WO2021136741A1 - Procédés et systèmes de conversion d'une charge d'alimentation paraffinique ayant une isomérisation accrue - Google Patents

Procédés et systèmes de conversion d'une charge d'alimentation paraffinique ayant une isomérisation accrue Download PDF

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Publication number
WO2021136741A1
WO2021136741A1 PCT/EP2020/087849 EP2020087849W WO2021136741A1 WO 2021136741 A1 WO2021136741 A1 WO 2021136741A1 EP 2020087849 W EP2020087849 W EP 2020087849W WO 2021136741 A1 WO2021136741 A1 WO 2021136741A1
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Prior art keywords
catalyst composition
composition
hydrocarbon fraction
platinum
catalyst
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PCT/EP2020/087849
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English (en)
Inventor
Johannes Petrus De Jonge
Gerrit Leendert BEZEMER
Marcello Stefano Rigutto
Andries Hendrik JANSSEN
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Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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Publication of WO2021136741A1 publication Critical patent/WO2021136741A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • 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
    • 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
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range

Definitions

  • the present disclosure relates, in some embodiments, to converting a paraffinic feedstock to a hydrocracked composition, using a platinum catalyst composition.
  • Paraffin feedstocks such as those obtained through a Fischer-Tropsch process, generally have too high of a melting point to be directly suitable for use as a liquid fuel or lubricant. Therefore, paraffin feedstocks are often converted into mixtures having more desirable mechanical and thermal properties (e.g., a lower viscosity, a lower boiling point, and/or a lower cloud point).
  • Some conversion technologies treat a paraffin feedstock with hydrogen and catalyst systems to isomerize, hydrogenate, and hydrogenolyze the paraffin feedstock to produce mixtures having desirable mechanical and thermal properties.
  • Some technologies use platinum based catalysts in their conversion processes.
  • palladium catalysts have lower hydrocracking activity than platinum and further have decreased overall effectiveness as a result of oxygenates in the feed.
  • New technologies are needed, for example, technologies allowing for high rates of conversion of paraffin feedstocks with increased isomerization and hydrogenation rates.
  • the present disclosure relates to methods and systems for converting a paraffinic feedstock to a fractionated composition using improved catalyst compositions.
  • such methods and systems including catalyst compositions having platinum and sulfate that provide for hydrocracking of a paraffinic feedstock with reduced hydrogenolysis.
  • the present disclosure describes a method for converting a paraffinic feedstock to a fractionated composition including both a hydrocracking step and a fractionating step.
  • a hydrocracking step may include combining a paraffinic feedstock, a hydrogen, and a catalyst composition in a reaction zone thereby forming a hydrocracked composition.
  • a catalyst composition may include a substrate, a platinum, and a sulfate content of from about 0.25 wt.
  • a method includes fractionating the hydrocracked composition into a fractionated composition in a fractionation zone to generate a fractionated composition having a heavy hydrocarbon fraction, an intermediate hydrocarbon fraction, and a light hydrocarbon fraction. Such a method may be performed in a system as disclosed herein.
  • the present disclosure further relates to a system for converting a paraffinic feedstock to a fractionated composition, the system including a reaction zone and a fractionation zone that are connected to each other through a transfer line.
  • a reaction zone may be configured to contain a reaction mixture comprising hydrogen, the paraffinic feedstock, and a catalyst composition.
  • a system may be further configured, in some embodiments, to allow for a hydrocracked composition to be transferred from a reaction zone to a fractionation zone through a transfer line, with the fractionation zone being configured to convert the hydrocracked composition into a fractionated composition that includes a heavy hydrocarbon fraction, an intermediate hydrocarbon fraction, and a light hydrocarbon fraction.
  • the disclosure further relates to methods of manufacturing a catalyst composition configured to convert a paraffinic feedstock to a hydrocracked composition.
  • a method of manufacturing is configured to generate a catalyst composition capable of producing a hydrocracked composition with minimal hydrogenolysis.
  • a method of manufacturing a catalyst composition may include providing a precursor catalyst composition having a substrate, analyzing the precursor catalyst composition to determine the sulfate content. Next, the sulfate content of the precursor catalyst composition may be adjusted at a range from about 0.25 wt. % to about 0.8 wt. % in the same step as the addition of the platinum compound, or as a separate step from the addition of the platinum compound, to form a catalyst composition.
  • the present disclosure relates, in some embodiments, to methods and systems for converting a paraffinic feedstock to a fractionated composition having highly isomerized products while also having minimal hydrogenolysis byproducts. Additionally, methods and systems may provide for highly hydrogenated products while having minimal hydrogenolysis byproducts. Minimizing hydrogenolysis byproduct synthesis avoids overproduction of low value light hydrocarbon products such as methane and ethane. To achieve this, a disclosed system and method uses a catalyst composition that reacts with a feed stream to selectively produce hydrocracked products having a high degree of isomerization.
  • Such hydrocracked products may have higher concentrations of a heavy hydrocarbon fraction (atmospheric boiling point of above about 540 °C) and an intermediate hydrocarbon fraction (atmospheric boiling point between about 370 °C and about 540 °C) while having a lower concentration of a light hydrocarbon fraction (atmospheric boiling point of lower than about 370 °C).
  • methods and systems for converting a paraffinic feedstock include a catalyst composition that includes a substrate, a platinum, and a sulfate, where the sulfate concentration may be from about 0.25 wt. % to about 0.8 wt. %, by weight of dry catalyst composition.
  • a paraffinic feedstock may include any feedstock including hydrocarbons having the formula C n H2 N +2 (e.g., paraffins), which may be obtained through chemical synthesis.
  • a paraffinic feedstock may be derived from a Fischer-Tropsch process that produces paraffin feedstocks by reacting hydrogen with carbon monoxide in the presence of a catalyst.
  • a paraffinic feedstock may also be derived from natural sources (e.g., a wellbore) and human created sources (e.g., recycling existing paraffinic products).
  • a paraffinic feedstock may include alkanes, alkenes, alkynes, oxygenates, and mixtures thereof.
  • a paraffinic feedstock may include a paraffin content of at least about 10 wt. %, or at least about 20 wt. %, or at least about 30 wt. %, or at least about 40 wt. %, or at least about 50 wt. %, or at least about 60 wt. %, or at least about 70 wt. %, or at least about 80 wt. %, or at least about 90 wt. %, or at least about 99 wt. %, by weight of the paraffinic feedstock, where about includes plus or minus 5 wt.
  • a paraffinic feedstock may include one or more aromatic structures including benzenes, naphthalenes, anthracenes, polycyclic aromatic hydrocarbons, analogues thereof, isomers thereof, and combinations thereof.
  • a paraffinic feedstock may include an aromatic content of less than about 10 wt. %, or less than about 9 wt. %, or less than about 8 wt. %, or less than about 7 wt. %, or less than about 6 wt. %, or less than about 5 wt. %, or less than about 4 wt. %, or less than about 3 wt. %, or less than about 2 wt.
  • a paraffinic feedstock may include an oxygenate content of less than about 10 wt. %, or less than about 9 wt. %, or less than about 8 wt. %, or less than about 7 wt. %, or less than about 6 wt. %, or less than about 5 wt. %, or less than about 4 wt. %, or less than about 3 wt. %, or less than about 2 wt. %, or less than about 1 wt. %, by weight of the paraffinic feedstock, where about includes plus or minus 0.5 wt. %.
  • the feedstock has a naphthenic content of less than 2 wt%, more in particular less than 1 wt%.
  • the present disclosure further relates to methods and systems involving a paraffinic feedstock that may include other non-carbon based contents (e.g., nitrogen, sulfur).
  • the feedstock has a sulphur content of less than 0.1 wt.%, more in particular less than 0.01 wt.%, still more in particular less than 0.001 wt.%.
  • the feedstock has a nitrogen content of less than 0.1 wt.%, more in particular less than 0.01 wt.%, still more in particular less than 0.001 wt.%.
  • a paraffinic feedstock may be characterized as a mixture of compounds where at least 50 wt. % of the compounds in the mixture have a boiling point above about 370 °C.
  • a paraffinic feedstock may include a mixture of compounds where at least about 50 wt. %, or at least about 60 wt. %, or at least about 70 wt. %, or at least about 80 wt. %, or at least about 90 wt. %, or at least about 99 wt. % of the compounds in the mixture have a boiling point above about 370 °C.
  • a disclosed catalyst composition may include a substrate that is bound to a platinum that permits the platinum to interact with a paraffinic feedstock so that hydrocracking of the feedstock can occur.
  • a catalyst composition may be combined with a paraffinic feedstock and hydrogen to form products including at least a light hydrocarbon fraction with a boiling point of less than about 370°C and a hydrocarbon fraction with a boiling point of at least about 370°C.
  • the hydrocarbon fraction with a boiling point of at least about 370°C may be separated into an intermediate hydrocarbon fraction (ie. waxy raffinate) comprising atmospheric boiling point between about 370°C and about 540°C and a heavy hydrocarbon fraction comprising an atmospheric boiling point of above about 540°C.
  • the heavy hydrocarbon fraction is recycled to the hydroprocessing reactor.
  • the heavy hydrocarbon fraction is further processed to produce extra heavy base oils.
  • the present disclosure relates to catalyst compositions having a calculable advantage over known catalyst compositions in that it provides for a higher selectivity for isomerization, hydrogenation, or both over hydrogenolysis products.
  • the present disclosure is drawn to methods and systems involving a catalyst composition having improved selectivity.
  • Such improved selectivity of a catalyst composition may include one or more of: (a) the catalyst composition having a sulfate content ranging from about 0.25 wt. % to about 0.8 wt. %; (b) the catalyst composition having a platinum content ranging from about 0.005 wt. % to about 5 wt. %, and (c) the catalyst composition having specific substrate characteristics as detailed below.
  • a catalyst composition having improved selectivity may include platinum.
  • a catalyst composition may include platinum bound to a substrate.
  • the present disclosure envisions various ways in which a platinum may be bound to a substrate in a catalyst composition.
  • platinum may: form a coordination complex with a substrate, or form an ionic bond with the substrate, or form a covalent bond with the substrate, or any combination thereof.
  • a platinum that is bound to a substrate can be derived from any platinum source.
  • a platinum source may include, but is not limited to, platinum metal, Pt(NH 3 ) (OH) 2 , Pt(NH 3 )4(N0 )2, Pt(NH 3 ) 2 (N0 2 ) 2 , (NH ⁇ PtCk, Pt(NH 3 ) 4 Cl 2 , K 2 Pt(CN) 4 , K 2 PtCl 6 , chloroplatinic acid, dichlorobis(triphenyl phosphine)platinum(II), platinum chloride, platinum oxide, platinum sulfate, platinum (II) acetate, Dichloro(cycloocta-l,5-diene)platinum(II), platinum (IV) oxide, Platinum(0)-1,3- divinyl-l,l,3,3-tetramethyldisiloxane, cis-dichlorobis(pyridine)platinum, platinum on carbon, platinum on alumina, and combinations thereof.
  • a catalyst composition including platinum derived from any platinum source and in any amount.
  • a catalyst composition may include a platinum content ranging from about 0.005 wt. % to about 5 wt. %, by weight of the catalyst composition. Catalyst compositions having a platinum content outside of this range may undesirably increase hydrogenolysis, leading to increased light hydrocarbon fractions.
  • a disclosed catalyst composition may have a platinum content of 0.005 to 5.0 wt.%, calculated as metal on the weight of the catalyst.
  • platinum is present in an amount of at least 0.02 wt.%, more in particular in an amount of at least 0.05 wt.%, still more particular in an amount of at least 0.1 wt.%.
  • platinum is present in an amount of at most 2.0 wt.%, more particular in an amount of at most 1 wt.%.
  • a platinum content of a catalyst composition used in disclosed methods and systems may be adjusted based on the ratio of hydrocarbon products generated when a paraffinic feedstock contacts the catalyst composition in the presence of hydrogen gas.
  • a catalyst composition having an adjusted sulfate content such that the hydrocarbon product mixture outcome includes a desirable amount of isomerization products, hydrogenation products, or both instead of hydrogenolysis products.
  • a catalyst composition may include a sulfate content from about 0.25 wt. % to about 0.8 wt. %, by weight of the catalyst composition. Catalyst compositions having a sulfate content outside of this range may undesirably produce larger amounts of hydrogenolysis products leading to increased light hydrocarbon fractions.
  • a disclosed catalyst composition may include a sulfate content of about 0.25 wt. % by weight of the catalyst composition, where about includes plus or minus 0.05 wt.
  • a catalyst composition may have a sulfate content of about 0.27 wt. %.
  • a sulfate content of a catalyst composition may be derived from various sulfate sources.
  • a sulfate content may be derived from one or more of ammonium sulfate, sodium sulfate, and potassium sulfate, preferably from ammonium sulfate.
  • a catalyst composition may include, in some embodiments, a sulfate bound to a platinum, a substrate, and combinations thereof.
  • a catalyst composition may include a sulfate bound to a substrate and a platinum in the form of a coordination complex, an ionic bond, a covalent bond, or combinations.
  • a sulfate may be introduced to a substrate in various different ways.
  • a sulfate may be introduced to a substrate through direct impregnation with a sulfate source, sorption of the sulfate, and combinations thereof.
  • the method may be performed at various temperatures. Adjusting the temperature used to introduce sulfate to a substrate may increase or decrease the concentration of the sulfate in the resulting catalyst composition.
  • a substrate of a catalyst composition may serve as a high surface area support for the platinum and sulfate to bind.
  • a substrate may include a ceramic including a silica, titania an alumina, a zeolite, a zeolite beta, a zirconia, a silicon carbide, a silicon nitride, an aluminum nitride, a zirconium nitride, an amorphous silica alumina, and combinations thereof.
  • the catalyst comprises 0 - 15 wt.% of zeolite beta, preferably 0.1 - 15 wt% of a zeolite beta.
  • Zeolite beta and its characteristics are well known in the art. It is a synthetic crystalline aluminosilicate, with a three dimensional pore system consisting of channels build up from 12-membered rings.
  • the silica: alumina molar ratio is at least 5.
  • the structure of zeolite beta has been characterized to be a highly faulted intergrowth of polymorphs, of which polymorph type A and polymorph type B are the dominant ones.
  • a description of the zeolite beta structure can be found in various articles i.e. J.B. Higgins, R.B. LaPierre, J.L.
  • Zeolite Beta is commercially available, for example from PQ Corporation, Zeochem AG and Siid- Chemie Group.
  • a substrate may include more than one substrate type.
  • a substrate may include about 15 wt. % of a zeolite beta and about 85 wt. % of another ceramic.
  • a substrate may include from about 0.1 wt. % to about 15 wt. % of a zeolite beta.
  • Mixing substrate types may desirably promote sulfate and/or platinum binding, which may optimize hydrogenation product production.
  • a method of converting a paraffinic feedstock to a fractionated composition may include the steps of (a) combining the paraffinic feedstock with hydrogen, a catalyst composition, and hydrogen to form a hydrocracked composition, and (b) fractionating the hydrocracked composition into a heavy hydrocarbon fraction, an intermediate hydrocarbon fraction, and a light hydrocarbon fraction.
  • Disclosed methods include the use novel catalyst compositions that minimize production of a light hydrocarbon fraction by reducing hydrogenolysis of a paraffin feedstock.
  • the feedstock is provided to a reaction zone, where it is contacted with hydrogen at a temperature in the range of 175 to 400°C and a pressure in the range of 20 to 100 bar in the presence of a catalyst.
  • Combining of a paraffinic feedstock with a catalyst composition and hydrogen to form a hydrocracked composition can be performed at various temperatures to increase conversion reaction rates, decrease conversion reaction rates, increase reaction selectivity, decrease reaction selectivity, and combinations thereof. For example, a temperature of a combining step may be increased, thereby increasing conversion reaction rates. In the reaction zone, the feedstock will undergo combined hydrocracking, hydrogenation and isomerisation.
  • the temperature in the reaction zone will depend on the nature of the feedstock, the nature of the catalyst, the pressure applied, the feed flow rate and the conversion aimed for. In one embodiment, the temperature is in the range of from 250 to 375°C.
  • the pressure applied in the reaction zone will depend on the nature of the feedstock, the hydrogen partial pressure, the nature of the catalyst, the product properties aimed for and the conversion aimed for.
  • This step may be operated at relatively low pressures, as compared to processes known in the art. Accordingly, in one embodiment the pressure is in the range of 20 to 80 bar, more in particular in the range of 30 to 80 bar.
  • the pressure is the total pressure at the exit of the reactor.
  • Hydrogen may be supplied at a gas hourly space velocity of from 100 to 10,000 normal litres (NL) per litre catalyst per hour, preferably of from 500 to 5,000 NL/L.hr.
  • the feedstock may be provided at a weight hourly space velocity of from 0.1 to 5.0 kg per litre catalyst per hour, preferably of from 0.5 to 2.0 kg/L.hr.
  • the ratio of hydrogen to feedstock may range of from 100 to 5,000 NL/kg and is preferably of from 250 to 2,500 NL/kg.
  • Reference herein to normal litres is to litres at conditions of standard temperature and pressure, i.e. at 0 C and 1 atmosphere.
  • a product formed during a combining step includes a hydrocracked composition, which may be fractionated into various products such as a heavy hydrocarbon fraction, an intermediate hydrocarbon fraction, and a light hydrocarbon fraction.
  • Fractionating a hydrocracked composition may include simple distillation, fractional distillation, steam distillation, vacuum distillation, short path distillation, zone distillation, or combinations thereof.
  • fractionating a hydrocracked composition produces a light hydrocarbon fraction, an intermediate hydrocarbon fraction, and a heavy hydrocarbon fraction, which may be formed in various weight percentages.
  • a light hydrocarbon fraction includes a mixture of hydrocarbons having an atmospheric boiling point of lower than about 370 °C.
  • An atmospheric boiling point includes the boiling point of a composition at 1 bar, which is the atmospheric pressure at sea level.
  • An intermediate hydrocarbon fraction includes an atmospheric boiling point between about 370 °C and about 540 °C.
  • a heavy hydrocarbon fraction includes an atmospheric boiling point of above about 540 °C.
  • a disclosed method may produce a light fraction, an intermediate fraction, and a heavy fraction at any ratio. Fractionated mixtures may be collected to be stored or treated to additional refinement steps including dewaxing.
  • a disclosed method of converting a paraffinic feedstock to a fractionated composition includes the steps of (a) combining the paraffinic feedstock with a catalyst composition and hydrogen to form a hydrocracked composition, and (b) fractionating the hydrocracked composition. Additionally, a disclosed method may include a step of dewaxing an intermediate hydrocarbon fraction and/or a heavy hydrocarbon fraction through catalytic dewaxing, solvent dewaxing, or combinations thereof.
  • a dewaxing step may include isomerizing paraffins with only a limited number of branches (e.g., straight chain paraffins, slightly branched paraffins) to form paraffins having a larger number of branches which have a lower overall boiling point as compared to the pre-isomerized paraffin material.
  • Some embodiments may include a catalytic dewaxing step, where a fractionated mixture including an intermediate hydrocarbon fraction may be combined with a zeolite catalyst, a molecular sieve, and a hydrogen in a dewaxing zone to produce a dewaxed product.
  • a zeolite catalyst includes a metal having a hydrocracked function, such as a Group 8 metal, which includes a nickel, a cobalt, a platinum, and a palladium.
  • a zeolite catalyst may include a binder including a clay, a metal oxide, a silica-alumina, a silica-magnesia, a silica, a titania, a zirconia, an alumina, and mixtures thereof.
  • a dewaxing step may be performed at any temperature ranging from about 200 °C to about 400 °C.
  • a disclosed method includes a step of dewaxing an intermediate hydrocarbon fraction and/or a heavy hydrocarbon fraction to produce a dewaxed product and a wax.
  • a dewaxing step may be performed at various pressures, such as those ranging from about 1 bar to about 200 bar.
  • solvent dewaxing includes combining an intermediate hydrocarbon fraction, a heavy hydrocarbon fraction, or a combination thereof with one or more solvents.
  • a solvent dewaxing step may incorporate solvents including C3-C6 ketones (e.g., methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof), C6-C10 aromatic hydrocarbons (e.g., toluene) mixtures of ketones and aromatics (e.g., methyl ethyl ketone and toluene), auto-refrigerative solvents such as liquefied, normally gaseous C2-C4 hydrocarbons such as a propane, a propylene, a butane, a butylene, and mixtures thereof.
  • a wax that is separated into a solvent through a dewaxing step may be separated through filtration such as through a filter.
  • Comparative catalyst A contained 0.8 wt. % of platinum on a carrier containing 70 wt. % of amorphous silica-alumina (alumina content of 29 wt. %) and 30 wt. % of alumina binder, by weight of the carrier.
  • Catalyst A contained 0.27 wt. % sulfate by XRF analyses.
  • Catalysts B, C, and D all according to the disclosure, were obtained by impregnating catalyst A with different concentrations of (NFLO2SO4 solution and subsequent calcination at 450 °C.
  • Catalysts B, C, and D contained 0.42 wt. %, 0.48 wt. % and 0.81 wt. % sulfate by XRF analysis.
  • the four catalysts were screened to determine how much they convert a feedstock to n-paraffins. This data directly relates to the isomerization ability of each catalyst samples since the more n-paraffins that are formed, the less isomerization products are formed. In this experiment, all three catalysts B, C, and D formed less n- paraffins than the comparative catalyst.
  • a feedstock was prepared by dissolving 8 wt. % of a hydrogenated Fischer-Tropsch wax fraction comprising C18-C32 n-paraffins in n-hexadecane. The feedstock was continuously fed to a hydrocracking step in once- through mode of operation.
  • Catalyst A particles were crushed and 250 mg of the 40-80 mesh fraction of the crushed particles were loaded in a nanoflow reactor and reduced at 30 bar in a flow of hydrogen at 400 °C for 2 hours prior to testing in the hydrocracking step.
  • a total pressure of 30 bar was used for the hydrocracking test.
  • Hydrogen with a purity of >99 %v was added with a gas-hourly-space-velocity of 1000 Nl/kg feed.
  • the fresh liquid feedstock weight-hourly-space-velocity was 4.0 kg/1 catalyst/h.
  • the reaction products were separated in a gaseous stream and a liquid stream.
  • the gaseous stream was analysed with on-line GC, while the liquid fractions were analysed on n- paraffin and i-paraffin contents on a WCOT Ultimetal HT Simdist column.
  • the total product yield was calculated on the compositional data obtained for both streams and the quantity of hydrocarbon product in each stream.
  • the conversion level was determined using atmospheric boiling point distributions for liquid feedstock and hydrocarbon products.
  • the conversion of 370 °C+ material in the feedstock was varied by changing the Weight Average Bed Temperature over the reactor.
  • the n-paraffin content in the kerosene boiling range (150-250 °C) as well as the n-paraffin content in the >370 °C boiling range at 50% 370 °C+ conversion were calculated by interpolation and are presented in Table 1.
  • Catalysts B, C, and D from Example 1 were tested in the same way as catalyst A in example 2.
  • the n-paraffin content in the 150-250 °C range and in the >370 °C range at 50% 370 °C+ conversion were calculated by interpolation and are presented in Table 1.
  • Catalyst F Three catalysts were prepared, one comparative catalyst (catalyst F) and two catalysts according to the disclosure (catalysts E & G).
  • Catalyst E (according to the present disclosure) was prepared by first preparing a catalyst carrier containing 65.1 wt. % of amorphous silica-alumina (alumina content of 29 wt. %), 4 wt. % zeolite beta, 0.9 wt. % Na and 30 wt. % of alumina binder. This carrier was subsequently impregnated with an impregnation solution containing the concentration of platinum tetramine nitrate required to arrive at a loading of 0.8 wt. % of platinum on the final catalyst. The impregnated carrier particles were calcined at a temperature of 450 °C for 2 hours. The sulfate content of catalyst E was 0.3 wt. % as measured with XRF.
  • Catalyst F (comparative example) was prepared by preparing a catalyst carrier with the same composition as the carrier for catalyst E, except that the sulfate content of the carrier was 0.14 wt. % as measured with XRF.
  • the carrier was subsequently impregnated with an impregnation solution containing the concentration of platinum tetramine nitrate required to arrive at a loading of 0.8 wt. % of platinum on the final catalyst.
  • the impregnated carrier particles were calcined at a temperature of 450 °C for 2 hours.
  • Catalyst G (according to the disclosure) was prepared by impregnating the carrier of catalyst F with an impregnation solution containing the concentration of platinum tetramine nitrate required to arrive at a loading of 0.8 wt. % of platinum on the final catalyst as well as the concentration ammonium sulfate required to arrive at an additional loading of 0.2 wt. % sulfate on the final catalyst.
  • the impregnated carrier particles were calcined at a temperature of 450 °C for 2 hours.
  • the sulfate content of catalyst G was 0.34 wt. % as measured with XRF.
  • a Fischer-Tropsch feedstock was obtained by fractionating the C5+ effluent from a Fischer Tropsch process to obtain a heavy Cl 4+ stream to be used in the experiments and a light ⁇ C14 stream that was not used.
  • the heavy Cl 4+ stream contained 80 wt. % boiling above 370 °C and 47 wt. % above 540° C as determined by ASTM D-7169.
  • the Fischer Tropsch feedstock was continuously fed to a hydrocracking step in once-through mode of operation.
  • catalysts E, F, and G were tested with the Fischer Tropsch feed.
  • the catalyst particles were mixed with silicon carbide (SiC) in a 1:2 catalyskSiC volume ratio and a total quantity of 50 ml catalyst was loaded in the reactor.
  • the catalyst was loaded into a fixed bed reactor. A total pressure of 60 bar was used. Hydrogen with a purity of >99 %v was added with a gas-hourly-space-velocity of 1000 Nl/lcatalyst/h. The fresh liquid feedstock weight-hourly-space-velocity was 1.0 kg/lcatalyst/h.
  • the reaction products were separated in a gaseous stream, a light liquid stream and a heavy liquid stream. Each fraction was analysed separately. The gaseous stream was analysed with on-line GC, the liquid fractions were collected over 24 h intervals and analysed by ASTM D-2887 (light liquid stream) and ASTM D-7169 (heavy liquid stream).
  • the total product yield was calculated on the compositional data obtained for each stream and the quantity of hydrocarbon product in each stream.
  • the conversion level was determined using atmospheric boiling point distributions for liquid feedstock and hydrocarbon products.
  • the conversion of 370 °C+ material in the feedstock was varied by changing the Weight Average Bed Temperature over the reactor.
  • the n-paraffin content of light- and heavy liquid stream was determined based on a GCxGC technique.
  • the C10-C22 n-paraffin content as a percentage of the total hydrocarbon content in the C10-C22 range are given in Table 2.
  • C10-C22 refers to molecules with a carbon number ranging from 10 to 22.
  • Table 2 C10-C22 n-paraffin content at 60% 370 °C+ conversion (Examples 3 & 4)
  • the disclosed endpoints may be treated as exact and/or approximations as desired or demanded by the particular embodiment. Where the endpoints are approximate, the degree of flexibility may vary in proportion to the order of magnitude of the range. In addition, it may be desirable, in some embodiments, to mix and match range endpoints. Also, in some embodiments, may form the basis of a range (e.g., depicted value +/- about 10%, depicted value +/- about 50%, depicted value +/- about 100%) and/or a range endpoint.
  • a range e.g., depicted value +/- about 10%, depicted value +/- about 50%, depicted value +/- about 100%
  • a value of 50 depicted in an example, table, and/or drawing may form the basis of a range of, for example, about 45 to about 55, about 25 to about 100, and/or about 0 to about 100.

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Abstract

La présente invention concerne un procédé de conversion d'une charge paraffinique en une composition fractionnée, le procédé comprenant : (A) la combinaison de la charge paraffinique, de l'hydrogène et d'une composition de catalyseur dans une zone de réaction pour former une composition hydrocraquée, la composition de catalyseur comprenant : un substrat ; un platine ; et une teneur en sulfate d'environ 0,25 % en poids à environ 0,8 % en poids, en poids de la composition de catalyseur ; et (b) fractionner la composition hydrocraquée en la composition fractionnée dans une zone de fractionnement, la composition fractionnée comprenant au moins une fraction d'hydrocarbure léger ayant un point d'ébullition inférieur à environ 370 °C et une fraction d'hydrocarbure ayant un point d'ébullition d'au moins environ 370° C.
PCT/EP2020/087849 2019-12-30 2020-12-24 Procédés et systèmes de conversion d'une charge d'alimentation paraffinique ayant une isomérisation accrue WO2021136741A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3274124A (en) * 1964-01-02 1966-09-20 Universal Oil Prod Co Process of preparing a silica-alumina supported group viii metal hydrocracking catalyst
US3629152A (en) * 1967-10-03 1971-12-21 American Cyanamid Co Process for preparing alumina-coated silica catalyst material and the material so prepared
US5120898A (en) * 1984-09-10 1992-06-09 Research Association For Utilization Of Light Oil Process for isomerizing hydrocarbons
EP0532116A1 (fr) * 1991-09-12 1993-03-17 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de combustibles hydrocarburés
WO2011064236A1 (fr) * 2009-11-27 2011-06-03 Shell Internationale Research Maatschappij B.V. Procédé de conversion d'une charge paraffinique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3274124A (en) * 1964-01-02 1966-09-20 Universal Oil Prod Co Process of preparing a silica-alumina supported group viii metal hydrocracking catalyst
US3629152A (en) * 1967-10-03 1971-12-21 American Cyanamid Co Process for preparing alumina-coated silica catalyst material and the material so prepared
US5120898A (en) * 1984-09-10 1992-06-09 Research Association For Utilization Of Light Oil Process for isomerizing hydrocarbons
EP0532116A1 (fr) * 1991-09-12 1993-03-17 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de combustibles hydrocarburés
WO2011064236A1 (fr) * 2009-11-27 2011-06-03 Shell Internationale Research Maatschappij B.V. Procédé de conversion d'une charge paraffinique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J.B. HIGGINSR.B. LAPIERREJ.L. SCHLENKERA.C. ROHRMANJ.D. WOODG.T. KERRW.J. ROHRBAUGH, ZEOLITES, vol. 8, 1998, pages 446
J.M. NEWSAMM.M. J. TREACYW.T. KOETSIERC.B. DE GRUYTER, PROC. R. SOC. LOND. A, vol. 420, 1988, pages 375

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