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CN-122003486-A - Method for producing transportation fuels and components thereof

CN122003486ACN 122003486 ACN122003486 ACN 122003486ACN-122003486-A

Abstract

The present invention relates to a process for producing jet fuel, diesel fuel, or components thereof from a pretreated feed comprising at least 90 wt% liquid paraffin by hydroisomerisation reaction using a support-based metal impregnated EU-2 based zeolite as catalyst. According to this process, the desired product distribution is adjusted by the hydroisomerization reaction temperature.

Inventors

  • Sylvia Albersberg
  • Karen Abreu Rezendi
  • Evelina makla

Assignees

  • 耐思特公司

Dates

Publication Date
20260508
Application Date
20240926
Priority Date
20231013

Claims (13)

  1. 1. A method for producing a transportation fuel comprising jet fuel, diesel fuel, or components thereof, the method comprising the steps of: a) Providing a pretreated liquid feed comprising at least 90 wt% of paraffins; b) Subjecting the feed to a hydroisomerisation reaction at a pressure of from 1 bar to 100 bar, preferably from 20 bar to 100 bar, more preferably from 20 bar to 90 bar, for example from 20 bar to 60 bar, in the presence of a hydrogen stream and a hydroisomerisation catalyst comprising an active metal selected from noble metals, nickel and any combination thereof, EU-2 zeolite, and a support selected from alumina, silica and alumina-silica, wherein the content of the active metal in the catalyst is from 0.1 wt to 7.0 wt, and wherein the SiO 2 /Al 2 O 3 molar ratio of the EU-2 zeolite is from 10 to 100, preferably from 15 to 85, for example from 40 to 80, and Adjusting the hydroisomerization reaction temperature between 270 ℃ and 370 ℃ to provide the desired hydroisomerized hydrocarbon composition, wherein I. For a weight ratio of hydrocarbon suitable for use as jet fuel or a component thereof to hydrocarbon suitable for use as diesel fuel or a component thereof of greater than 1, adjusted from 330 ℃ to 370 ℃, preferably from 336 ℃ to 370 ℃, more preferably from 336 ℃ to 360 ℃, and For a weight ratio of hydrocarbon suitable for use as diesel fuel or a component thereof to hydrocarbon suitable for use as jet fuel or a component thereof of greater than 1, adjusted from 270 ℃ to 324 ℃, preferably from 270 ℃ to 320 ℃, more preferably from 280 ℃ to 320 ℃, and C) Hydrocarbons suitable for use as jet fuel or components thereof, or as diesel fuel or components thereof, are recovered as the primary product from the desired hydroisomerization stream by separation.
  2. 2. The method of claim 1, wherein the EU-2 zeolite further comprises one or more of the following features: Crystallinity of 50% to 95%, as measured by X-ray diffraction (XRD) according to ASTM D5758-01 (2021), BET specific surface areas of 180m 2 /g to 450m 2 /g, for example 200m 2 /g to 300m 2 /g, as determined by nitrogen physisorption, Acidity is from 80 to 700. Mu. Mol/g, preferably from 150 to 500. Mu. Mol/g, more preferably from 200 to 400. Mu. Mol/g, for example from 350 to 400. Mu. Mol/g, as measured by pyridine-FTIR, The ratio of Bronsted acid sites to Lewis acid sites is from 0.5 to 20, as measured by pyridine-FTIR, and The crystalline EU-2 zeolite particles are essentially needle-shaped particles.
  3. 3. The method of claim 1 or 2, wherein the pretreated liquid feed comprises no greater than 1 W-ppm, preferably not more than 0.5 w-ppm, of alkali metal and alkaline earth metal impurities, calculated as elemental alkali metal and alkaline earth metal; 1 w-ppm, preferably not more than 0.5 w-ppm, of other metals, calculated as elemental metals; 5 w-ppm, preferably not more than 1 w-ppm, more preferably not more than 0.2 w-ppm of nitrogen-containing impurities, calculated as elemental nitrogen; 5 w-ppm, e.g., no more than 1 w-ppm, of phosphorus-containing impurities, calculated as elemental phosphorus; 1 w-ppm of silicon-containing impurities, calculated as elemental silicon; 10 w-ppm, preferably no more than 5 w-ppm, more preferably no more than 1 w-ppm, most preferably no more than 0.4 w-ppm of sulfur-containing impurities, calculated as elemental sulfur; 10 w-ppm, preferably not more than 5 w-ppm, of chlorine-containing impurities, calculated as elemental chlorine.
  4. 4. A process according to any one of claims 1 to 3, wherein the hydroisomerisation temperature is adjusted between 330 ℃ and 370 ℃, preferably between 336 ℃ and 370 ℃, more preferably between 336 ℃ and 360 ℃, thereby producing a hydroisomerisation stream, wherein the weight ratio of hydrocarbons suitable for use as jet fuel or components thereof to hydrocarbons suitable for use as diesel fuel or components thereof is greater than 1, and separating from the hydroisomerisation stream at least a fraction boiling from 107 ℃ to 280 ℃ at atmospheric pressure (1 bar absolute), thereby recovering jet fuel or components thereof.
  5. 5. A process according to any one of claims 1 to 3, wherein the hydroisomerisation temperature is adjusted between 270 ℃ and 324 ℃, preferably between 270 ℃ and 320 ℃, more preferably between 280 ℃ and 320 ℃, thereby producing a hydroisomerisation stream, wherein the weight ratio of hydrocarbons suitable for use as diesel fuel or components thereof to hydrocarbons suitable for use as jet fuel or components thereof is greater than 1, and separating from the hydroisomerisation stream at least a fraction boiling between 170 ℃ and 360 ℃ at atmospheric pressure (1 bar absolute), thereby recovering diesel fuel or components thereof.
  6. 6. The process of any one of claims 1 to 5, wherein in step b) the H 2 flow is from 100 to 800N-L H 2 /L feed.
  7. 7. The process according to any one of claims 1 to 6, wherein the active metal is platinum, palladium, or rhodium, which is impregnated on the support, and wherein the active metal content of the hydroisomerisation catalyst is from 0.4 wt to 0.6 wt%, such as about 0.5 wt.
  8. 8. The method according to any one of claims 1 to 7, wherein step a) comprises I. Providing a renewable raw material, wherein the renewable raw material comprises, Pretreating the renewable feedstock to reduce the amount of impurities therein so that the renewable feedstock does not include greater than 10 w-ppm of alkali metal and alkaline earth metal impurities calculated as elemental alkali metal and alkaline earth metal, greater than 10 w-ppm of other metals calculated as elemental metal, greater than 1000 w-ppm of nitrogen-containing impurities calculated as elemental nitrogen, greater than 30 w-ppm of phosphorus-containing impurities calculated as elemental phosphorus, greater than 5 w-ppm of silicon-containing impurities calculated as elemental silicon to produce a pretreated renewable feedstock, Subjecting the pretreated renewable feedstock to a hydrodeoxygenation reaction to produce a hydrodeoxygenation effluent, wherein the hydrodeoxygenation reaction comprises one or more of: a.250 ℃ to 400 ℃, preferably 260 ℃ to 380 ℃, more preferably 280 ℃ to 360 ℃, such as 300 ℃ to 330 ℃, B. At a pressure in the range from 10 to 200 bar, preferably from 20 to 100 bar, more preferably from 20 to 80 bar, C. WHSV in the range from 0.25 h -1 to 3 h -1 , preferably from 0.5 h -1 to 3.0 h -1 , more preferably from 0.7 h -1 to 2.5 h -1 , most preferably from 1.0 h -1 to 2.0 h -1 , D.350 to 1500N-L H 2 /L feed, preferably 350 to 1100N-L H 2 /L feed, more preferably 350 to 1000N-L H 2 /L feed H 2 stream, and E. A hydrodeoxygenation catalyst on a support, the hydrodeoxygenation catalyst selected from Pd, pt, ni, co, mo, ru, rh and W or any combination thereof, to produce a hydrodeoxygenation stream, and Subjecting the hydrodeoxygenation stream to gas-liquid separation, thereby producing a gaseous stream and the pretreated liquid feed comprising at least 90wt. -% paraffins.
  9. 9. The process of claim 8, wherein the hydrodeoxygenation stream comprises at least 92 wt%, preferably at least 95 wt%, more preferably at least 99 wt%, of paraffins, based on the total weight of hydrocarbon products.
  10. 10. The method according to any one of claims 1 to 7, wherein step a) comprises I. Providing a feedstock comprising CO 2 and H 2 ; Converting the feedstock to synthesis gas; Upgrading the synthesis gas to hydrocarbons by oligomerization, preferably by Fischer-Tropsch synthesis or methanol synthesis, to produce an upgraded effluent, Subjecting said upgraded effluent to gas-liquid separation to produce a gas stream and a liquid effluent, and Separating a feed comprising at least 90 wt% paraffins from the liquid effluent.
  11. 11. Use of a catalyst comprising an active metal selected from noble metals, nickel and any combination thereof, EU-2 zeolite and a support selected from alumina, silica and alumina-silica, wherein the content of the active metal in the catalyst is from 0.1 wt to 7.0 wt-%, the SiO 2 /Al 2 O 3 molar ratio of the EU-2 zeolite is from 10 to 100, preferably from 15 to 85, such as 40 to 80, at a temperature of 270 to 370 ℃, at a pressure of 1 to 100 bar, preferably from 20 to 100 bar, more preferably from 20 to 90 bar, such as from 20 to 60 bar, under H 2 for adjusting the product distribution of the hydroisomerisation reaction to produce mainly diesel fuel or a component thereof at 270-324 ℃, preferably at 270-320 ℃, more preferably at 280-320 ℃, and to produce mainly jet fuel or a component thereof at 330-370 ℃, preferably at 336-370 ℃, more preferably at 336-360 ℃.
  12. 12. The use of claim 11, wherein the EU-2 zeolite further comprises one or more of the following features: Crystallinity of 50% to 95%, as measured by X-ray diffraction (XRD) according to ASTM D5758-01 (2021), BET specific surface areas of 180m 2 /g to 450m 2 /g, for example 200m 2 /g to 300m 2 /g, as determined by nitrogen physisorption, Acidity is from 80 to 700. Mu. Mol/g, preferably from 150 to 500. Mu. Mol/g, more preferably from 200 to 400. Mu. Mol/g, for example from 350 to 400. Mu. Mol/g, as measured by pyridine-FTIR, The ratio of Bronsted acid sites to Lewis acid sites is from 0.5 to 20, as measured by pyridine-FTIR, and The crystalline EU-2 zeolite particles are essentially needle-shaped particles.
  13. 13. Use according to claim 11 or 12, wherein the H 2 stream is 100 to 800N-LH 2 /L feed, preferably 200 to 600N-LH 2 /L feed.

Description

Method for producing transportation fuels and components thereof Technical Field The present disclosure relates to a process for producing transportation fuels or components thereof, particularly jet fuel, diesel fuel or components thereof, from a paraffinic feed, particularly to a process comprising hydroisomerizing a paraffinic feed in the presence of a catalyst comprising an active metal and an EU-2 based zeolite. Background Transportation fuels such as aviation gasoline (avgas), jet fuel, gasoline and diesel can be produced from a variety of feedstocks including crude oil, coal, vegetable oil, animal fat, waste oil and residual oil and fat, municipal waste, waste plastics and even used tires. Furthermore, it has been proposed to produce transportation fuels starting from the reduction of carbon dioxide with renewable hydrogen, by means of a reverse water gas shift reaction, followed by a Fischer-Tropsch (Fischer-Tropsch) reaction, for example, to form the desired hydrocarbons. The process includes one or more steps for converting the feedstock to a paraffinic feedstock. The paraffinic feed is typically further processed by, for example, hydrocracking and/or hydroisomerization to obtain the desired properties of the transportation fuel or components thereof. It is known that the type of transportation fuel can be controlled by hydroisomerization reaction conditions. For example, EP 2138552B1 discloses a process for converting renewable feedstocks into diesel by hydrotreating at temperatures in the range of 150 ℃ to 500 ℃ using a catalyst comprising at least one group VIII metal and/or at least one group VIB metal and a one-dimensional 10MR zeolite molecular sieve selected from at least ZSM-48 and ZBM-30, followed by the use of the catalyst in the mixture. EP 2275514 in turn converts renewable feedstocks into light fuels by a process comprising deoxygenation of natural fats or derivatives thereof followed by hydrocracking and isomerization steps. The isomerisation reaction is carried out at a temperature ranging from 100 ℃ to 500 ℃ in the presence of a catalyst based on a hydrogen transfer component and an acid component. The hydrogen transfer component is a transition metal selected from groups 5-10 of the periodic Table (IUPAC 1990), preferably selected from Ni, pd, pt, co, mo and V, most preferably platinum. The acid component is preferably an inorganic oxide compound having acid sites, more preferably selected from the group consisting of chlorinated alumina and protonated 10-and 12-membered zeolites, even more preferably selected from the group consisting of protonated PSH-3, beta-and MCM-22 zeolites. Most preferably the acid component is protonated mordenite, protonated beta zeolite or protonated ZSM-12. WO 2023126565 discloses a process for the preparation of renewable aviation fuel or components thereof from renewable feedstock, wherein the process comprises separate hydrodeoxygenation and hydroisomerisation steps, wherein the hydroisomerisation is catalysed by metal impregnation classification ZSM-23. Disclosure of Invention The present invention is based on the observation that when a feed comprising at least 90 wt% of pretreated liquid paraffins is hydroisomerized using as hydroisomerization catalyst a catalyst comprising an active metal selected from the group consisting of noble metals, nickel and any combination thereof and EU-2 zeolite supported on a carrier, the product distribution can be adjusted to produce mainly jet fuel or components thereof or to produce mainly diesel or components thereof by adjusting the hydroisomerization temperature. It is therefore an object of the present invention to provide a method of producing a transportation fuel comprising jet fuel, diesel fuel or a component thereof, the method comprising: a) Providing a pretreated liquid feed comprising at least 90 wt% of paraffins; b) Subjecting the pretreated liquid feed to a hydroisomerisation reaction in the presence of a hydrogen stream, and a hydroisomerisation catalyst comprising an active metal selected from noble metals, nickel and any combination thereof, EU-2 zeolite, and a support selected from alumina, silica, and alumina-silica, at a pressure of from 1 bar to 100 bar, preferably from 20 bar to 100 bar, more preferably from 20 bar to 90 bar, for example from 20 bar to 60 bar, wherein the active metal content in the catalyst is from 0.1 wt to 7.0 wt-%, wherein the SiO 2/Al2O3 molar ratio of EU-2 zeolite is from 10 to 100, preferably from 15 to 85, for example from 40 to 80, and the hydroisomerisation reaction temperature is adjusted to between 270 ℃ and 370 ℃ to provide a hydroisomerisation stream comprising the desired hydroisomerised hydrocarbon composition, wherein I. For a weight ratio of hydrocarbons suitable for use as jet fuel or components thereof to hydrocarbons suitable for use as diesel fuel or components thereof of greater than 1, the adjustment is from 330 ℃ to 370 ℃, preferably from 336 ℃ to 3