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WO2018118347A1 - Procédé intégré de fabrication d'essence à indice d'octane élevé et de gazole à indice de cétane élevé - Google Patents

Procédé intégré de fabrication d'essence à indice d'octane élevé et de gazole à indice de cétane élevé Download PDF

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Publication number
WO2018118347A1
WO2018118347A1 PCT/US2017/063385 US2017063385W WO2018118347A1 WO 2018118347 A1 WO2018118347 A1 WO 2018118347A1 US 2017063385 W US2017063385 W US 2017063385W WO 2018118347 A1 WO2018118347 A1 WO 2018118347A1
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WIPO (PCT)
Prior art keywords
iso
cetane
naphtha
heavy
paraffins
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PCT/US2017/063385
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English (en)
Inventor
Kun Wang
Shamel Merchant
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ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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Publication date
Priority claimed from US15/388,013 external-priority patent/US9637423B1/en
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Priority to EP17817491.8A priority Critical patent/EP3559168A1/fr
Priority to CA3045986A priority patent/CA3045986A1/fr
Publication of WO2018118347A1 publication Critical patent/WO2018118347A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to an integrated process to upgrade relatively low-value paraffinic materials to high-octane gasoline and high-cetane diesel.
  • the process is particularly applicable to the upgrading of low-value paraffinic feeds, such as iso-butane and heavy virgin naphtha to make high-octane alkylate and high-cetane diesel via oxidation.
  • Alkylate is composed of a mixture of high-octane, branched-chain paraffinic hydrocarbons (mostly iso-heptane and iso-octane). Alkylate is a premium gasoline blending stock because it has exceptional antiknock properties, relatively low Reid Vapor Pressure (RVP), and is clean burning.
  • RVP Reid Vapor Pressure
  • the octane number of an alkylate depends mainly upon the kind of feeds used and upon operating conditions. For example, iso-octane results from combining C4 olefins with iso- butane and has an octane rating of 100 by definition. There are other products in the alkylate, so the octane rating will vary accordingly.
  • High-cetane diesel diesel with a cetane number in the range of about 40- 110, preferably about 45-90, and more preferably about 50-80
  • Fischer- Tropsch synthesis diesel molecules with a cetane number in the range of about 40- 110, preferably about 45-90, and more preferably about 50-80
  • Low octane naphtha such as heavy virgin naphtha, is typically converted to aromatics, a high octane gasoline blend, using catalytic reforming.
  • the process involves: (1) oxidation of an iso-paraffin to alkyl hydroperoxide and alcohol; (2) converting the alkyl hydroperoxide and alcohol to dialkyl peroxide; (3) converting low-octane, paraffinic gasoline molecules using the dialkyl peroxides as radical initiators, thereby forming high-cetane diesel, while the dialkyl peroxide is converted to an alcohol; (4) converting the alcohol to an olefin; and (5) alkylating the olefin with iso-butane to form high-octane alkylate.
  • Step 5 An alternative embodiment to Step 5 is dimerization of the olefin giving another type of high octane fuel.
  • the net reaction is thus conversion of iso-paraffin to high-octane gasoline alkylate, and conversion of low-octane paraffinic gasoline to high-cetane diesel.
  • the process involves (1) oxidation of iso-butane to t-butyl hydroperoxide and t-butyl alcohol; (2) converting the t-butyl hydroperoxide and the t-butyl alcohol to di-t-butyl peroxide; (3) converting heavy naphtha, such as heavy virgin naphtha, heavy cat naphtha, or coker naphtha, using the di-t-butyl peroxide as radical initiators, thereby forming high-cetane diesel, while the di-t-butyl peroxide is converted to t-butyl alcohol; (4) converting the t-butyl alcohol to iso-butylene; and (5) alkylating the iso-butylene with iso- butane to form high-octane alkylate.
  • Step 5 An alternative to Step 5 is dimerization of the olefin giving another type of high octane fuel.
  • the net reaction is thus conversion of iso-butane to high-octane gasoline alkylate, and conversion of heavy virgin naphtha to high-cetane diesel.
  • the present invention relates to an integrated process for upgrading low-value paraffinic materials to high octane gasoline and high-cetane diesel.
  • the process of the present invention involves three primary steps: (1) oxidation of an iso-paraffin to alkyl hydroperoxide and alcohol; (2) converting the alkyl hydroperoxide and alcohol to dialkyl peroxide; (3) converting low-octane, paraffinic gasoline molecules using the dialkyl peroxides as radical initiators, thereby forming high-cetane diesel, while the dialkyl peroxide is converted to an alcohol; (4) converting the alcohol to an olefin; and (5) alkylating the olefin with iso-butane to form high-octane alkylate.
  • the net reaction is thus conversion of iso-paraffin to high-octane gasoline alkylate, and conversion of low-octane paraffinic gasoline to high-cetane diesel.
  • the iso-paraffin feedstock is iso- butane.
  • the process proceeds as described generally above: (1) oxidation of iso-butane to t-butyl hydroperoxide and t-butyl alcohol; (2) converting the t-butyl hydroperoxide and the t-butyl alcohol to di-t-butyl peroxide; (3) converting heavy naphtha, such as heavy virgin naphtha, heavy cat naphtha, or coker naphtha, using the di-t-butyl peroxide as radical initiators, thereby forming high- cetane diesel, while the di-t-butyl peroxide is converted to t-butyl alcohol; (4) converting the t- butyl alcohol to iso-butylene; and (5) alkylating the iso-butylene with iso-butane to form high- octane alkylate.
  • Step 5 An alternative to Step 5 is dimerization of the olefin giving another type of high octane fuel.
  • the net reaction is thus conversion of iso-butane to high-octane gasoline alkylate, and conversion of heavy virgin naphtha to high-cetane diesel.
  • Equation 1 Equation 2:
  • Steps 1 and 2 have been previously described with respect to mixed paraffinic feedstocks in applicant's co-pending application, U.S. Publ. App. No. 2016/0168048, incorporated by reference herein in its entirety.
  • U.S. Publ. App. No. 2016/0168048 describes a process to convert light paraffins to heavier hydrocarbons generally, for example, distillates and lubricant base stocks, using coupling chemistry analogous to Steps 1 and 2 described above.
  • 2016/0168048 is directed to mixed paraffinic feed to create distillates and lubricant base stocks
  • the present invention utilizes analogous coupling chemistry to create high-cetane diesel utilizing iso-paraffins such as iso-butane and iso-paraffinic gasoline as feedstock.
  • Iso-butane oxidation in Step 1/Equation 1 is well-established commercially for making t-butyl hydroperoxide (TBHP) for propylene oxide manufacture, with variants of the process also described, for example, in U.S. Pat. No. 2,845,461; U.S. Pat. No. 3,478,108; U.S. Pat. No. 4,408,081 and U.S. Pat. No. 5, 149,885.
  • EP 0567336 and U.S. Pat. No. 5,162,593 disclose co- production of TBHP and t-butyl alcohol (TBA).
  • Step 1 As TBA is another reactant used in Step 2 of the present invention, the present inventive process scheme utilizes Step 1 as a practical source of these two reactants.
  • Air (- 21% oxygen), a mixture of nitrogen and oxygen containing 2-20 vol% oxygen, or pure oxygen, can be used for the oxidation, as long as the oxygen-to-hydrocarbon vapor ratio is kept outside the explosive regime.
  • air is used as the source of oxygen.
  • Typical oxidation conditions for Step 1 of the present invention are: 110-150 °C (preferably 130 to 140 °C, at a pressure of about 300-800 psig (preferably about 450-550 psig), with a residence time of 2-24 hours (preferably 6-8 h), to give a targeted conversion of 15%-70% (preferably 30-50%).
  • Selectivity to TBHP of 50-80% and to TBA of 20-50% is typical.
  • Step 2/Equation 2 the conversion of the TBHP and TBA to di-t-butyl peroxide (DTBP) is performed using an acid catalyst.
  • DTBP di-t-butyl peroxide
  • U.S. Pat. No. 5,288,919 describes the use of an inorganic heteropoly and/or isopoly acid catalyst (such as for the reaction of TBA with TBHP.
  • the conjoint production of DTBP and TBA from TBHP is also described in U.S. Pat. No. 5,345,009.
  • a preferred configuration for the present invention uses reactive distillation where product water is continuously removed as overhead by-product.
  • Typical reaction temperature is in the range of 50 - 200 °C, preferably 60 - 150 °C, more preferably 80-120 °C.
  • the TBHP to TBA mole ratio is in the range of 0.5 - 2, preferably 0.8 - 1.5, more preferably 0.9 - 1.1.
  • the reaction can be performed with or without a solvent. Suitable solvents comprise hydrocarbons having a carbon number greater than 3, such as paraffins, naphthenes, or aromatics. Conveniently, the unreated iso-butane from Step 1 can be used as solvent for Step 2. Pressure for the reaction is held at appropriate ranges to ensure the reaction occurs substantially in the liquid phase, for example, 0 - 300 psig, preferably 5 - 100 psig, more preferably 15 - 50 psig.
  • An acid catalyst such as AmberlystTM resin, NafionTM resin, aluminosilicates, acidic clay, zeolites (natural or synthetic), silicoaluminophosphates (SAPO), heteropolyacids, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfunated zirconia, liquid acids such sulfuric acid, or acidic ionic liquids may be used in Step 2/Equation 2 to promote the conversion of TBHP and TBA into DTBP.
  • SAPO silicoaluminophosphates
  • Step 3/Equation 3 DTBP is introduced to a coupling reactor to initiate free radical coupling of heavy virgin naphtha (HVN).
  • Typical reaction conditions for Step 3 of the present invention are: 100-170 °C (preferably about 145-155 °C), with pressure maintained to ensure that paraffins stay in the liquid or supercritical phase, typically 300-1500 psig (preferably about 500- 1200 psig).
  • Residence time is normally in the range of 2-24 hours (preferably 4-16 hours).
  • the molar ratio of DTBP to HVN to be coupled is in the range of about 0.01-100, preferably in the range of about 0.05-10, and more preferably in the range of 0.1-2.
  • Step 3 By controlling the reaction severity for radical coupling (Equation 3), higher molecular weight products can also be obtained. Complete conversion of DTBP is normally achieved in this step. Following Step 3, the mixed product stream is fractionated, with unreacted HVN being recycled to the coupling reactor, TBA being sent to Step 4, and byproduct acetone being removed. Due to the nature of the coupling chemistry, the diesel fraction (C14-C28) are branched with short chain alkyl groups such as methyl and ethyl, yielding a resulting product having a high cetane value. It is envisioned that other heavy naphtha feeds, such as heavy cat naphtha (i.e. the heavy naphtha fraction from a catalytic cracker) or coker naphtha, are acceptable feedstock for Step 3 of this invention.
  • heavy cat naphtha i.e. the heavy naphtha fraction from a catalytic cracker
  • coker naphtha are acceptable feedstock for Step 3 of this invention.
  • TBA is sent to a dehydration reactor, where it is dehydrated over an acid catalyst to yield iso-butylene and water.
  • An acid catalyst such as AmberlystTM resin, NafionTM resin, aluminosilicates, acidic clay, alumina, zeolites (natural or synthetic), silicoaluminophosphates (SAPO), heteropolyacids, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfunated zirconia, liquid acids such sulfuric acid, or acidic ionic liquids may be used.
  • AmberlystTM resin AmberlystTM resin, NafionTM resin, aluminosilicates, acidic clay, alumina, zeolites (natural or synthetic), silicoaluminophosphates (SAPO), heteropolyacids, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia
  • Typical reaction temperature is in the range of 150 - 400 °C, preferably 200 - 350 °C, more preferably 250 - 350 °C.
  • Typical pressure for the reaction is 50 - 500 psig, preferably 100 - 400 psig, more preferably 200 - 300 psig.
  • the reaction can be performed in fixed-bed or batch reactor. A preferred embodiment of this step utilizes reactive distillation to continuously remove co-product water.
  • Step 5/Equation 5 iso-butylene (from Step 4) is sent to an alkylation reactor, where it is alkylated with iso-butane to yield high-octane alkylate.
  • the alkylation reaction can be conducted in a wide range of reactor configurations including fixed bed (single or in series), slurry reactors, and/or catalytic distillation towers.
  • the alkylation reaction can be conducted in a single reaction zone or in a plurality of reaction zones, preferably in a plurality of reaction zones.
  • the mole ratio of iso-butane to iso-butylene may be in the range of 1 - 100, preferably 5 - 80, more preferably 10 - 50.
  • the alkylation is conducted in the presence of an acid catalyst.
  • Any catalyst suitable for isoparaffin alkylation, whether homogeneous or heterogeneous, may be used.
  • suitable acidic homogeneous catalysts include hydrofluoric acid, sulfuric acid, and mixtures thereof.
  • suitable acidic heterogeneous catalysts include chlorided alumina, fluorided alumina, zeolites, acidic metal oxides and mixed metal oxides, and mixtures thereof.
  • zeolites include those of the MOR, BEA, FAU, MTW, and MWW families, preferably the FAU, MWW, and MOR families.
  • Non-limiting examples of acidic metal oxides or mixed metal oxides include tungsten oxides (WOx), molybdenum oxide (MoOx), mixed oxides such as WOx/Zr02, WOx/Ce02, MoOx/Zr02, MoOx/Ce02, and sulfated zirconia.
  • tungsten oxides WOx
  • MoOx molybdenum oxide
  • suitable reaction temperatures range from about 0°C and about 50°C, such as from about 5°C and about 40°C, or from about 10°C and about 25°C.
  • suitable reaction temperatures range from about 100°C to about 400°C, preferably from about 125°C to about 300°C, more preferably from about 150°C to about 250°C.
  • the reaction pressure is preferably maintained so that the C4 olefinic feed remains in liquid form within the reactor.
  • suitable reaction pressures are from about 100 kPa to about 7000 kPa absolute (e.g., atmospheric to about 1000 psia), such as from about 500 kPa to about 5000 kPa absolute.
  • This example illustrates the general procedure for coupling n-heptane (to demonstrate HVN) using DTBP to form high-cetane diesel.
  • a 300 cc autoclave the following were loaded: 60 g of n-heptane and 30 g of DTBP (trade name Luperox DI from Aldrich Chemicals, 98%).
  • the autoclave was sealed, connected to a gas manifold, and pressurized with 600 psig nitrogen.
  • the reactor content heated under stirring (500 rpm) at a rate of 2 °C/min to 150 °C and held for 4 hours. The heat was turned off and the autoclave allowed to cool down to room temperature.
  • a high-cetane diesel composition can be produced according to certain teachings of the present invention. Due to the nature of the coupling chemistry, the diesel fraction (C14-C28) are branched with short chain alkyl groups such as methyl and ethyl, yielding a resulting product having a high cetane value.
  • the reaction severity for radical coupling Equation 3
  • higher molecular weight products can also be obtained.
  • the TBA co-product can be further upgraded to high-octane alkylate using known dehydration and alkylation technologies, as described in Steps 4-5 above.
  • Embodiment 1 A process for upgrading substantially paraffinic feed to high-cetane diesel, comprising oxidizing a first feed stream comprising one or more iso-paraffins to form alkyl hydroperoxides and first alcohols, catalytically converting the alkyl hydroperoxides and first alcohols to dialkyl peroxides, and coupling a second feed stream substantially comprising paraffins using the dialkyl peroxides as a radical initiator to create high-cetane diesel and second alcohols.
  • Embodiment 2 A process according to embodiment 1, further comprising converting the second alcohols to olefins.
  • Embodiment 3 A process according to embodiment 2, further comprising alkylating the olefins with iso-paraffins to form high-octane gasoline.
  • Embodiment 4 A process according to embodiment 2, further comprising dimerizing the olefins to form high octane gasoline.
  • Embodiment 5 An integrated process for upgrading low-value paraffinic materials to high octane gasoline and high-cetane diesel, comprising oxidizing a first feed stream comprising one or more iso-paraffins to form alkyl hydroperoxides and first alcohols, catalytically converting the alkyl hydroperoxides and first alcohols to dialkyl peroxides, coupling a second feed stream substantially comprising paraffins using the dialkyl peroxides as a radical initiator to create high-cetane diesel and second alcohols, converting the second alcohols to olefins, and alkylating the olefins with iso-butane to form high-octane gasoline.
  • Embodiment 6 A process according to any of the previous embodiments, wherein the first feed stream comprises iso-butane.
  • Embodiment 7 A process according to any of the previous embodiments, wherein the second feed stream comprises heavy virgin naphtha.
  • Embodiment 8 A process according to any of the previous embodiments, wherein the second feed stream comprises coker naphtha.
  • Embodiment 9 A process according to any of the previous embodiments, wherein the second feed stream comprises heavy cat naphtha.
  • Embodiment 10 A process according to any of the previous embodiments, wherein the second feed stream comprises paraffins in the carbon number range of 7-12.
  • Embodiment 11 An integrated process for upgrading low-value paraffinic materials to high octane gasoline and high-cetane diesel, comprising, oxidizing iso-butane to form t-butyl hydroperoxide and t-butyl alcohol, catalytically converting the t-butyl hydroperoxide and the t- butyl alcohol to di-t-butyl peroxide, coupling heavy naphtha using di-t-butyl peroxide as a radical initiator to create high-cetane diesel and t-butyl alcohol, converting the t-butyl alcohol to iso- butylene, and alkylating the iso-butylene with iso-butane to form high-octane gasoline.
  • Embodiment 12 A process according to embodiment 11, wherein the heavy naphtha comprises heavy virgin naphtha.
  • Embodiment 13 A process according to embodiment 11, wherein the heavy naphtha comprises coker naphtha.
  • Embodiment 14 A process according to embodiment 11, wherein the heavy naphtha comprises heavy cat naphtha.
  • Embodiment 15 A process according to embodiment 11, wherein the second feed stream comprises paraffins in the carbon number range of 7-12.
  • Embodiment 16 An integrated process for upgrading low-value paraffinic materials to high octane gasoline and high-cetane diesel, comprising, oxidizing iso-butane to form t-butyl hydroperoxide and t-butyl alcohol, catalytically converting the t-butyl hydroperoxide and the t- butyl alcohol to di-t-butyl peroxide, coupling heavy naphtha using di-t-butyl peroxide as a radical initiator to create high-cetane diesel and t-butyl alcohol, converting the t-butyl alcohol to iso- butylene, and dimerizing the iso-butylene to form high-octane gasoline.
  • Embodiment 17 A process according to any of the previous embodiments, wherein the high-cetane diesel has a cetane number greater than 40.
  • Embodiment 18 A process according to any of the previous embodiments, wherein the high-cetane diesel has a cetane number greater than 45.
  • Embodiment 19 A process according to any of the previous embodiments, wherein the high-cetane diesel has a cetane number greater than 50.

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé intégré de conversion de matières paraffiniques de moindre valeur en essence à indice d'octane élevé et en gazole léger à indice de cétane élevé. Le procédé comprend : (1) l'oxydation d'une iso-paraffine en hydroperoxyde d'alkyle et en alcool ; (2) la conversion de l'hydroperoxyde d'alkyle et de l'alcool en peroxyde de dialkyle ; (3) la conversion de molécules d'essence paraffinique à faible indice d'octane en utilisant les peroxydes de dialkyle en tant qu'initiateurs de radicaux, ce qui permet de former un gazole à indice de cétane élevé, tandis que le peroxyde de dialkyle est converti en un alcool ; (4) la conversion de l'alcool en une oléfine ; et (5) l'alkylation de l'oléfine avec de l'iso-butane pour former un alkylate à indice d'octane élevé. La réaction nette consiste ainsi en la conversion d'iso-paraffine en alkylat d'essence à indice d'octane élevé et en la conversion d'essence paraffinique à faible indice d'octane en gazole à indice de cétane élevé.
PCT/US2017/063385 2016-12-22 2017-11-28 Procédé intégré de fabrication d'essence à indice d'octane élevé et de gazole à indice de cétane élevé Ceased WO2018118347A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP17817491.8A EP3559168A1 (fr) 2016-12-22 2017-11-28 Procédé intégré de fabrication d'essence à indice d'octane élevé et de gazole à indice de cétane élevé
CA3045986A CA3045986A1 (fr) 2016-12-22 2017-11-28 Procede integre de fabrication d'essence a indice d'octane eleve et de gazole a indice de cetane eleve

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15/388,013 US9637423B1 (en) 2014-12-16 2016-12-22 Integrated process for making high-octane gasoline
US15/388,013 2016-12-22

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Citations (10)

* Cited by examiner, † Cited by third party
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US2845461A (en) 1956-04-12 1958-07-29 Shell Dev Non-catalytic liquid phase isobutane oxidation
US3478108A (en) 1966-02-21 1969-11-11 Atlantic Richfield Co Isobutane oxidation
US4408081A (en) 1981-10-05 1983-10-04 Shell Oil Company Process for oxidation of isobutane
US5149885A (en) 1992-02-20 1992-09-22 Arco Chemical Technology, L.P. Oxidation of isobutane to tertiary butyl hydroperoxide
US5162593A (en) 1991-11-25 1992-11-10 Arco Chemical Technology, L.P. Tertiary butyl alcohol preparation
EP0567336A1 (fr) 1992-04-22 1993-10-27 ARCO Chemical Technology, L.P. Oxydation d'isobutane en hydroperoxyde de butyle tertiaire
US5288919A (en) 1993-05-13 1994-02-22 Arco Chemical Technology, L.P. Preparation of dialkyl peroxides
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