WO2010071989A1 - Procédé fischer-tropsch basse pression - Google Patents

Procédé fischer-tropsch basse pression Download PDF

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Publication number
WO2010071989A1
WO2010071989A1 PCT/CA2009/001862 CA2009001862W WO2010071989A1 WO 2010071989 A1 WO2010071989 A1 WO 2010071989A1 CA 2009001862 W CA2009001862 W CA 2009001862W WO 2010071989 A1 WO2010071989 A1 WO 2010071989A1
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Prior art keywords
catalyst
fischer
cobalt
weight
tropsch
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PCT/CA2009/001862
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English (en)
Inventor
Conrad Ayasse
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Canada Chemical Corporation
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Publication date
Priority claimed from PCT/CA2008/002306 external-priority patent/WO2010071967A1/fr
Priority claimed from US12/318,106 external-priority patent/US8053481B2/en
Application filed by Canada Chemical Corporation filed Critical Canada Chemical Corporation
Priority to AU2009329785A priority Critical patent/AU2009329785B2/en
Priority to CN200980157057.XA priority patent/CN102325858B/zh
Priority to CA2748216A priority patent/CA2748216C/fr
Priority to RU2011130432/04A priority patent/RU2487159C2/ru
Priority to EP09833974A priority patent/EP2379676A4/fr
Priority to MX2011006743A priority patent/MX2011006743A/es
Publication of WO2010071989A1 publication Critical patent/WO2010071989A1/fr

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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
    • B01J23/89—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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    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
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    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
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    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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Definitions

  • This invention relates generally to a low pressure Fischer-Tropsch process for converting carbon monoxide and hydrogen to diesel fuel or diesel blending stock.
  • 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.
  • the gas is rich in CO 2 , this can be advantageous because the desired H2/CO ratio can then be achieved directly in the reformer gas without the need to remove excess hydrogen, and some of the CO 2 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,
  • FT Fischer-Tropsch
  • the reformers usually use some form of autothermal reforming with oxygen that is produced cryogenically from air, an expensive process in terms of operating cost and capital cost.
  • the economies 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 economical FT plant design has not been developed for small plants with capacities of less than 100 million scfd.
  • Fischer-Tropsch synthesis The catalytic hydrogenation of carbon monoxide to produce a variety of products ranging from methane to heavy hydrocarbons (up to Cgo 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 cannot 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 so that component separation or hydrocracking are not necessary.
  • Catalytically active group VM in particular, iron, cobalt and nickel are used as Fischer-Tropsch catalysts; 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,
  • Fischer-Tropsch (FT) process having a cobalt catalyst with crystallites, wherein the crystallites have an average diameter greater that 16 nanometers.
  • the process produces a liquid hydrocarbon product containing less than 10 weight percent wax PC 23 ) and greater than 65% diesel (Ce-C 23 ),
  • the process can have a FT catalyst support for the cobalt catalyst, wherein the catalyst support is selected from the group of catalyst supports consisting of alumina, zirconia, titania and silica,
  • the cobalt catalyst can have a catalyst loading that is greater than 10 weight %,
  • the operating pressure for the Fischer-Tropsch process can be less than 200 psia.
  • Promoters can be utilized in this process, in which case the promoters are selected from the group consisting of : ruthenium, rhenium, rhodium, nickel, zirconium, titanium, and mixtures thereof.
  • a flash distillation can be conducted on the process to reduce the naphtha cut.
  • the process can use a FT reactor that does not use tailgas recycle.
  • the process can also use a reformer that uses air as an oxygen source.
  • the reactor can be a fixed-bed FT reactor or a slurry bubble bed FT reactor.
  • a FT process operating at less than 200 psia, using an air autothermal reformer, and having a CO conversion of at least 65 % and providing a diesel yield greater than 60% by weight in a single ⁇ pass FT reactor using a cobalt catalyst.
  • the catalyst has a metallic cobalt loading greater than 5% by weight and rhenium loading of less than 2% by weight on a catalyst support material selected from the group of catalyst support materials comprising alumina, zirconia, and silica.
  • the cobalt catalyst is in the form of crystallites, wherein the crystallites have an average diameter greater that 16 nanometers.
  • the FT catalyst support material can be comprised of alumina.
  • This process can have a feed gas, wherein selective membranes or molecular sieves are employed to remove hydrogen from the feed gas.
  • the cobalt catalyst loading can be greater than 6 weight % and operating pressure can be less than 100 psia.
  • the reactor can further have a promoter, wherein said promoter comprises a promoter selected from the group of promoters consisting of ruthenium and rhenium or mixtures thereof.
  • a FT process operating at less than 200 psia, using an oxygen autothermal reformer, and having a CO conversion of at least 65 % and providing a diesel yield greater than 60% by weight in a FT reactor using a cobalt catalyst.
  • the catalyst has a metallic cobalt loading greater than 5% by weight and a rhenium loading of less than 2% by weight on a catalyst support selected from the group of catalyst supports comprised of alumina, zirconia and silica materials.
  • the cobalt catalyst is in the form of crystallites, said crystallites having an average diameter greater that 16 nanometers.
  • the FT catalyst support can be comprised of alumina.
  • the process can include a tailgas from the reformer, wherein the tailgas is partially recycled to the reformer.
  • the process can also include a feed gas wherein selective membranes or molecular sieves are employed to remove hydrogen from the gas.
  • the cobalt catalyst loading can be greater than 6 weight % and the operating pressure can be less than 100 psia.
  • the reactor can further have a promoter, wherein said promoter comprises a promoter selected from the group of promoters consisting of ruthenium or rhenium, or mixtures thereof
  • a FT process operating at less than 200 psia, using an oxygen steam reformer, and having a CO conversion of at least 65 % and providing a diesel yield greater than 60% in by weight in a FT reactor using a cobalt catalyst with a metallic cobalt loading greater than 5% by weight and rhenium loading of less than 2% by weight on a catalyst support selected from the group of catalyst supports comprised of alumina, zirconia, or silica materials, or mixtures thereof.
  • the cobalt catalyst is in the form of crystallites, wherein the crystallites have an average diameter greater that 16 nanometers.
  • the FT catalyst support can be comprised of alumina.
  • the process can include a feed gas, wherein selective membranes or molecular sieves are employed to remove hydrogen from the feed gas.
  • the process can further include a tailgas from the reformer, wherein some or all of the tailgas is burned to provide heat to the reformer.
  • the cobalt catalyst loading can be greater than 6 weight % and the operating pressure can be less than 100 psia.
  • the reactor can further have a promoter, wherein said promoter comprises a promoter selected from the group of promoters consisting of ruthenium or rhenium, or mixtures thereof.
  • a FT process operating at less than 200 psia, using an air or oxygen partial oxidation reformer, and having a CO conversion of greater than 65 Vo and providing a diesel yield greater than 60% by weight in a FT reactor using a cobalt catalyst with a metallic cobalt loading greater than 5% by weight and rhenium loading of less than 2% by weight on a FT catalyst support selected from the group of catalyst supports comprising alumina, zirconia, and silica materials.
  • the cobalt catalyst is in the form of crystallites, and the crystallites have an average diameter greater that 16 nanometers,
  • the FT catalyst support can be comprised of alumina.
  • the process can include a feed gas, wherein selective membranes or molecular sieves are employed to remove hydrogen from the feed gas.
  • the process can further include a tailgas from the reformer, wherein some or all of the tailgas is burned to provide heat to the reformer.
  • the cobalt catalyst loading can be greater than 6 weight % and the operating pressure can be less than 100 psia.
  • the reactor can further have a promoter, wherein said promoter comprises a promoter selected from the group of promoters consisting of ruthenium or rhenium, or mixtures thereof.
  • Figure 1 is a process flow diagram for a particular embodiment of the invention
  • FIG. 2 is a flow diagram for flash separation of naphtha and diesel hydrocarbon fractions as a subsequent step to the Fischer-Tropsch process
  • Figure 3 is a graph showing C5+ carbon number distribution for the catalyst of Example 3 (trilobes) at 190 0 C; 0
  • Figure 4 is a graph showing the effect of pressure on the performance of the catalyst of Example 4.
  • Figure 5 is a graph of C5+ carbon number distribution of the catalyst of Example 7 at5 190 0 C, 70 psia;
  • Figure 6 is a graph of the C5+ carbon number distribution for the catalyst of Example 8a (LD-5) at 200"C s 70 psia; 0
  • Figure 7 is a graph of the C5+ carbon number distribution for the catalyst of Example 9 (F-220) at I90 o C., 70 psia
  • Figure 8 is a graph of the C5+ carbon number distribution for the catalyst of Example
  • Figure 9 is a graph of the C5+ carbon number distribution for Catalyst of Example
  • Figure 10 is a graph showing the relationship of cobalt catalyst crystallite size to wax o content of a C5+ FT product.
  • Figure 11 is a graph showing a comparison of catalyst used in Example 9 carbon distribution with a traditional Anderson-Shultz-FIory distribution. ⁇ In all Figures showing graphs of carbon numbers, naphtha is indicated by large squares, diesel by diamonds and light waxes by small squares.
  • cobalt metal and oxide supports Under certain pretreatnient and activation conditions, a strong interaction between cobalt metal and oxide supports forms undesirable cobalt-support structures, for example, cobalt alwninate, 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 title 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.
  • Fischer-Tropsch process and a catalyst that produces a high diesel-ftaction yield.
  • Process pressure can be 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. %, and have crystallites having an average diameter greater than 16 nanometers. It has been discovered that this catalyst is very effective at low pressures in converting synthesis gas into diesel in high yield, producing a liquid hydrocarbon product containing less than 10 wt,% wax (>C23) and greater than 65% diesel (C9-C23),
  • the present embodiments are 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 separated from the hydrocarbon product by flash distillation at low cost to generate & 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.
  • the present embodiments can be applied to world-scale gas-to-liquid plants, but also to small FT plants using less than 100 million scfd.
  • the present embodiments strive for optimized economics with an emphasis on simplicity and minimized capital cost, possibly at the expense of efficiency.
  • the following is a comparison of existing FT technologies compared to the present embodiment as applied to small FT plants:
  • 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 in one 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 catalyst is made to have a relatively large average cobalt crystallite size and this gives selectivity to a substantially diesel product.
  • 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 (OQu, Chevron definition).
  • diesel fuel OQu, Chevron definition
  • a common approach is to strive to make mostly wax in the PT reactor and then, in a separate operation, to hydrocrack the wax to mostly diesel and naphtha.
  • the process and catalyst of the present embodiments make 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 FT process of the present embodiment, wherein the letters A-K signify the following:
  • Letter A represents the raw hydrocarbon-containing process reed 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.
  • Other natural gas sources which may or may not be stranded (no access to a pipeline) may already be at or above the desired process operation pressure and these are also candidates.
  • Another candidate is natural gas that is too high in inert
  • 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. Nevertheless, 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 i.e. 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 Hj/CO 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 700 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 minimize 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.
  • H ⁇ /CO ratio is 2.0-2.1, whereas the raw synthesis gas may have a ratio of 3.0 or higher. 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 ⁇ represents typical FT reactors, which are of the fixed- bed or slurry bubble type and either may be used.
  • the fixed-bed is preferred in small plants because of 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 partial separation process employed.
  • Letter K represents product cooling and reoovery.
  • 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 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:
  • 1 is a fixed-bed Fischer Tropsch reactor.
  • 2 is a mixture of gases, water, naphtha, diesel and light waxes at ca.190-240 °C and pressure greater than atmospheric.
  • S is stream 2 at reduced temperature due to gas expansion and at 14.7 psia.
  • S 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 knowledgeable in the art.
  • the catalyst support was alumina trilobe extrudate obtained 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 peirhenic 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 (Catalyst 1).
  • the catalyst was oxidized in three steps:
  • Step 1 the catalyst was heated to 85 0 C and held for 6 hours.
  • Step 2 the temperature was raised to 100 ⁇ C at 0.5 0 C per minute and held for 4-hours;
  • Step 3 the temperature was raised to 350 0 C at 0.3 0 C per minute and held for 12 hours.
  • the drying rate of the wet catalyst was somewhat dependent upon the size of catalyst particles. Smaller particles will dry more quickly than larger particles and the size of the crystals formed inside the pores can vary with crystallization rate.
  • a volume of 29 cc of oxidized catalyst was placed in a 14 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 placed in the tube side. The inlet gas and water were both at the targeted reaction temperature. Catalyst reduction was accomplished by the following procedure:
  • the catalyst used in this example was the same as the catalyst used in Example I 1 except that the cobalt metal loading was 10 wt%.
  • the catalyst used in this example was the same as the catalyst used in Example 1, except that the cobalt metal loading was 15 wt%.
  • the catalyst used in this example was the same as the catalyst used in Example 1 , except that the cobalt metal loading was 20 wt%.
  • Example 5 The catalyst used in this example (Catalyst S) was the same the catalyst used in Example 1, except that the cobalt metal loading was 26 wt%.
  • the catalyst used in this example was the same the catalyst used in Example 1 , except that the cobalt metal loading was 35 wt%.
  • the catalyst used in this example was the same as the catalyst 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. Examples 8a. 8b. 8c ⁇ fe 8d
  • Catalysts 8a, 8b, 8c, and Sd were the same as used in Example I 5 except as follows: Catalyst 8a was identical to Catalyst 1, except that the alumina support was LD-5, 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 smaller sieve sizes: Catalysts 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 Catalyst 8a.
  • the catalyst used in this example was the same as the catalyst used in Example 1 , except that the alumina support was F-220, obtained from Alcoa, and the cobalt loading was 20 weight percent.
  • F-.&0 is a spherical support with a mesh size distribution of 7/14.
  • Catalyst 10 The catalyst used in this example (Catalyst 10) was the same as Catalyst 4, except that the promoter was ruthenium rather than rhenium.
  • Catalyst 11 was the same as Catalyst 3, except that Aerolyst 3038 silica catalyst support from Degussa was used instead of alumina.
  • the catalyst used in this example was identical with Catalyst 8d having the same catalyst support, particle size and catalyst loading, except that the oxidizing process hold times were doubled during catalyst synthesis, That is, the temperature hold times were respectively to 12, 8 and 24 hours for the 3-oxidizing steps described for Catalyst 1.
  • the intention of slower catalyst oxidation rates of the small Catalyst 12 particles was to achieve a larger cobalt crystallite size (21.07 nm) within the pores of the small support particle in comparison with the crystallite size under faster crystallization conditions of Catalyst 8d (15.72).
  • the method used herein to control drying rate and catalyst cobalt crystallite size is not meant to exclude any other method to achieve larger crystallite sizes. For example, the relative humidity or pressure of the drying chamber could be varied to control the catalyst drying rate and therefore cobalt crystallite size.
  • Cobalt crystallite size was calculated from: d(CoO> » (96/D%) DOR
  • the performance data for Catalyst 1 at 202.5 is shown in Table 8.
  • the level of wax (C>23) on the C5+ liquid was only 6.8 % and the diesel fraction was 73,5% (C9- C23). It was found that for all Catalysts tested where the crystallite average diameter was greater than 16 ran, the C5+ wax was less than 10 weight %, enabling the product to be used directly as diesel blend.
  • Figure 3 shows the carbon number distribution for Catalyst 3 (trilobe) in
  • Diesel was 90.8%, naphtha 6.1% and light waxes 3.1%. Cetane number was very high at 88. In all graphs of carbon numbers, naphtha is indicated by large squares, diesel by diamonds and light waxes by small squares,
  • Influence of pressure Catalyst 4 in 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 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 70-450 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, Catalyst 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.
  • Catalysts 8b, 8c and 8d showed Co metal dispersion higher than for Catalyst 8a.
  • Catalysts that contain Co 0 average crystallite sizes below 16 nanometers gave a high wax cut in the FT product of 17.6- 19,3% wt
  • Catalyst 8a and Catalyst 12 which contained Co 0 crystallites larger than 16 nm gave lower wax cuts of 6,6 and 7.8 wt.% respectively in the C5+ liquid, enabling the product to be used as a diesel blend.
  • Catalysts 8a and 12 had very different particle sizes, but gave similar low wax cuts. This shows that the controlling variable for low wax concentrations was crystallite size, and not particle size.
  • Catalyst 9 was tested at 70 psia, As shown in Table 6 and Figure 7, 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 nm and the wax fraction was 2.3 %, enabling the product to be directly as a diesel fuel.
  • the hydrocarbon liquid production rate was 0.55 ml/h at 210 0 C.
  • the carbon distribution curve shown in Figure 9 demonstrates a narrow distribution with a high diesel cut.
  • the crystallite size was 33,1 nm and the wax fraction was 5.2 %, enabling the product to be used as a diesel blend, perhaps after flashing off the naphtha fraction.
  • Catalysts 1 to 12 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 (the large squares are not part of this embodiment).
  • small catalyst particles e.g. Catalyst 12
  • A-S-F 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 embodiments provide > 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 can be a simple onoe-through process, it can entail low capital cost.

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Abstract

L'invention concerne un procédé Fischer-Tropsch utilisé pour produire un carburant diesel ou une base pour mélange diesel avec un indice de cétane élevé, suivant une concentration de 65 à 90 % en poids à des pressions inférieures à 200 psia, en utilisant un catalyseur à base de cobalt avec un promoteur rhénium et/ou ruthénium. Le catalyseur est un catalyseur à base de cobalt présentant des cristallites ayant un diamètre moyen supérieur à 16 nanomètres, et l'hydrocarbure résultant après une vaporisation instantanée brute contient moins de 10 % en poids de cires (> C23).
PCT/CA2009/001862 2008-12-22 2009-12-21 Procédé fischer-tropsch basse pression WO2010071989A1 (fr)

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CN200980157057.XA CN102325858B (zh) 2008-12-22 2009-12-21 低压费-托法
CA2748216A CA2748216C (fr) 2008-12-22 2009-12-21 Procede fischer-tropsch basse pression
RU2011130432/04A RU2487159C2 (ru) 2008-12-22 2009-12-21 Способ осуществления процесса фишера-тропша при низком давлении
EP09833974A EP2379676A4 (fr) 2008-12-22 2009-12-21 Procédé fischer-tropsch basse pression
MX2011006743A MX2011006743A (es) 2008-12-22 2009-12-21 Proceso fischer-tropsch de baja presion.

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US12/318,106 US8053481B2 (en) 2006-11-08 2008-12-22 Low-pressure Fischer-Tropsch process

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GB2527372A (en) * 2014-06-21 2015-12-23 Inventure Fuels Ltd Synthesising hydrocarbons
RU2725983C2 (ru) * 2017-01-17 2020-07-08 Андрей Владиславович Курочкин Автотермический реактор

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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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BR0111557A (pt) * 2000-06-12 2003-07-08 Sasol Tech Pty Ltd Catalisador de fischer-tropsch à base de cobalto, precursor de catalisador à base de cobalto, e, processos para preparação de um precursor de catalisador e de um catalisador
GB0226514D0 (en) * 2002-11-13 2002-12-18 Statoil Asa Fischer-tropsch catalysts

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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
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MY160250A (en) 2017-02-28
EP2379676A1 (fr) 2011-10-26
CA2748216C (fr) 2016-06-07
CA2748216A1 (fr) 2010-07-01
RU2011130432A (ru) 2013-01-27
MX2011006743A (es) 2011-10-06
CN102325858B (zh) 2014-10-22
RU2487159C2 (ru) 2013-07-10
AU2009329785A1 (en) 2011-08-11
EP2379676A4 (fr) 2012-06-20
CN102325858A (zh) 2012-01-18
AU2009329785B2 (en) 2012-11-08

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