0.05-0.30. Total micropore volumes were determined by the t-plot method in the statistical thickness range of 3.5-5 Angstroms.
  • the macroscopic particle size of the catalysts was adjusted and determined using calibrated Retsch solid stainless steel sieves tested according to the ISO 3310 norm.
  • the particle size range was defined as the opening size of the two sieves between which more than 80% of the catalyst particles were retained.
  • the cobalt metal loading in the catalysts was determined by means of hydrogen temperature-programmed reduction (H 2 -TPR) in a Micromeritics Autochem 2910 device.
  • H 2 -TPR hydrogen temperature-programmed reduction
  • a Micromeritics Autochem 2910 device In a typical experiment, about 100 mg of sample were initially flushed with Ar flow (50 cm 3 min "1 ) at room temperature for 30 min, then the gas was switched to 10 vol% H 2 in argon (Ar) and the temperature increased up to 1 123 K at a heating rate of 10 K min "1 .
  • a downstream 2-propanol/dry ice trap was used to retain the water generated during the reduction.
  • the H 2 consumption rate was monitored in a thermal conductivity detector (TCD) previously calibrated via the injection of known volumes of hydrogen using a gas syringe.
  • TCD thermal conductivity detector
  • the cobalt loading was determined form the total hydrogen consumption assuming all cobalt to be present as Co3O 4 in the calcined catalysts, i.e. prior to the H 2 -TPR experiment, and full reduction to metallic cobalt, which results in a reduction stoichiometric H 2 /Co molar ratio of 4/3.
  • the hydrogen consumption associated to the Ru promoter was considered negligible.
  • a ruthenium-promoted cobalt-based Fischer-Tropsch catalyst was synthesized as follows. High-purity dispersible nano-boehmite (75% AI 2 O3, Sasol) was used as precursor and a polyethyleneglycolether non-ionic surfactant (Tergitol 15-S-7, Sigma-Aldrich) was employed as porogen to synthesize the gamma-AI 2 O3 support.
  • a synthesis gel was prepared by dispersing the nano-boehmite precursor in a solution of the surfactant in Dl water to achieve a final gel molar composition of AI :EO:H 2 O 1 :1 1 .5:49, where EO represents the ethylenoxide building units in the polymer (ca. 7 mol EO/mol surfactant).
  • the gel was stirred vigorously at room temperature using a laboratory vertical stirrer (450 rpm) for 5 hours, transferred into a polypropylene autoclavable bottle and treated hydrothermally at 343 K in an oven for 48 h.
  • the resulting gel was transferred into an evaporation dish and let dry at 343 K for 72 hours in an oven with internal air circulation.
  • the solid was transferred into a muffle oven, dried at 393 K for 3h, and then heated to 813 K (0.5 K min "1 ) for the crystallization of gamma-AI 2 O3 and the combustion of the organic porogen.
  • the muffle oven is equipped with convective air-extraction as required to rapidly evacuate volatile organic material and avoid the generation of igniting gas mixtures in the chamber.
  • the solid was sieved and the 0.4-0.6 mm fraction was further employed.
  • the volume of solution applied was equivalent to the total mesopore volume of the support material as determined by N 2 physisorption.
  • one ruthenium-promoted cobalt- based Fischer-Tropsch catalyst was synthesized as follows.
  • Commercial high- purity gamma-AI 2 O3 microgranules (Sasol Materials, Germany) were sieved and the 0.4-0.6 mm fraction was further employed as support materials.
  • Analysis of the porosity of the calcined material using mercury intrusion porosimetry revealed one single level of porosity (drawing 2 shows the corresponding pore diameter distribution), in the range of mesopores (2-50 nm in diameter), peaking at ca. 9 nm.
  • metal species were incorporated by impregnation.
  • the volume of solution applied was equivalent to the total mesopore volume of the support material as determined by N 2 physisorption.
  • the solid was dried at 343 K under N 2 flow (200 cm 3 g ca t "1 min "1 ) for 10 hours and the nitrate metal precursors further decomposed by calcination at 623 K for 3h under N 2 flow (heating rate of 2 K min "1 ). The impregnation and calcination steps were repeated to achieve a cobalt weight loading of 20.0 wt% in the final catalyst.
  • the Pt loading as determined by quantitative Energy Dispersion X-ray (EDX) spectroscopy in a S-3500 N (Hitachi) Scanning Electron Microscope was 0.6 wt%.
  • one hybrid catalyst composed of both a Fischer-Tropsch and a hydrotreating catalyst in very close intimacy, blended at the single catalyst particle (pellet) level was prepared as follows.
  • High-purity dispersible nano-boehmite (75% AI2O3, Sasol) was used as precursor for gamma- AI2O3.
  • the dispersible nano-boehmite and the nanocrystalline H-ZSM-5 zeolite were co-suspended in deionized water (4.8 g nano-boehmite, 10 g H-ZSM-5, 180 ml_ Dl water).
  • the suspension was stirred vigorously in a polypropylene bottle at room temperature using a laboratory vertical stirrer (450 rpm) while heated to 343 K and let dry overnight in an oil bath.
  • the dried composite material (support) was grinded in a mortar and calcined at 623 K for 5h.
  • the calcined composite was pelletized at 80 bar and sieved between 0.4-0.6 mm.
  • the Fischer-Tropsch/hydrotreating composite catalyst was then prepared by incipient wetness impregnation of said pre-sieved support material.
  • the volume of solution applied was equivalent to the total mesopore volume of the support as determined by N 2 physisorption.
  • the solid was dried at 343 K under N2 flow (200 cm 3 g ca t " 1 min "1 ) for 10 hours and the nitrate metal precursors further decomposed by calcination at 623 K for 3h under N 2 flow (heating rate of 2 K min "1 ).
  • the Fischer-Tropsch catalyst prepared according to Example I in accordance to the present invention, was tested under reaction conditions representative of an industrial Fischer-Tropsch process.
  • the reaction experiment was performed in a 316L stainless-steel packed-bed tubular reactor (12 mm inner diameter). Gas feeds, i.e. H 2 (99.999%, Air Liquide) and a premixed syngas mixture (CO:H 2 :Ar 3:6:1 , Ar as internal standard for chomatography, from Air Liquide) were fed using calibrated mass flow controllers (Bronkhorst).
  • the catalyst particles (400-600 ⁇ ) were blended and diluted with SiC (350-560 ⁇ , grit 46) granules and loaded into the reactor to achieve a constant packed-bed volume of 6.5 cm 3 .
  • a closed capillary sheathing two thermocouples was axially inserted in the bed enabling independent temperature reading and control at the upper and bottom halves of the catalyst bed.
  • the catalyst Prior to catalysis, the catalyst was reduced at atmospheric pressure under H 2 flow (200 mL min "1 ) at 673 K for 8 h. After reduction, the reactor was cooled to 423 K and the gas flow was switched to syngas. After 5 min, the system was pressurized to the reaction pressure of 20 bar, which was further controlled during the reaction experiments using a membrane dome pressure regulator (GO regulator).
  • GO regulator membrane dome pressure regulator
  • the reactor temperature was slowly and stepwise increased to the desired reaction temperature (0.5 K min " 1 to 453 K followed by 0.1 K min "1 to 483 K).
  • the syngas WHSV was adjusted in the range of (1 -5 gCO g ca t "1 h "1 ), in order to achieve a pre-set CO conversion of 30 ⁇ 5 % in the pseudo-steady state, reached after >30 h on-stream, and characterized by CO conversion variations of ⁇ 0.2% h "1 .
  • Downstream of the tubular reactor two consecutive cold traps were set at temperatures of 423 and 373 K, respectively, at the reaction pressure, to collect heavy hydrocarbon products and part of the produced water. The rest of all pipelines downstream of the reactor were kept at a temperature of 443 K to prevent condensation.
  • Example II In a general comparison method, the Fischer-Tropsch catalyst prepared according to Example II, hence not in accordance to the present invention, was tested under reaction conditions representative of an industrial Fischer-Tropsch process. Aside from the different catalyst employed, the reaction experiment was performed as described in Example V. The performances of the Fischer-Tropsch catalyst prepared according to the present invention (Example I) and a comparative catalyst prepared by state of the art procedures on a commercially available support material (Example II) are compared in Table 1 . Table 1
  • Example V Mass ratio of alpha-olefin to paraffin (O/P) for hydrocarbon products with the corresponding chain-length.
  • a Fischer-Tropsch catalyst prepared according to the present invention produces a hydrocarbon product stream with a similar chain-length distribution but a notably higher alpha- olefin to paraffin mass ratio in the hydrocarbon chain length range of C3-C10 than a Fischer-Tropsch catalyst prepared, for comparative purposes, on a commercially available support material (Example VI) following state-of-the-art procedures.
  • the Fischer-Tropsch catalyst prepared according to Example I was integrated with a hydrotreating catalyst prepared according to Example III, and tested for the direct conversion of syngas to liquid hydrocarbons. Both catalysts were blended and loaded into a single packed bed in a tubular reactor, a process configuration not in accordance to the present invention and presented for reference purposes.
  • the reaction experiments were performed in a 316L stainless-steel packed-bed tubular reactor (12 mm inner diameter). Gas feeds, i.e.
  • H 2 (99.999%, Air Liquide) and a premixed syngas mixture (CO:H 2 :Ar 3:6:1 , Ar as internal standard for chomatography, from Air Liquide) were fed using calibrated mass flow controllers (Bronkhorst).
  • the particles (400-600 ⁇ ) of the Fischer-Tropsch catalyst were blended with the required amount of the particles (400-600 ⁇ ) of the hydrotreating catalyst, the resulting blend further diluted with SiC (350-560 ⁇ , grit 46) granules and loaded into the reactor to achieve a constant packed-bed volume of 6.5 cm 3 .
  • thermocouples were axially inserted in the bed enabling independent temperature reading and control at the upper and bottom halves of the catalyst bed.
  • the catalysts Prior to catalysis, the catalysts were reduced at atmospheric pressure under H 2 flow (200 mL min "1 ) at 673 K for 8 h. After reduction, the reactor was cooled to 423 K and the gas flow was switched to the above mentioned syngas mixture. After 5 min, the system was pressurized to the reaction pressure of 20 bar, which was further controlled during the reaction experiments using a membrane dome pressure regulator (GO regulator). Next, the reactor temperature was slowly and stepwise increased to the desired reaction temperature using heating rates of: 0.5 K min "1 to 453 K followed by 0.1 K min "1 to the final reaction temperature of 523 K.
  • GO regulator membrane dome pressure regulator
  • the syngas weight hourly space velocity (WHSV) was adjusted in the range of (1 -5 g CO g ca t "1 h "1 ), in order to achieve a pre-set CO conversion level of 30 ⁇ 5% in the pseudo steady state, reached after > 30 h on-stream, and characterized by CO conversion variations of ⁇ 0.2% h ⁇ 1 .
  • the mass ratio of the Fischer-Tropsch and the hydrotreating catalyst was selected to achieve an overall ratio between the molar flow of carbon in the Fischer-Tropsch products generated per pass in the reactor and the mass of hydrotreating catalyst of 0.075 mol C h "1 g ca t "1 - Downstream of the tubular reactor two consecutive cold traps were set at temperatures of 423 and 373 K, respectively, at the reaction pressure, to collect heavy hydrocarbon products and part of the produced water. The rest of all pipelines downstream of the reactor were kept at a temperature of 443 K to prevent condensation. The lighter fraction of hydrocarbons leaving the traps was depressurized in the dome pressure controller and analyzed online by gas chromatography (GC). The trapped hydrocarbons were collected, separated from the water fraction and weighed.
  • GC gas chromatography
  • the Fischer-Tropsch catalyst prepared according to Example II was integrated with a hydrotreating catalyst prepared according to Example III, and tested for the direct conversion of syngas to liquid hydrocarbons. Both catalysts were blended and loaded into a single packed bed in a tubular reactor, a process configuration not in accordance to the present invention and presented for reference purposes. Aside from the fact that a different Fischer-Tropsch catalyst was employed, the reaction experiment was performed as described in Example VII.
  • Example VII the hybrid Fischer-Tropsch/hydrotreating catalyst prepared according to Example IV, hence not according to the present invention, was tested for the direct conversion of syngas to liquid hydrocarbons.
  • the catalyst was loaded into a single packed bed in a tubular reactor, a process configuration not in accordance to the present invention and presented for reference purposes.
  • the reaction experiment was performed as described in Example VII.
  • the Fischer-Tropsch catalyst prepared according to Example I was combined with a hydrotreating catalyst prepared according to Example III, and tested for the direct conversion of syngas to liquid hydrocarbons.
  • Each catalyst was placed in a different, and spatially distant packed bed along a tubular reactor, enabling independent control of the working temperature for each of the catalysts, a process configuration in accordance to one of the embodiments of the present invention.
  • the reaction experiment was performed in a 316L stainless-steel packed-bed tubular reactor (12 mm inner diameter). Gas feeds, i.e. H 2 (99.999%, Air Liquide) and a premixed syngas mixture (CO:H 2 :Ar 3:6:1 , Ar as internal standard for chomatography, from Air Liquide) were fed using calibrated mass flow controllers (Bronkhorst).
  • the particles (400-600 ⁇ ) of the hydrotreating catalyst prepared according to Example III were diluted with SiC (350-560 ⁇ , grit 46) granules and loaded into a packed bed at the bottom half of the reactor.
  • the particles (400-600 ⁇ ) of the Fischer-Tropsch catalyst were diluted with SiC (350-560 ⁇ , grit 46) granules and loaded as a separate packed bed at the upper half or the reactor bed, upstream from the packed bed containing the hydrotreating catalyst.
  • Both catalyst packed-beds were had a constant volume of 4 cm3, were held by means of plugs of quartz wool and spaced at least 4 cm.
  • a closed capillary sheathing two thermocouples was axially inserted through the center axis of both beds. The tips of the thermocouples were placed corresponding with the overall center of both packed-beds, enabling independent temperature control on the two catalysts.
  • the catalysts Prior to catalysis, the catalysts were reduced at atmospheric pressure under H2 flow (200 ml_ min "1 ) at 673 K for 8 h. The same temperature was set for both beds during the reduction pre-treatment. After reduction, the reactor was cooled to 423 K and the gas flow was switched to the above mentioned syngas mixture. After 5 min, the system was pressurized to the reaction pressure of 20 bar, which was further controlled during the reaction experiments using a membrane dome pressure regulator (GO regulator). Next, the reactor temperature was slowly and stepwise increased to the desired reaction temperature using heating rates of: 0.5 K min "1 to 453 K followed by 0.1 K min "1 to the final reaction temperature, which was 483K and 523 K for the upper bed and bottom beds, respectively.
  • H2 flow 200 ml_ min "1
  • the syngas weight hourly space velocity (WHSV) was adjusted in the range of (1 -5 g CO g ca t " 1 h "1 ), in order to achieve a CO in the range of 50 ⁇ 15%.
  • the mass ratio of the Fischer-Tropsch and the hydrotreating catalyst were selected to achieve an overall ratio between the molar flow of carbon in the Fischer-Tropsch products generated per pass in the reactor and the mass of hydrotreating catalyst of 0.075 mol C 1 h "1 g ca t " 1 - Downstream of the tubular reactor two consecutive cold traps were set at temperatures of 423 and 373 K, respectively, at the reaction pressure, to collect heavy hydrocarbon products and part of the produced water.
  • the Fischer-Tropsch catalyst prepared according to Example II was combined with a hydrotreating catalyst prepared according to Example III, and tested for the direct conversion of syngas to liquid hydrocarbons.
  • Each catalyst was placed in a different, and spatially distant packed bed along a tubular reactor, enabling independent control of the working temperature for each of the catalysts.
  • the reaction experiment was performed as described in Example X.
  • Syngas weight space velocity based on the total mass of the two catalysts.
  • a Fischer-Tropsch catalyst prepared according to the present invention and integrated with a hydrotreating catalyst in a process configuration according to the present invention, i.e. with both catalysts operated in a spatially compartmentalized fashion and with individual temperature control (Example X), leads to an ultimate hydrocarbon product distribution with a significantly higher (54-96% higher) contribution from hydrocarbons in the middle-distillate range (C10-C25) and a significantly lower (36- 47% lower) contribution from tail-gas hydrocarbons (C 4- ) than either alternative process configurations or the same process configuration employing comparative Fischer-Tropsch catalysts or hybrid Fischer-Tropsch/hydrotreating catalysts not prepared according to the present invention.

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Abstract

Selon un premier aspect, l'invention concerne un procédé de conversion d'un débit d'entrée comprenant du monoxyde de carbone et de l'hydrogène en tant que composants majeurs (gaz de synthèse) en hydrocarbures liquides au moyen de la combinaison d'un catalyseur solide de Fischer-Tropsch et d'un catalyseur solide d'hydrotraitement dans des lits de catalyseur séparés fonctionnant à différentes températures de réaction. Dans un second aspect, l'invention concerne un catalyseur de Fischer-Tropsch à porosité multimodale à appliquer dans ledit procédé et le procédé de préparation dudit catalyseur de Fischer-Tropsch.
PCT/EP2018/055237 2017-03-06 2018-03-04 Procédé série de conversion de gaz de synthèse en hydrocarbures liquides, dispositif utilisé à cet effet comprenant des catalyseurs ft et ht, catalyseur ft WO2018162363A1 (fr)

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GB2582220B (en) * 2019-03-14 2022-08-24 Johnson Matthey Plc Cobalt catalysts and precursors therefor
US11865523B2 (en) 2019-03-14 2024-01-09 JohnsonMatthey Public Limited Company Cobalt catalysts and precursors therefor

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