WO2024107632A1 - Catalyseurs amorphes pour hydrocraquage de cire fischer-tropsch - Google Patents

Catalyseurs amorphes pour hydrocraquage de cire fischer-tropsch Download PDF

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WO2024107632A1
WO2024107632A1 PCT/US2023/079488 US2023079488W WO2024107632A1 WO 2024107632 A1 WO2024107632 A1 WO 2024107632A1 US 2023079488 W US2023079488 W US 2023079488W WO 2024107632 A1 WO2024107632 A1 WO 2024107632A1
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silica
feedstock
alumina
hydrocracking
catalyst
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PCT/US2023/079488
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English (en)
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Matthew T. Kapelewski
III Raymond G. Burns
Lei Zhang
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ExxonMobil Technology and Engineering Company
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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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/04—Oxides

Definitions

  • Amorphous catalysts are provided, along with corresponding systems and methods, for using hydrocracking to improve the yield of liquid products from Fischer-Tropsch synthesis.
  • One pathway for production of liquid fuels from bio-derived sources is to convert biomass into a synthesis gas and then use Fischer-Tropsch (FT) synthesis to form fuel boiling range products.
  • FT Fischer-Tropsch
  • This type of pathway is advantageous because it avoids the need to directly form molecules of a target type and/or in a target boiling range. Instead, any convenient type of biomass can be broken down to form synthesis gas, and then FT synthesis is used to generate hydrocarbons.
  • the output from FT synthesis typically corresponds to a product with a distribution of chain lengths according to the Anderson-Schulz-Flory distribution. Due to the nature of the distribution of chain lengths, using FT synthesis to form fuels boiling range also results in formation of a substantial amount of Fischer-Tropsch wax. Even under optimal conditions for producing distillate boiling range products, a Fischer-Tropsch synthesis process can typically produce 20 wt% or more of C22+ compounds that include a high proportion of paraffins. Such a C22+ fraction is an example of an FT wax.
  • FT wax produced from syngas conversion is typically a highly paraffinic and high melting wax that is free of sulfur and nitrogen impurities.
  • fuels boiling range compounds such as distillate boiling range compounds, jet boiling range compounds or naphtha boiling range compounds
  • Typical processing includes hydrocracking to form lighter molecules, with a range targeted based on the hydrocracking catalyst being used. It would be desirable to have improved catalysts, systems, and/or methods for converting such FT wax into fuels boiling range compounds.
  • U.S. Patent 7,704378 describes a catalyst for hydrocracking of a heavy Fischer- Tropsch fraction.
  • the catalyst includes a silica-alumina support where the distribution of silica and alumina in the support is not uniform. Instead, there are distinct regions within the support having different ratios of silica to alumina.
  • U.S. Patent 8,679,323 describes hydrocracking of a heavy Fischer-Tropsch fraction.
  • the catalyst includes base-modified dealuminated USY with a Si / Al ratio prior to base modification and prior to mixing with a binder or support of 2.5 to 20.
  • U.S. Patent 8,142,644 describes hydrocracking and hydroisomerization of a Fischer-Tropsch fraction where 50 wt% or more of the fraction boils at 370°C or higher.
  • the catalyst includes a carrier with a pore volume of 0.8 ml/g or more and a median pore diameter of 85 Angstroms or more. Additionally, the pores have a high degree of cylindrical character.
  • U.S. Patent 8,685,231 describes hydrocracking and hydroisomerization of a Fischer-Tropsch fraction where 50 wt% or more of the fraction boils at 370°C or higher.
  • the catalyst includes 15 wt% or less of zeolite Beta and 40 wt% or more of a silica-alumina binder or carrier.
  • U.S. Patent 6,583, 186 describes a method for processing Fischer-Tropsch feed.
  • the Fischer-Tropsch feed is separated into a lighter fraction and a heavier fraction.
  • the heavier fraction is then hydrocracked and optionally isomerized.
  • the lighter fraction is then mixed with the resulting hydrocracked effluent.
  • U.S. Patent 10,227,537 describes processing of Fischer-Tropsch wax in a multi-step process that includes hydrocracking in the presence of a hydrocracking catalyst containing a zeolite and amorphous silicon- alumina.
  • U.S. Patent Application Publication 2011/0049011 describes hydrocracking of Fischer-Tropsch wax fractions.
  • the hydrocracking catalysts correspond to mixtures of zeolites with silica-alumina, alumina-boria, or silica-zirconia.
  • U.S. Patent Application Publication 2004/0256287 describes hydrocracking of waxy feeds using a catalyst containing an acidic matrix such as amorphous silica alumina.
  • the catalyst can further include up to 2 wt% of a zeolite, such as USY.
  • U.S. Patent 6,399,530 describes an amorphous silica-alumina carrier that can optionally be combined with crystalline materials for use as a hydrocracking catalyst.
  • the amorphous silica-alumina is described as having a pore volume of 0.8 ml/g or more, with an SiO2 content of 50 wt% or less.
  • a method for hydrocracking a waxy feedstock includes a feedstock containing 70 wt% or more of paraffins and having a T10 distillation point of 280°C or higher to a catalyst under hydrocracking conditions including 20 wt% or more conversion relative to 371 °C to form a hydrocracking effluent.
  • the catalyst can have 0. 1 wt% to 3.0 wt% of a Group 8 - 10 noble metal on an extruded silica-alumina support.
  • the extruded silica-alumina support can have a surface area of 360 m 2 /g or more and/or a pore volume of 0.55 cm 3 /g to 0.90 cm 3 /g.
  • the extruded silica-alumina support can be extruded from an extrusion mixture containing nitric acid as a peptizing agent and methylcellulose as an extrusion aid.
  • a weight ratio of silica-alumina to methylcellulose in the extrusion mixture is between 50 and 250.
  • a weight ratio of methylcellulose to nitric acid in the extrusion mixture is 0.2 to 0.8.
  • FIG. 1 shows distillate yield versus feed conversion relative to 371 °C for hydrocracking of a waxy feed in the presence of various hydrocracking catalysts.
  • FIG. 2 shows the reaction temperature for achieving 50 wt% conversion relative to 371 °C for hydrocracking of the waxy feed in the presence of various hydrocracking catalysts.
  • FIG. 3 shows conversion versus reaction temperature for hydrocracking of the waxy feed in the presence of hydrocracking catalyst as described herein.
  • FIG. 4A shows distillate yield and naphtha yield versus temperature during hydrocracking of the waxy feed in the presence of various hydrocracking catalysts.
  • FIG. 4B shows distillate yield and gas phase product yield versus temperature during hydrocracking of the waxy feed in the presence of various hydrocracking catalysts.
  • catalysts and corresponding methods are provided for conversion of Fischer-Tropsch wax to distillate boiling range products.
  • the catalyst for performing the conversion can correspond to a noble metal catalyst supported on an amorphous silica-alumina support.
  • the amorphous silica-alumina support can have a beneficial combination of surface area, pore volume, and acidity that provides for unexpectedly beneficial activity for conversion of Fischer-Tropsch wax. This can allow a target level of conversion during hydrocracking to be achieved at a reduced or minimized temperature and/or reaction severity.
  • the unexpected properties for the amorphous silica-alumina support can be achieved in part by forming the support using an extrusion process where the extrusion mixture includes silica-alumina, nitric acid as a peptizing agent, and methylcellulose as an extrusion aid. The methylcellulose is then removed from the support via calcination, which contributes in part to the properties of the resulting support.
  • a zeotype is defined to refer to a crystalline material having a porous framework structure built from tetrahedra atoms connected by bridging oxygen atoms.
  • Examples of known zeotype frameworks are given in the “Atlas of Zeolite Frameworks” published on behalf of the Structure Commission of the International Zeolite Association”, 6 th revised edition, Ch. Baerlocher, L.B. McCusker, D.H. Olson, eds., Elsevier, New York (2007) and the corresponding web site, stmcture.org/databases/.
  • a zeolite refers specifically to an aluminosilicate having a zeotype framework structure.
  • a zeotype can refer to aluminosilicates (i.e., zeolites) having a zeotype framework structure as well as crystalline structures containing oxides of heteroatoms different from silicon and aluminum.
  • heteroatoms can include any heteroatom generally known to be suitable for inclusion in a zeotype framework, such as gallium, boron, germanium, phosphorus, zinc, and/or other transition metals that can substitute for silicon and/or aluminum in a zeotype framework.
  • a zeotype can include materials such as silicoaluminophosphate (SAPO) materials or aluminophosphate (A1P0) materials.
  • conversion of a feedstock relative to 700°F (371°C) is defined based on the net weight percentage of the feedstock that boils at or above 371 °C prior to a process that is converted to compounds that boil below 371 °C after the conversion process.
  • conversion values described herein correspond to single-pass conversion values.
  • Tx refers to the temperature at which a weight fraction “x” of a sample can be boiled or distilled. For example, if 40 wt% of a sample has a boiling point of 350°F (177°C) or less, the sample can be described as having a T40 distillation point of 350 °F (177°C).
  • the distillate boiling range is defined as 160°C (320°F) to 371 °C.
  • a fraction that has a T10 distillation point of 160°C or more and a T90 distillation point of 371 °C or less is defined as a distillate boiling range fraction.
  • the naphtha boiling range is defined as the boiling point of a Cs paraffin (roughly 29°C) to 160°C.
  • a fraction having a T10 boiling point of 29°C or more and a T90 distillation point of 160°C or less is defined as a naphtha boiling range fraction.
  • T10 distillation point of a fraction must be equal to or less than the T90 distillation point, and that similarly the T90 distillation point of a fraction must be equal to or greater than the T10 distillation point.
  • the distillation profile of a fraction, feed, or product is determined according to ASTM D2887. For a sample where ASTM D2887 is not appropriate for some reason, D86 (for lower boiling fractions) or D7169 (higher boiling fractions) may be used instead.
  • the “cloud point” of a sample is the temperature below which paraffin wax or other solid substances begin to crystallize or separate from the solution, imparting a cloudy appearance to the oil when the oil is chilled under prescribed conditions. Cloud point can be determined according to ASTM D2500 [0028] Unless otherwise specified, the “Liquid Hourly Space Velocity (LHSV)” for a feed or portion of a feed to a reactor is defined as the volume of feed per hour relative to the volume of catalyst in the reactor. In some specific instances, a liquid hourly space velocity may be specified relative to a specific catalyst within a reactor that contains multiple catalyst beds.
  • LHSV Liquid Hourly Space Velocity
  • a “Cx” hydrocarbon refers to a hydrocarbon compound that includes “x” number of carbons in the compound.
  • a stream containing “Cx-Cy” hydrocarbons refers to a stream composed of one or more hydrocarbon compounds that includes at least “x” carbons and no more than “y” carbons in the compound. It is noted that a stream containing “Cx-Cy” hydrocarbons may also include other types of hydrocarbons, unless otherwise specified.
  • references to a “gas portion” or a “liquid portion” of a reaction effluent refer to the phase the effluent portion would be in at 20°C and 100 kPa-a.
  • references to a “gas phase portion” or a “liquid phase portion” of a reaction effluent refer to the phase the effluent portion is in at the specified conditions.
  • a “gas phase portion” of a hydrocracking effluent as the effluent exits from the reactor would refer to the portion of the hydrocracking effluent that is in the gas phase under the conditions present at the exit from the hydrocracking reactor.
  • hydrocracking effluent would only correspond to the components of the effluent that are gas phase at 20°C and 100 kPa-a, such as Q. hydrocarbons, carbon oxides, hydrogen, H2S, and other low boiling compounds.
  • references to a periodic table are defined as references to the current version of the IUPAC Periodic Table.
  • a noble metal catalyst on an amorphous silica-alumina support can be used for hydrocracking of a waxy feedstock, such as wax produced by Fischer-Tropsch synthesis.
  • Fischer-Tropsch synthesis is generally performed by exposing synthesis gas to an appropriate catalyst under Fischer-Tropsch synthesis conditions.
  • Fischer-Tropsch synthesis reactions generally produce products containing a large proportion of paraffins (alkanes). Paraffins containing more than roughly 20 carbons typically correspond to compounds with boiling points above 371 °C.
  • a waxy feedstock corresponds to a feedstock with a T10 distillation point of 280°C or higher, or 300°C or higher, or 315°C or higher, or 343°C or higher, or 371 °C or higher.
  • the T90 distillation point of a waxy feedstock and/or the final boiling point can be any convenient value, so long as the waxy feedstock has a sufficiently low viscosity to be able to be transported into the hydrocracking reactor using conventional methods.
  • a waxy feedstock can have a T90 distillation point of 500°C or more.
  • a waxy feedstock can have a T90 distillation point of 650°C or less. Such a waxy feedstock can be formed in any convenient manner.
  • the resulting liquid products can be separated to form one or more lower boiling fractions (such as a naphtha fraction and/or a distillate fraction and/or a light ends or gas fraction) and at least one higher boiling fraction with a T10 distillation point of 315°C or higher, or 343 °C or higher, or 371 °C or higher.
  • one or more lower boiling fractions such as a naphtha fraction and/or a distillate fraction and/or a light ends or gas fraction
  • a higher boiling fraction with a T10 distillation point of 315°C or higher, or 343 °C or higher, or 371 °C or higher.
  • a waxy feedstock can have a relatively high content of paraffins, as determined according to D5442.
  • a waxy feedstock can have a total paraffin content of 70 wt% or more, relative to a weight of the waxy feedstock, or 80 wt% or more, or 90 wt% or more, such as up to substantially all of the waxy feedstock corresponding to paraffins.
  • a waxy feedstock can have an n-paraffin content of 70 wt% or more, relative to a weight of the waxy feedstock, or 80 wt% or more, or 90 wt% or more, such as up to substantially all of the waxy feedstock corresponding to n-paraffins.
  • a waxy feedstock produced by Fischer-Tropsch synthesis may have an oxygenate content of 5.0 wt% or less, or 2.5 wt% or less, or 1.0 wt% or less, such as down to 0.1 wt%, or possibly down to having substantially no content of oxygenates. If desired, such oxygenates can be removed from a waxy feedstock by any convenient method prior to hydrocracking, such as by performing an initial hydrotreatment process on the waxy feedstock. [0034] In some aspects, such as aspects where a substantial portion of the waxy feedstock is based on Fischer-Tropsch material, the waxy feedstock can have a relatively low content of sulfur and/or nitrogen.
  • the sulfur content of the waxy feed can be 100 wppm or less, or 15 wppm or less, such as down to having substantially no sulfur content (0. 1 wppm or less).
  • the nitrogen content of the waxy feed can be 50 wppm or less, or 15 wppm or less, such as down to having substantially no nitrogen content (0.1 wppm or less).
  • the waxy feedstock can have a relatively low content of aromatics.
  • the aromatics content of the waxy feed can be 10 wt% or less, or 2.5 wt% or less, such as down to having substantially no aromatics content. In this discussion, aromatics content is determined according to ASTM D5186.
  • any aromatics content less than 1.5 wt% corresponds to a sample that is substantially free of aromatics.
  • 50 wt% or more of a waxy feedstock can correspond to compounds formed by Fischer-Tropsch synthesis, or 60 wt% or more, or 75 wt% or more, or 90 wt% or more, such as up to substantially all of the waxy feedstock corresponding to Fischer-Tropsch synthesis products.
  • 50 wt% or more of a waxy feedstock can correspond to a mineral feed or fraction, or 60 wt% or more, or 75 wt% or more, such as up to 95 wt% or possibly still higher.
  • the Fischer-Tropsch material can correspond to 5.0 wt% to 50 wt% of the waxy feedstock, or 5.0 wt% to 40 wt%, or 5.0 wt% to 25 wt%, or 15 wt% to 50 wt%, or 15 wt% to 40 wt%, or 15 wt% to 25 wt%.
  • a portion of the waxy feedstock can correspond to bio-derived components.
  • a portion of the waxy feedstock can correspond to bioderived components that are not formed by a Fischer-Tropsch synthesis process.
  • bio-derived components can correspond to 1.0 wt% to 50 wt% of a waxy feedstock, or 1.0 wt% to 20 wt%, or 1.0 wt% to 10 wt%, or 10 wt% to 50 wt%.
  • a waxy feedstock can be exposed to a hydrocracking catalyst under hydrocracking conditions to produce a hydrocracked effluent.
  • the hydrocracking catalyst can correspond to a noble metal catalyst supported on a silica-alumina support material having a beneficial combination of surface area, pore volume, and acidity.
  • the unexpected properties for the amorphous silica-alumina support can be achieved in part by forming the support using an extrusion process where nitric acid (as a peptizing agent) and methylcellulose (as an extrusion aid) are included with the silica-alumina during the extrusion.
  • the silica-alumina support material can have a surface area of 360 m 2 /g or more, or 400 m 2 /g or more, such as up to 500 m 2 /g or possibly still higher.
  • This surface area corresponds to a BET (Brunauer-Emmett-Teller) surface area that is determined prior to addition of the catalytic metal to the support.
  • BET Brunauer-Emmett-Teller
  • a variety of commercially available devices can determine BET surface areas, such as a Tristar gas adsorption instrument. It is noted that even though the surface area is high, the amount of micropore surface area (as determined by BET) can be relatively low.
  • the micropore surface area can be 60 m 2 /g or less, or 35 m 2 /g or less, or 15 m 2 /g or less, such as down to substantially no micropore surface area (less than 1.0 m 2 /g).
  • Micropore surface area corresponds to surface area in pores having a pore size of 2.0 nm or less.
  • the silica-alumina support material can have a pore volume of 0.55 ml/g to 0.9 ml/g, or 0.55 ml/g to 0.79 ml/g, or 0.60 ml/g to 0.9 ml/g, or 0.60 ml/g to 0.79 ml/g. Pore volume can be determined via BET.
  • the silica-alumina support material can have a sufficiently high acidity.
  • the acidity can be characterized, for example, by collidine adsorption using a thermogravimetric balance instrument. The sample was dried under N2 at 200C for 60 min. Collidine vapor carried by a N2 flow was introduced at 200 C for 60 min followed by a N2 flow stripping for 60 min.
  • the silica-alumina support material can have an acidity that corresponds to a collidine adsorption of 110 pmoles/g or more, or 120 pmoles/g or more, such as up to 170 pmole/g or possibly still higher.
  • TPAA temperature programmed ammonia adsorption
  • TPAD temperature programmed ammonia desorption
  • Ammonia is a weak base that binds with acidic sites on a support if the temperature is sufficiently low, but will desorb at higher temperatures.
  • ammonia can be used to characterize the amount of acidic sites present in a support material on a per gram basis.
  • TPAA is the reverse process, where a sample with substantially no adsorbed ammonia is exposed to a partial pressure of ammonia while the temperature is reduced to 250°C after drying at 500°C in air.
  • the weight gain of the sample can be used to determine the amount of ammonia that is adsorbed.
  • TPAA and TPAD should result in similar acidity values.
  • a support material (or a catalyst formed by adding metal to a support material) can have an acidity measured by TPAA and/or TPAD of 0.30 meq/g to 0.70 meq/g, or 0.30 meq/g to 0.55 meq/g, or 0.40 meq/g to 0.70 meq/g.
  • silica-alumina can be the silica content.
  • the molar ratio of silica to alumina can be 0.7 or less, or 0.5 or less, such as down to 0.2 or possibly still lower. It is noted that by definition, a zeolitic material must have a silica to alumina ratio of roughly 1.0 or higher, as zeolitic materials by definition cannot include any Al - Al bonds.
  • the combination of surface area, pore volume, and acidity for the silica-alumina can be achieved in part by using a methylcellulose as an extrusion aid during the extrusion of the silica-alumina, in combination with nitric acid as a peptizing agent.
  • a methylcellulose as an extrusion aid during the extrusion of the silica-alumina
  • nitric acid as a peptizing agent.
  • a silica-alumina can be mixed with methylcellulose and nitric acid.
  • the weight ratio of silica-alumina to methylcellulose in the extrusion mixture can be between 25 to 500, or 25 to 250, or 50 to 500, or 50 to 250, or 75 to 250, or 75 to 150.
  • the weight ratio of methylcellulose to nitric acid in the mixture can be 0.2 to 0.8, or 0.2 to 0.7, or 0.3 to 0.8, or 0.3 to 0.7.
  • nitric acid can typically be added to an extrusion mixture as a water based solution.
  • the weight ratio of methylcellulose to nitric acid is based on the actual weight of nitric acid, not the weight of the nitric acid solution. The mixture is mixed until it is an appropriate consistency for extrusion.
  • the methylcellulose can be introduced into the extrusion mixture prior to adding the nitric acid.
  • the solids content of the extrusion mixture can be between 40 wt% and 55 wt%.
  • the resulting extrudates can be dried for a suitable time at a lower temperature, such as a temperature of 150°C or less.
  • the extrudates can then be calcined at a temperature that is sufficiently high to remove the methylcellulose from the extrudate, such as a temperature 500°C or more.
  • the desired amount of metal for the final hydrocracking catalyst can then be added in any convenient manner, such as via an incipient wetness impregnation.
  • the amount of Group 8 - 10 noble metal on the support can correspond to 0.1 wt% to 3.0 wt%, relative to the total weight of the catalyst (metal plus support), or 0.1 wt% to 2.0 wt%, or 0.1 wt% to 1.0 wt%, or 0.3 wt% to 3.0 wt%, or 0.3 wt% to 2.0 wt%, or 0.3 wt% to 1.0 wt%.
  • the Group 8 - 10 noble metal can be Pt, Pd, or a combination thereof.
  • the noble metal can be added to the support by any convenient method, such as by incipient wetness.
  • the waxy feedstock Prior to hydrocracking, can optionally be exposed to a hydrotreatment catalyst under hydrotreating conditions. This can allow for removal of at least a portion of oxygen, sulfur, and/or nitrogen that may be present in the waxy feedstock. Such hydrotreatment can potentially also saturate olefins and/or aromatics present in the waxy feedstock.
  • the hydrocracking conditions can include a temperature 500°F (260°C) to 840°F (449°C), or 572°F (300°C) to 779°F (415°C), or 355°C to 449°C, or 355°C to 415°C, a hydrogen partial pressure of 500 psig to about 3000 psig (3.45 MPag to 20.7 MPag), liquid hourly space velocities of from 0.05 tr 1 to 10 h 1 , and hydrogen treat gas rates of from 35.6 m 3 /m 3 to 1781 m 3 /m 3 (200 SCF/B to 10,000 SCF/B). It is noted that hydrocracking can potentially be performed at temperatures greater than 415°C.
  • reaction conditions can be selected to produce 30 wt% or more conversion of the waxy feedstock relative to 371 °C, or 50 wt% or more, or 70 wt% or more, such as up to substantially complete conversion of the 371°C+ portions of the waxy feedstock to compounds boiling below 371 °C.
  • the hydrocracked effluent will typically include a gas portion (at 20°C and 100 kPa-a) and a liquid portion.
  • the liquid portion of the hydrocracked effluent can include a naphtha boiling range fraction, a distillate boiling range fraction, and optionally an unconverted portion corresponding to components that still have a boiling point of 371 °C or higher.
  • recycle of unconverted bottom with a boiling point of 371 °C or higher can be used to provide for full conversion of the feedstock over multiple passes, even though the single-pass conversion for the feed is less than 100 wt%.
  • Catalyst 1 A silica-alumina self-bound support material was prepared using Siral 30 (available from Sasol) as a source of silica-alumina. This silica alumina was extruded using nitric acid as a peptizing agent and methyl cellulose as an extrusion aid. To form the extrudate, the extrusion process included mulling 253.98 g of Siral 30 with 2 grams of methylcellulose (Methocel) extrusion aid for 10 minutes. 102.33 g 3.91% HNO3 solution was added as a peptizing agent and the mixture was mulled for 10 minutes.
  • Siral 30 available from Sasol
  • Catalyst 2 (comparative): A silica-alumina support material was used that was a commercial extrudate with a SiO content of 20%. [0049] After forming / selecting the extrudates, a Group 8 - 10 noble metal (either Pt or Pd) was impregnated on the extrudates. The calcined extrudates were impregnated via incipient wetness with tetraamine complexes of platinum metal.
  • Table 1 Data for the Siral 30 silica-alumina prior to extrusion is also shown.
  • Table 1 the characterization data for the comparative catalysts is provided for a Pd-based catalyst.
  • the comparative catalyst in Table 1 contains Pd instead of Pt, it is believed that the properties in Table 1 are representative of the properties of a Pt-based catalyst having the comparative support.
  • Example 1 The catalyst supports from Example 1 were tested for their ability to hydrocrack a Fischer-Tropsch wax feed.
  • the targeted product is distillate-range molecules, so all yields and conversion are focused on this range of molecules.
  • the wax fraction of the feed and products is defined as having a boiling point above 371 °C, and the distillate range molecules are considered to have a boiling point in the range of I60°C - 371 °C.
  • yields of a given fraction after conversion indicate the total amount of molecules in that boiling range present, including both pre-existing molecules that were not converted as well as those that were cracked from higher boiling fractions, in an effort to give the full picture of the yields relevant to further downstream processing.
  • the Fischer-Tropsch feed used for generating the examples herein included roughly 25 wt% of components boiling in the range of 160 °C to 370°C. Thus, if exposed to conditions where no conversion of wax occurs, the expected distillate yield would be near 25 wt%.
  • FIG. 1 shows the distillate yield versus amount of conversion for Catalyst 1 in Table 1, and for a Pt-based comparative catalyst based on the comparative support used for Catalyst 2 in Table 1.
  • Catalyst 1 and the Pt-based comparative catalyst had similar profiles for the amount of distillate yield relative to the amount of conversion, with distillate yield steadily increasing until the conversion level reached roughly 90 wt% relative to 371 °C. Beyond 90 wt% conversion, the distillate yield rapidly fell due to over-cracking of the products.
  • Table 2 the yield of distillate is actually slightly higher for Catalyst 1 at a given level of conversion.
  • Catalyst 1 and the Pt-based comparative catalyst have similar profiles for producing distillate at a given level of conversion.
  • the temperature required to achieve a target level of conversion for Catalyst 1 is substantially lower than the corresponding temperature that is needed for the Pt-based comparative catalyst.
  • FIG. 2 shows the temperature required to achieve 50 wt% conversion of the feed relative to 371 °C.
  • the temperature required for Catalyst 1 to achieve 50 wt% conversion is roughly 30°C lower than the temperature required for the Pt-based comparative catalyst under similar conditions.
  • the temperature for achieving 50 wt% conversion (relative to 371 °C) is important based on run length considerations. Over time, hydrocracking catalysts tend to deactivate, resulting in less conversion at a given temperature. In order to maintain conversion at a constant value during an extended run, the temperature for the hydrocracking process is increased over time. While this is effective, it is typically desirable to avoid increasing the temperature above roughly 400°C, in order to avoid the onset of substantial thermal cracking. Thus, the lower the temperature is for a fresh catalyst to achieve 50 wt% conversion, the lower the starting hydrocracking temperature will be for that catalyst for a given feed at a target level of conversion. This means that more temperature increase is available for performing an extended run length process prior to reaching 400°C.
  • FIG. 3 shows the amount of diesel yield relative to the hydrocracking temperature for Catalyst 1 .
  • FIG. 4A and FIG. 4B provide additional details about the product yields for the two catalysts relative to the amount of feed conversion.
  • FIG. 4A shows distillate and naphtha yield for Catalyst 1 and the Pt-based comparative catalyst
  • FIG. 4B shows yields for distillate and gas phase products for the two catalysts.
  • the yields of naphtha and gas phase products are also substantially similar for the two catalysts. This confirms that the unexpected activity benefit for the inventive catalyst is achieved while maintaining a desirable product slate.
  • the resulting diesel fuel generated from a catalyst as described herein also has improved properties relative to a conventional catalyst based on amorphous silica-alumina.
  • Table 2 provides a comparison of how the product slate changes with conversion for both Catalyst 1 and comparative Catalyst 2 (the Pd-based comparative catalyst).
  • Catalyst 1 provides a small but substantial yield advantage for diesel at all conversion levels between 50% and 80%, while reducing the yield of light ends. In addition to the yield improvement, the resulting diesel product generated using Catalyst 1 had improved cold flow properties. Table 3 shows characterization of diesel fractions generated using both Catalyst 1 and Catalyst 2.
  • Embodiment 1 A method for hydrocracking a waxy feedstock, comprising: exposing a feedstock comprising 70 wt% or more of paraffins and having a T10 distillation point of 280°C or higher to a catalyst under hydrocracking conditions comprising 20 wt% or more conversion relative to 371 °C to form a hydrocracking effluent, the catalyst comprising 0.1 wt% to 3.0 wt% of a Group 8 - 10 noble metal on an extruded silica-alumina support, the extruded silica-alumina support comprising a surface area of 360 m 2 /g or more and a pore volume of 0.55 cm 3 /g to 0.90 cm 3 /g, the hydrocracking conditions optionally comprising a temperature of 355°C or less.
  • Embodiment 2 The method of Embodiment 1, wherein the extruded silica-alumina support is extruded from an extrusion mixture comprising silica-alumina, nitric acid as a peptizing agent, and methylcellulose as an extrusion aid, wherein a weight ratio of silica- alumina to methylcellulose in the extrusion mixture is between 50 and 250, or wherein a weight ratio of methylcellulose to nitric acid in the extrusion mixture is 0.2 to 0.8, or a combination thereof.
  • an extrusion mixture comprising silica-alumina, nitric acid as a peptizing agent, and methylcellulose as an extrusion aid, wherein a weight ratio of silica- alumina to methylcellulose in the extrusion mixture is between 50 and 250, or wherein a weight ratio of methylcellulose to nitric acid in the extrusion mixture is 0.2 to 0.8, or a combination thereof.
  • Embodiment 3 The method of any of the above embodiments, wherein the extruded silica-alumina support comprises a pore volume of 0.55 cm 3 /g to 0.79 cm 3 /g.
  • Embodiment 4 The method of any of the above embodiments wherein the extruded silica-alumina support comprises a surface area of 400 m 2 /g or more.
  • Embodiment 5 The method of any of the above embodiments, wherein the extruded silica-alumina support comprises a silicon to aluminum ratio of 0.2 to 0.7; or wherein the extruded silica-alumina support comprises an acidity measured by temperature programmed ammonia desorption of 0.3 meq/g to 0.7 meq/g; or wherein the extruded silica- alumina support comprises an acidity measured by collidine adsorption of 110 pmols/g or more; or a combination thereof.
  • Embodiment 6 The method of any of the above embodiments, wherein the extruded silica-alumina support comprises a micropore surface area of 60 m 2 /g or less.
  • Embodiment 7 The method of any of the above embodiments, wherein the feedstock comprises 70 wt% or more of n-paraffins; or wherein the feedstock comprises 50 wt% or more of Fischer-Tropsch synthesis products; or a combination thereof.
  • Embodiment 8 The method of any of the above embodiments wherein the feedstock comprises 1.0 wt% or more of bio-derived components.
  • Embodiment 9 The method of any of the above embodiments, wherein the feedstock comprises a T10 distillation point of 315°C or more.
  • Embodiment 10 The method of any of the above embodiments, wherein the feedstock comprises a T10 distillation point of 343°C or more, a T90 distillation point of 650°C or less, or a combination thereof.
  • Embodiment 11 The method of any of the above embodiments, wherein the feedstock comprises a T90 distillation point of 500°C or more.
  • Embodiment 12 The method of any of the above embodiments, wherein the Group 8 - 10 noble metal comprises Pt, Pd, or a combination thereof.
  • Embodiment 13 The method of any of the above embodiments, wherein the feedstock comprises 1.0 wt% or less of oxygenates.
  • Embodiment 14 The method of any of the above embodiments, the method further comprising hydrotreating a feed under hydrotreating conditions to form a hydrotreated effluent, the feedstock comprising a portion of the hydrotreated effluent.
  • Embodiment 15 The method of claim 1, wherein the feedstock comprises 80 wt% or more of paraffins; or wherein the feedstock comprises 2.5 wt% or less of aromatics; or a combination thereof.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne des catalyseurs et des procédés correspondants pour la conversion d'une cire de Fischer-Tropsch en produits dans la plage d'ébullition du distillat. Le catalyseur pour effectuer la conversion peut correspondre à un catalyseur de métal noble supporté sur un support de silice-alumine amorphe. Le support de silice-alumine amorphe peut avoir une combinaison bénéfique de surface, de volume de pores et d'acidité qui fournit une activité étonnamment bénéfique pour la conversion de cire de Fischer-Tropsch. Ceci peut permettre d'obtenir un niveau cible de conversion pendant l'hydrocraquage à une température et/ou une sévérité de réaction réduites ou réduites au minimum. Les propriétés inattendues pour le support de silice-alumine amorphe peuvent être obtenues en partie par formation du support à l'aide d'un procédé d'extrusion où le mélange d'extrusion comprend de la silice-alumine, de l'acide nitrique en tant qu'agent peptisant, et de la méthylcellulose en tant qu'adjuvant d'extrusion. La méthylcellulose est ensuite retirée du support par calcination, ce qui contribue en partie aux propriétés du support résultant.
PCT/US2023/079488 2022-11-14 2023-11-13 Catalyseurs amorphes pour hydrocraquage de cire fischer-tropsch WO2024107632A1 (fr)

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EP0532118A1 (fr) * 1991-09-12 1993-03-17 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'essence
US6399530B1 (en) 1998-11-13 2002-06-04 China Petrochemical Corporation Amorphous silica-alumina, a carrier combination and a hydrocracking catalyst containing the same, and processes for the preparation thereof
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US7704378B2 (en) 2003-01-27 2010-04-27 Institut Francais Du Petrole Method for the production of middle distillates by hydroisomerisation et hydrocracking of charges arising from the Fischer-Tropsch method
US20110049011A1 (en) 2008-03-14 2011-03-03 Yuichi Tanaka Method of processing fischer-tropsch synthetic oil to manufacture diesel fuel base stock and method of calculating cracking rate upon hydrocracking wax fraction
US8142644B2 (en) 2007-09-10 2012-03-27 Shell Oil Company Process for hydrocracking and hydro-isomerisation of a paraffinic feedstock
US8679323B2 (en) 2009-11-10 2014-03-25 Eni S.P.A. Process for middle distillate production from Fischer-Tropsch waxes using a modified-zeolite-based catalyst by a basic treatment
US8685231B2 (en) 2009-11-27 2014-04-01 Shell Oil Company Process for conversion of paraffinic feedstock
US20160214094A1 (en) * 2015-01-22 2016-07-28 Chevron U.S.A. Inc. Noble metal zeolite catalyst for second-stage hydrocracking
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FR2351071A1 (fr) * 1976-05-10 1977-12-09 American Cyanamid Co Aides d'extrusion pour l'alumine rehydratable
EP0532118A1 (fr) * 1991-09-12 1993-03-17 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'essence
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US8142644B2 (en) 2007-09-10 2012-03-27 Shell Oil Company Process for hydrocracking and hydro-isomerisation of a paraffinic feedstock
US20110049011A1 (en) 2008-03-14 2011-03-03 Yuichi Tanaka Method of processing fischer-tropsch synthetic oil to manufacture diesel fuel base stock and method of calculating cracking rate upon hydrocracking wax fraction
US8679323B2 (en) 2009-11-10 2014-03-25 Eni S.P.A. Process for middle distillate production from Fischer-Tropsch waxes using a modified-zeolite-based catalyst by a basic treatment
US8685231B2 (en) 2009-11-27 2014-04-01 Shell Oil Company Process for conversion of paraffinic feedstock
US20160214094A1 (en) * 2015-01-22 2016-07-28 Chevron U.S.A. Inc. Noble metal zeolite catalyst for second-stage hydrocracking
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