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WO2010071967A1 - Procédé fischer-tropsch à basse pression - Google Patents

Procédé fischer-tropsch à basse pression Download PDF

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Publication number
WO2010071967A1
WO2010071967A1 PCT/CA2008/002306 CA2008002306W WO2010071967A1 WO 2010071967 A1 WO2010071967 A1 WO 2010071967A1 CA 2008002306 W CA2008002306 W CA 2008002306W WO 2010071967 A1 WO2010071967 A1 WO 2010071967A1
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Prior art keywords
catalyst
fischer
tropsch
cobalt
weight
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PCT/CA2008/002306
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English (en)
Inventor
Conrad Ayasse
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Canada Chemical Corp
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Canada Chemical Corp
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Priority to PCT/CA2008/002306 priority Critical patent/WO2010071967A1/fr
Priority to PCT/CA2009/001862 priority patent/WO2010071989A1/fr
Priority to MYPI2011002900A priority patent/MY160250A/en
Priority to AU2009329785A priority patent/AU2009329785B2/en
Priority to EP09833974A priority patent/EP2379676A4/fr
Priority to CA2748216A priority patent/CA2748216C/fr
Priority to CN200980157057.XA priority patent/CN102325858B/zh
Priority to MX2011006743A priority patent/MX2011006743A/es
Priority to RU2011130432/04A priority patent/RU2487159C2/ru
Priority to ARP090105016A priority patent/AR074831A1/es
Publication of WO2010071967A1 publication Critical patent/WO2010071967A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
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    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C01B2203/0894—Generation of steam
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C01B2203/1294—Evaporation by heat exchange with hot process stream
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • Y02T50/678—Aviation using fuels of non-fossil origin

Definitions

  • This invention relates to a Fischer-Tropsch process for converting carbon monoxide and hydrogen to diesel fuel or diesel blending stock with a high cetane number in a concentration of 65-90+wt %, at pressures below 200 psia, using a particular defined cobalt catalyst with crystallites of a size greater than 16 nanometers.
  • the Fischer-Tropsch (FT) process for converting carbon monoxide and hydrogen to liquid motor fuels and/or wax has been known since the 1920' s.
  • Another factor in selecting the best reformer type is the nature of the reformer hydrocarbon feed gas. If the gas is rich in CO 2 , this can be advantageous because the desired H 2 /CO ratio can then be achieved directly in the reformer gas without the need to remove excess hydrogen, and some of the CO ⁇ is converted to CO, increasing the potential volume of liquid hydrocarbon product that can be produced. Additionally, the volume of steam that is required is reduced, which reduces the process energy requirements,
  • the reformers use some form of autothermal reforming with oxygen produced cryogenically from air, an expensive process in terms of operating cost and capital cost.
  • the ecomonies of scale justify the use of high operating pressure, the use of oxygen natural gas reforming, extensive tail gas recycling to the FT reactor for increasing synthesis gas conversion and controlling heat removal and product wax hydrocracking.
  • an ecomomical FT plant design has not been developed for small plants with capacities of less than 100 million scfd.
  • the present invention strives for optimized economics in a completely different market: small FT plants using less than 100 million scfd. The emphasis is on simplicity and minimized capital cost, somewhat at the expense of efficiency.
  • the catalytic hydrogenation of carbon monoxide to produce a variety of products ranging from methane to heavy hydrocarbons (up to do and higher) as well as oxygenated hydrocarbons is usually referred to as Fischer-Tropsch synthesis.
  • the high molecular weight hydrocarbon product primarily comprises normal paraffins which can not be used directly as motor fuels because their cold properties are not compatible.
  • Fischer-Tropsch hydrocarbon products can be transformed into products with a higher added value such as diesel, jet fuel or kerosene. Consequently, it is desirable to maximize the production of high value liquid hydrocarbons directly to that component separation or hydrocracking are not necessary.
  • CatalytJcally active group VIII in particular, iron, cobalt and nickel are used a"? Fiseh p r-TrrmKeii mtalysts; cobalt/ruthenium is one of the most common catalyzing systems.
  • the catalyst usually contains a support or carrier metal as well as a promoter, e.g., rhenium.
  • Metal oxides e.g., silica, alumina, titania, zirconia or mixture thereof, have been utilized as catalyst supports in Fischer-Tropsch hydrocarbons synthesis.
  • U.S. Pat. No. 4,542,122 disclosed a cobalt or cobalt thoria on titania as a hydrocarbon synthesis catalyst
  • U.S. Pat, No. 4,088,671 disclosed a cobalt-ruthenium catalyst where alumina was used as a support.
  • European Pat No. 142,887 described a silica supported cobalt catalyst together with zirconium, titanium, ruthenium and/or chromium.
  • U.S. Pat, No. 4,801,573 described a promoted cobalt and rhenium catalyst supported on alumina.
  • the amount of cobalt is most preferably about 10-40wt% of the catalyst.
  • rhenium is preferably about 2-20wt of cobalt content.
  • U.S. Pat. No, 5,248,701 disclosed a copper promoted cobalt-manganese spinel that was said to be useful as a Fischer-Tropsch catalyst with selectivity for olefins and higher paraffins.
  • U.S. Pat, No. 4,738,948, issued in Apr. 19, J 988 describes a catalyst comprising cobalt ruthenium at an atomic ratio of 10-400, on a refractory carrier, such as titania or silica,
  • the catalyst is used for conversion of synthesis gas with an H 2 :C0 ratio of 0.5-10, preferably 0.5-4, to Cs-Cw hydrocarbons at a pressure of 80-6O0psig and at a temperature of 160-300 0 C, at a gas hourly space velocity of 100-5000 v/hr/v.
  • This catalyst was achieved by using a gas containing carbon monoxide and less than 30% hydrogen at a temperature more than 1O°C above Fischer-Tropsch conditions in the range 100-500"C at a pressure of 0.5-1 Obar, for air, at least lOmin preferably 1-12 hours.
  • Fischer-Tropsch synthesis performed at low pressure, 17-21 atmospheres, and relatively high temperature, usually produces short chain hydrocarbons of 0.6-0.7 chain growth probability factor.
  • U.S. Pat App. No 20050209348 published on Sep. 22, 2005 described a Fischer-Tropsch process performed at an elevated temperature between 230-280 0 C, for example 24O 0 C and at elevated pressure typically between 1.7MPa and 2.IMPa, for example 1.8MPa, using a compact reactor.
  • the preferred catalyst comprised a coating of gamma alumina support with 10-40% cobalt (by weight compared to the alumina) and with a promoter such as ruthenium, platinum or gadolinium which is less than 10% of the cobalt weight.
  • the gas hourly space h for example 20000hr " ' and the produced hydrocarbon liquid consisted of saturated linear alkanes of chain lengths range between about 6-17. Consequently, it is rich in aircraft fuel.
  • the selectivity to the production of Cs + hydrocarbon was less than 65% and the conversion of carbon monoxide was no greater than 75%.
  • Fischer-Tropsch processes which can be used to directly produce different types of fuel such as, diesel fuel,
  • cobalt metal and oxide supports Under certain pretreatment and activation conditions, a strong interaction between cobalt metal and oxide supports forms undesirable cobalt-support structures, for example, cobalt aluminate, which may require high reduction temperature.
  • High reduction temperature can result in sintering cobalt crystallites and forming large cobalt metal clusters.
  • cobalt metal precursors and metal loading, as well as metal promoters affect the size of cobalt crystallites.
  • Low cobalt metal loading could result in high metal dispersion and small crystallites but enhances the metal-support interaction leading to poor reducibility and low catalyst activity.
  • the invention in one broad aspect comprises a low-pressure Fischer-Tropsch process and a catalyst that produces a high diesel-fraction yield.
  • Process pressure is below 200 psig.
  • the catalyst is cobalt deposited at greater than 5 weight percent on gamma alumina, optionally along with rhenium or ruthenium at 0.01 -2 wt. %. It has been discovered that this catalyst is very effective at low pressures in converting synthesis gas into diesel in high yield.
  • the present invention is particularly well suited to conversion of low pressure gases containing low molecular weight hydrocarbons into FT liquids. Examples of applications are landfill gas, oil field solution gas and low pressure gas from de-pressured gas fields. In all these cases, multiple-stage gas and air compression would be required in traditional FT plants.
  • the high efficiency of the present FT catalyst enables high CO conversion and produces a product stream containing up to 90+ wt. % diesel in a single pass.
  • the use of air in the natural gas reformer provides a synthesis gas containing approximately 50% nitrogen, which facilitates heat removal in the FT reactor as sensible heat and increases gas velocity and heat transfer efficiency, so that tail gas recycling is not needed.
  • Naphtha can be partially sepaiated from the hydrocarbon product by flash distillation at low cost to generate a more pure diesel product. This also serves to provide some product cooling.
  • the liquid hydrocarbon product is excellent for blending with petroleum diesel to increase cetane number and reduce sulfur content.
  • Tropsch process (hereinaftert "FT process") of the present invention is particularly ⁇ . « ⁇ «.,*; protest» ,, «. ; r,/ y * TM Kalt catalyst comprised of crystallites, wherein said crystallites have an average diameter greater than 16 nanometers.
  • Diesel fuel or diesel blending stock with high cetane number is prosuced as a Fischer-Tropsch product in a concentration of 65-90+ weight percent at pressures below 200 psia using a cobalt catalyst having such crystallites, in combination with rhenium and /or ruthenium promoter. After a rough flash, a substantially pure diesel can be produced,
  • Figure 1 is a process flow diagram for a particular embodiment of the invention
  • Figure 2 is a flow diagram for flash separation of naphtha and diesel hydrocarbon fractions as a subsequent step to the Fischer-Tropsch process of the present invention
  • Figure 3 is a graph showing C5+ carbon number distribution for the catalyst of Example 3 (trilobes) at 190 0 C;
  • Figure 4 is a graph showing the effect of pressure on the performance of the catalyst of Example 4.
  • Figure S is a graph showing the effect of carbon number on the % weight production of liquid fuels and/or waxes, at 190"C, 70 psia, using a CSS-350 alumina support (ie Example 7);
  • Figure 6 is a graph showing the effect of carbon number distribution on the % weight production of liquid fuels and/or waxes, at 200 9 C and 70 psia, using an LD-5 alumina support (ie. Example 8a);
  • Figure7 is a graph showing the effect of carbon number distribution on the % weight production of liquid fuels and/or waxes, at 19O 0 C at 70 spia using an n ⁇ _» — :_ a supp0]rt (je Example 9);
  • Figure 8 is a graph showing the effect of carbon number distribution on the % weight production of liquid fuels and/or waxes, for the catalyst of Example 10 using ruthenium promoter;
  • Figure 9 is a graph showing the effect of carbon number distribution on the % weight production of liquid fuels and/or waxes for the catalyst of Example 11 , using an Aerolyst 3038 silica catalyst support instead of alumina;
  • Figure 10 is a graph showing the relationship of cobalt catalyst crystallite size to wax content of C5+ F-T product.
  • Figure 11 is a graph showing a comparison of catalyst used in Example 9 carbon distribution with a traditional Anderson-Shultz-Flory distribution.
  • naphtha is indicated by large squares, diesel by diamonds and light waxes by small squares.
  • tail gas recycling is a very energy and capital intensive activity.
  • the separation of oxygen from air is also an energy and capital intensive activity.
  • the approach taken in the present process is to use air in the reformer, which gives a synthesis gas containing approximately 50 % nitrogen as inert diluent, eliminating the need for tail gas recycling to moderate FT reactor heat removal requirements.
  • Others employing air- blown synthesis gas in FT processes have achieved the desired high CO conversions by using multiple FT reactors in series, which entails high capital costs and complex operation.
  • the present process achieves high CO conversion in a simple single pass and a high diesel cut by using a special catalyst as more particularly described below.
  • the catalyst of the present invention in a preferred embodiment employs an alumina support with high cobalt concentration, along with a low level of rhenium to facilitate catalyst reduction.
  • the high cobalt concentrations increase catalyst activity, enabling high single-pass synthesis gas conversion.
  • the Anderson-Shultz-Florey theory predicts the FT hydrocarbons to cover a very wide range of carbon numbers, from 1-60, whereas the most desirable product is diesel fuel (C9-C13, Chevron definition).
  • diesel fuel C9-C13, Chevron definition.
  • a common approach is to strive to make mostly wax in the FT reactor and then, in a separate operation, to hydrocrack the wax to mostly diesel and naphtha.
  • the process and catalyst of the present invention makes diesel in high yield (to 90 wt%) directly in the FT reactor, obviating the need for expensive and complex hydrocracking facilities.
  • the present process can be applied economically in much smaller plants than hitherto considered possible for FT technology.
  • Figure 1 shows the process flow diagram for the present invention, wherein the letters A-k signify the following:
  • Letter A represents the raw hydrocarbon-containing process feed gas. This could be from a wide variety of sources: for example, from a natural gas field, a landfill facility (biogenic gas), a petroleum oil processing facility (solution gas), among others.
  • the pressure of the gas for the present process can vary widely, from atmospheric pressure to 200 psia or higher. Single-stage or two-stage compression may be required, depending on the source pressure and the desired process operating pressure. For example, for landfill gas, the pressure is typically close to atmospheric pressure and blowers are used to transmit the gas into combustion equipment. Solution gas, which is normally flared, must also be compressed to the process operating pressure.
  • Letter B represents hydrocarbon gas conditioning equipment.
  • the gas may require clean-up to remove components that would damage reformer or FT catalyst. Examples of these are mercury, hydrogen sulfide, silicones and organic chlorides. Organic chlorides, such as found in land-fill gas, produce hydrochloric acid in the reformer) which can cause severe corrosion. Silicones form a continuous silicon dioxide coating on the catalyst, blocking pores. Hydrogen sulphide is a powerful FT catalyst poison and is usually removed to 1.0 ppm or lower, Some gas, from sweet- gas fields, may not require any conditioning (clean-up). The hydrocarbon concentration in the raw gas affects the economics of the process because less hydrocarbon product is formed from the same volume of feed gas.
  • the process can operate with 50% or lower methane concentration, for example, using land-fill gas. There may even be reasons to operate the process even at a financial loss: for example to meet greenhouse gas government or corporate emission standards.
  • the process can operate with feed gases containing only methane hydrocarbon or containing natural gas liquids by the application of known reformer technologies. The presence of carbon dioxide in the feed gas is beneficial,
  • Letter C represents the reformer, which may be of several types depending on the composition of the feed gas.
  • a significant benefit of low pressure reformer operation is the lower rate of the Brouard reaction and diminution of metal dusting.
  • Partial oxidation reformers normally operate at very high pressure ie. 450 psia or greater, and so are not optimum for a low-pressure FT process. It is energetically inefficient, and can easily make soot, however, it does not require water, and makes a syngas with a H 2 ZCO ratio near 2,0, optimum for FT catalysts. Partial oxidation reformers may be employed in the present process,
  • Steam reformers are capital expensive and require flue gas heat recovery to maximize efficiency in large plants. Because the synthesis gas contains relatively low levels of inerts such as nitrogen, temperature control in the FT reactor can be difficult without tail gas recycling to the FT reactor. However, the low level of inerts enables recycling of some tail gas to the reformer tube-side, supplementing natural gas feed, or to the shell side to provide heat. Keeping in mind that FT tail gas must be combusted before venting in any event, this energy can be used for electrical generation or, better yet, to provide the reformer heat which would be otherwise be provided from burning natural gas. For small FT plants, steam reformers are a viable choice. Steam reformers may be employed in the present process.
  • Letter D represents the optional water that is injected as steam into the reformer. All reformer technologies except partial oxidation require the injection of steam.
  • Letter E represents an oxidizing gas, which could be air, oxygen or oxygen- enriched air.
  • Letter F represents a cooler for reducing the reformer outlet temperature from greater than 800 0 C. to close to ambient.
  • the cooling may be done in several stages, but preferably in a single stage.
  • the cooling may be achieved with shell- and- tube or plate- and- frame heat exchangers and the recovered energy may be utilized to preheat the reformer feed gases, as is well known in the industry.
  • Another way of cooling the reformer tail gas is by direct injection of water into the stream or by passing the stream through water in a vessel.
  • Letter G represents a separator for separating the reformer synthesis gas from condensed water, so as to minize the amount of water entering downstream equipment.
  • Letter H represents optional hydrogen removal equipment such as PrismTM hydrogen-selective membranes which are sold by Air Products, or Cynara membranes from Natco,
  • Certain reformer processes produce a synthesis gas too rich in hydrogen, some of which must be removed to achieve optimum FT reactor performance.
  • High hydrogen concentrations give rise to larger CO loss to producing methane instead of the desired motor fuels or motor fuel precursor such as naphtha.
  • Letter I represents typical FT reactors, which are of the fixed- bed or slurry 5 bubble type and either may be used. However, the fixed-bed is preferred because if its simplicity of operation and ease of scale-up.
  • Letter J represents a back-pressure controller which sets the process pressure. It may be placed in other locations depending on the product recovery and possible i o partial separation process employed.
  • Letter K represents product cooling and recovery.
  • Product cooling is typically accomplished by heat exchange with cold water and serves to pre-heat the water for use elsewhere in the FT plant. Separation is accomplished in a separator vessel 15 designed for oil/water separation.
  • a second alternative is to flash- cool the FT reactor product before the aforementioned cooler-separator as shown in Figure 2. This serves two purposes- firstly to reduce the product temperature and secondly to enable partial separation of the naphtha component in the produced hydrocarbon product, enriching the remaining liquid in the diesel component.
  • Figure 2 shows a process diagram, for flash separation of naphtha and diesel hydrocarbons, in which:
  • 5 1 is a fixed-bed Fischer Tropsch reactor.
  • 5 2 is a mixture of gases, water, naphtha, diesel and light waxes at ca.190-240 0 C and pressure greater than atmospheric.
  • 0 5 is a flash drum vessel.
  • 6 is a vapour phase consisting of stream 2 minus diesel and light waxes.
  • 7 is a cooler
  • 9 is a vessel to retain naphtha and water.
  • waste tailgas stream consisting mainly of inert gases and light hydrocarbons.
  • the FT products 2 flow through a pressure let-down valve 3 and into a flash drum 5.
  • the inert gases and lower-boiling hydrocarbons, water and naphtha go overhead as vapour out of the flash drum and through cooler 7.
  • the diesel and light waxes collect in vessel 5.
  • the remaining gases exit overhead in stream 10 and are typically combusted, sometimes with energy recovery, or are used to generate electricity.
  • Catalyst synthesis was conducted by ordinary means as practiced by those knowledgable in the art.
  • the catalyst support was alumina trilobe exmidate obtained 5 from Sasol Germany GmbH (hereafter referred to as 'trilobe').
  • the extrudate dimensions were 1.67 mm diameter and 4.1 mm length.
  • the support was calcined in air at 500 0 C. for 24 hours.
  • a solution mixture of cobalt nitrate and perrhenic acid was added to the support by the method of incipient wetness to achieve 5 wt% cobalt metal and 0.5 wt.% rhenium metal in the finished catalyst.
  • the catalyst was dried i o slowly and then heated in a convection oven at the rate of 1.0 0 C per minute to 350 0 C. and held at that temperature for 12 hours.
  • a volume of 29 cc of oxidized catalyst was placed in a Vi inch OD tube that had an outer annular space through which temperature-control water was flowed under pressure in order to remove the heat of reaction.
  • the FT reactor was a shell-and-tube heat exchanger with catalyst
  • the catalyst used was the same as Example 1, except that the cobalt metal loading was 10 wt%.
  • the catalyst used was the same as Example 1 , except that the cobalt metal loading was 15 wt%.
  • EXAMPLE 4 The catalyst used was the same as Example 1. except that the cobalt metal loading was 20 wt%.
  • the catalyst used was the same as Example 1 , except that the cobalt metal loading was 26 wt%.
  • the catalyst used was the same as Example 1, except that the cobalt metal loading was 35 wt%.
  • the catalyst used was the same as used in Example 1 , except that the alumina support was CSS-350, obtained from Alcoa, and the cobalt loading was 20 weight percent. This support is spherical with a diameter of 1/16 inch.
  • the catalyst used was the same as used in Example 1, except as follows:
  • Catalyst 8a was identical to Catalyst I, except that the alumina support was LD-S, obtained from Alcoa, and the cobalt loading was 20 weight percent. This support is spherical with an average particle distribution of 1963 microns. Example 8a used the particle size mixture as received. Some of the original particles were ground to
  • Atalysts 8b, 8c and 8d were made with particles of diameter 214, 359 and 718 microns respectively, The cobalt loading in Examples 8b, 8c and 8d was identical to Example 8a.
  • EXAMPLE 9 The catalyst used was the same as used in Example 1, except that the alumina support was F-220, obtained from Alcoa, and the cobalt loading was 20 weight percent.
  • F-220 is a spherical support with a mesh size distribution of 7/14.
  • EXAMPLE 10 The catalyst used was the same as used in Example 4, except that the promoter was ruthenium rather than rhenium.
  • the catalyst used was the same as used in Example 3, except that Aerolyst 3038 silica catalyst support from Degussa was used instead of alumina.
  • the above catalysts were each analyzed for average crystallite size (d(CoO), Dispersion (D%) and Degree of Reduction (DOR) using a Chembet 3000 (Quantachrome Instruments) TPR/TPD analyzer.
  • the catalyst was reduced at 325 0 C in H 2 flow and cobalt dispersion was calculated assuming that one hydrogen molecule covers two cobalt surface atoms.
  • Oxygen chemisorption was measured with a series of (027He) pulses passed through the catalyst at 38O 0 C temperature after reducing the catalyst at 325 0 C.
  • Examples 1-6 were conducted at various temperatures, and the temperature that gave the largest amount of hydrocarbon product is listed, It is clear that 5% cobalt was not enough to provide a useful amount of liquid hydrocarbons: the best concentration was 20 wt% Co, which gave 1.03 ml/h. The concentration of diesel range hydrocarbons in the hydrocarbon product was 75.3-92.5 % at cobalt loadings of
  • Figure 3 shows the carbon number distribution for the catalyst of Example 3.
  • the catalyst of Example 4 was run in the standard testing rig as described above at a temperature of 202.5 0 C. at a variety of pressures. Results in Table 3 (below) and Figure 4 indicate that productivity of the catalyst for production of liquid hydrocarbons was significant at low pressures down to 70 psia, with the optimum results obtained at pressures between 70 psia and 175 psia. Preferred pressures are 70-350 psia and most preferably from 70 to 175 psia. The diesel fraction over that pressure range was fairly constant at 70.8-73.5 weight percent. As shown in Table 8, the catalyst of Example 4, with 20 % cobalt had an average crystallite size of 22.26 nm and a C5+ wax fraction of 6.8 wt % enabling the product to be used as a diesel blend.
  • FIG. 5 is a graph showing the effect of carbon number on the % weight production of liquid fuels and/or waxes, at 190 0 C, 70 psia, using a CSS-350 alumina support (ie Example 7).
  • Figure 5 shows the narrow carbon number range in the liquid product at 190 ° C, with 89.6% in the diesel range. Cetane number was 81.
  • the crystallite size was 18.26 nm, and the wax fraction was 7.2% enabling the product to be used as a diesel blend.
  • catalysts 8b, 8c and 8d showed Co metal dispersion higher than for Catalyst 8a.
  • Catalysts that contain CoO average crystallite sizes below 16 nanometers gave a high wax cut in the FT product of 17.6-19.3% wt
  • catalyst 8a which contained CoO crystallites larger than 16 nm (actually, 23.06 nm) gave a lower wax cut of 7.4 weight percent in the C5+ liqiud, enabling the product to be used as a diesel blend.
  • Example 8a (LD-5) at 200 0 C, 70 psia.
  • Example 9 catalyst was tested at 70 psia.
  • the 190 0 C hydrocarbon product contained 99.1% "naphtha plus diesel". Diesel itself was at 93.6%. There was very little light wax. Cetane number was 81. As shown in Table 8, the crystallite size was 22.22 run and the wax fraction was 2.3 %, enabling the product to be directly as a diesel fuel.
  • Figure 7 shows C5+ carbon number distribution for Example 9 (F-220) at 190 0 C, 70 psia
  • the crystallite size was 20.89 ran and the wax fraction was 3,73 %, enabling the product to be used as a diesel blend.
  • Figure 8 shows C5+ carbon number distribution for the catalyst of Example 10 using a ruthenium promoter.
  • the crystallite size was 33.1 run and the wax fraction was 5.2 %, enabling the product to be used as a diesel blend, perhaps after flashing off the naphtha fraction.
  • Figure 9 shows a graph of the C5+ carbon number distribution for the catalyst of Example 11 (Aerolyst 3038 silica) .
  • the catalysts of Examples 1 -11 (except catalysts 8 b, c and d), as may be seen from the above discussion, show that a narrow distribution of hydrocarbons, mainly in the diesel range, having low wax content ( ⁇ 10 wt.%) is obtained when the FT catalyst has cobalt crystallites larger than 16 nm, as shown in Figure 10 showing the relationship of cobalt catalyst c ⁇ ystallite size to wax weight content (%) of C5+ FT product [ naphtha is indicated by large squares, diesel by diamonds and light waxes by small squares].
  • Figure 11 compares this result with expectations from the Anderson-Shultz- Flory (A-S-F) carbon number distribution based on chain growth.
  • the A-S-F distribution provides only 50 wt. % diesel fraction, whereas the present invention provides > 65 wt, %.
  • the liquid hydrocarbon product of the present catalysts is more valuable than the broad A-S-F type of product because it can be used directly as a diesel-blending stock without hydrocracking to increase cetane number and decrease sulphur content of petroleum diesels. Because the present process is a simple once-through process, it entails low capital cost.

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Abstract

L'invention porte sur un procédé Fischer-Tropsch pour la production de carburant diesel ou d'une base pour mélange diesel ayant un indice de cétane élevé, en une concentration de 65-90 % en poids à des pressions au-dessous de 200 psia, à l'aide d'un catalyseur au cobalt avec un promoteur au rhénium et/ou au ruthénium. Le catalyseur est un catalyseur au cobalt comprenant des cristallites ayant un diamètre moyen supérieur à 16 nanomètres et le produit hydrocarbure résultant, après une détente brusque brutale, contient moins de 10 % en poids de cires (> C23).
PCT/CA2008/002306 2008-12-22 2008-12-22 Procédé fischer-tropsch à basse pression Ceased WO2010071967A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
PCT/CA2008/002306 WO2010071967A1 (fr) 2008-12-22 2008-12-22 Procédé fischer-tropsch à basse pression
PCT/CA2009/001862 WO2010071989A1 (fr) 2008-12-22 2009-12-21 Procédé fischer-tropsch basse pression
MYPI2011002900A MY160250A (en) 2008-12-22 2009-12-21 Low-pressure fischer-tropsch process
AU2009329785A AU2009329785B2 (en) 2008-12-22 2009-12-21 Low-pressure Fischer-Tropsch process
EP09833974A EP2379676A4 (fr) 2008-12-22 2009-12-21 Procédé fischer-tropsch basse pression
CA2748216A CA2748216C (fr) 2008-12-22 2009-12-21 Procede fischer-tropsch basse pression
CN200980157057.XA CN102325858B (zh) 2008-12-22 2009-12-21 低压费-托法
MX2011006743A MX2011006743A (es) 2008-12-22 2009-12-21 Proceso fischer-tropsch de baja presion.
RU2011130432/04A RU2487159C2 (ru) 2008-12-22 2009-12-21 Способ осуществления процесса фишера-тропша при низком давлении
ARP090105016A AR074831A1 (es) 2008-12-22 2009-12-21 Proceso fischer -tropsch a baja presion

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CA2567425A1 (fr) * 2006-11-08 2008-05-08 Canada Chemical Corporation Procede de fischer-tropsch a basse pression simple
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US7452844B2 (en) * 2001-05-08 2008-11-18 Süd-Chemie Inc High surface area, small crystallite size catalyst for Fischer-Tropsch synthesis
US20050119116A1 (en) * 2003-10-16 2005-06-02 Conocophillips Company Silica-alumina catalyst support, catalysts made therefrom and methods of making and using same
CA2567425A1 (fr) * 2006-11-08 2008-05-08 Canada Chemical Corporation Procede de fischer-tropsch a basse pression simple

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US20140374660A1 (en) * 2013-06-25 2014-12-25 Massachusetts Institute Of Technology Engine Chemical Reactor With Catalyst

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