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WO2023001695A1 - Procédé et installation d'amélioration de l'indice d'octane de l'essence - Google Patents

Procédé et installation d'amélioration de l'indice d'octane de l'essence Download PDF

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Publication number
WO2023001695A1
WO2023001695A1 PCT/EP2022/069776 EP2022069776W WO2023001695A1 WO 2023001695 A1 WO2023001695 A1 WO 2023001695A1 EP 2022069776 W EP2022069776 W EP 2022069776W WO 2023001695 A1 WO2023001695 A1 WO 2023001695A1
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Prior art keywords
methanol
stream
gasoline
process according
oxygenates
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PCT/EP2022/069776
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Inventor
Angelica HIDALGO VIVAS
Thoa Thi Minh NGUYEN
Rickard Vannby
Mathias Jørgensen
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Topsoe AS
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Haldor Topsoe AS
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Priority to AU2022316323A priority Critical patent/AU2022316323A1/en
Publication of WO2023001695A1 publication Critical patent/WO2023001695A1/fr
Anticipated expiration legal-status Critical
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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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only 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
    • C10L1/06—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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention relates to a process and plant for converting a methanol feed stream into a gasoline product.
  • Embodiments of the invention include converting the methanol feed into raw gasoline, subsequently producing a stabilized gasoline by re moving C2-compounds and C3-C4 compounds from the raw gasoline, subsequently upgrading the stabilized gasoline, suitably by a hydroisomerization (HDI) and/or a hy drocracking step (HDC), conducting a methanol stream, suitably a portion of said meth anol feed stream, to an optional water removal step for producing a dehydrated metha nol stream, and blending the methanol stream, suitably the dehydrated methanol stream together with a separate stream comprising oxygenates other than methanol, with at least a portion of the upgraded gasoline stream for producing said gasoline product.
  • HDI hydroisomerization
  • HDC hy drocracking step
  • Embodiments of the invention further include combining the dehydrated meth anol and the oxygenates other than methanol into a multi-oxygenate blend prior to blending with the at least a portion of the upgraded gasoline stream.
  • the proportion of the dehydrated methanol to the oxygenates other than methanol in the multi-oxygenate blend is suitably 35 wt% or lower.
  • the octane rating of the gasoline product is thereby improved by incorporating into the upgraded gasoline stream methanol already availa ble in the process/plant produced by upstream methanol synthesis, so that the octane rating improvement is conducted in-situ i.e. during the operation of the process.
  • the methanol feed stream is produced upstream by methanol synthesis of a methanol syn thesis gas.
  • TIGASTM technology - Topsoe Improved Gasoline Synthesis provides for the option of producing gasoline from methanol (MTG), but also producing gasoline from a synthesis gas (STG).
  • synthesis of methanol, dimethyl ether (DME) and gasoline are inte grated by passing synthesis gas (gas mixture of H2, CO and CO2) to an oxygenate (methanol/DME) reactor and then converting the oxygenate(s) into gasoline in gasoline reactors.
  • synthesis gas gas mixture of H2, CO and CO2
  • oxygenate methanol/DME
  • the former is also a known technology for gasoline synthesis from oxygenates such as methanol. It involves a process/plant comprising a MTG section (methanol-to- gasoline section) and a downstream distillation section.
  • the MTG section may also be referred as MTG loop and comprises: a MTG reactor; a product separator for withdraw ing a bottom water stream, an overhead recycle stream from which an optional fuel gas stream may be derived, as well as a raw gasoline stream comprising C2 compounds, C3-C4 paraffins (LPG) and C5+ hydrocarbons (gasoline boiling components); and a re cycle compressor for recycling the overhead recycle stream by combining it with the oxygenate feed stream, e.g. methanol feed stream.
  • LPG C3-C4 paraffins
  • C5+ hydrocarbons gasoline boiling components
  • the overhead recycle stream acts as diluent, thereby reducing the exothermicity of the oxy genate conversion.
  • C2 compounds are removed in a de-ethanizer, such as de-ethanizer column, and then a C3-C4 fraction (C3-C4 compounds) is removed as LPG as the overhead stream in a LPG-splitting column (LPG splitter), while stabilized gasoline is withdrawn as the bottoms product.
  • the stabi lized gasoline or the heavier components of the stabilized gasoline may optionally be further upgraded and thereby refined, e.g. by conducting hydroisomerization (HDI) and/or hydrocracking (HDC) thus producing an upgraded gasoline product.
  • HDI hydroisomerization
  • HDC hydrocracking
  • US 2019040331 discloses a method for preparing a fuel composition a the distribution point, i.e. , at fuel terminals, which comprises a base fuel such as a Blendstock for Oxy genate Blending “BOB”, an oxygenate and an octane-boosting additive described therein as N-methyl aniline, which method comprises: blending an additised oxygenate with a base fuel, wherein the additised oxygenate comprises an oxygenate and an oc tane-boosting additive.
  • the oxygenate can be e.g. methanol or preferably ethanol.
  • US 4564643 discloses a particular process and catalyst for producing, from a synthesis gas, a mixed alcohol comprising methanol and higher alcohols than methanol. These mixed alcohols are used as an alcohol component to be added to gasoline.
  • the metha nol content in the mixture is at least 45 wt%.
  • Methanol is readily available in MTG or STG plant or process and a small amount could be blended to the gasoline as an octane booster, however, it also has a signifi cant negative effect by increasing vapor pressure.
  • US 2008/0216391 discloses a pProcesses and reactor system for the conversion of ox ygenated hydrocarbons to hydrocarbons, ketones and alcohols useful as liquid fuels, such as gasoline, jet fuel or diesel fuel, and industrial chemicals.
  • WO 2011/060116 discloses a process for producing renewable gasoline and fuel com positions produced therefrom.
  • the renewable gasoline is produced from a methanol feed stream.
  • Applicant’s WO 2016116612 A1 discloses a process for converting methanol to hydro carbons suitable for use as gasoline or blend-stock.
  • CN 102732332 A discloses a preparation method of a methanol/butanol mixed vehicle fuel, by adding 10-20 wt% of methanol, 40-60 wt% of butanol and 0.5-3 wt% of additive into a mixing tank at normal temperature, mixing for 10-20 minutes, adding 17-50 wt% of petrochemical 93# gasoline into the mixed solution in the mixing tank, and standing for 4-6 hours for use.
  • the gasoline content is low, i.e. less than 50 wt% while the methanol and butanol content is high, i.e. methanol/butanol higher than 50 wt%, and thus inherently the vehicle fuel is prepared at the distribution point, i.e. at a fuel ter minal.
  • the invention is a process for producing a gasoline prod uct from a methanol feed stream, the process comprising the steps of: i) conducting a portion of the methanol feed stream to a methanol-to-gasoline reactor under the presence of a catalyst active for converting the methanol feed stream into a raw gasoline stream comprising C2-compounds, C3-C4 compounds such as C3-C4 paraffins, and C5+ hydrocarbons; ii) separating from the raw gasoline stream: ii-1) a stream comprising the C2-compounds, ii-2) a stream comprising the C3-C4 compounds, and ii-3) a gasoline stream comprising the C5+ hydrocarbons, i.e.
  • the methanol to gasoline reactor is suitably for producing gas oline from methanol (MTG), or for producing gasoline from a synthesis gas (STG).
  • the term “comprising” includes “comprising only” i.e. “consisting of”.
  • Methanol is available upstream for gasoline production and a small amount is blended with the gasoline being produced as an octane booster i.e. to increase the octane num ber of the gasoline; however, adding methanol has also a significant negative impact by increasing vapor pressure (e.g. > 3 psi).
  • the increase in vapor pressure caused by methanol addition is by the present invention at least partly off-set by oxygenate(s) other than methanol.
  • the octane number is the Research Octane Number, RON, measured according to ASTM D2699; or Motor Octane Number, MON, measured according to ASTM D2700; or Anti Knock Index (AKI) measured as the average of RON and MOM i.e. (RON+MOM)/2.
  • RON Research Octane Number
  • MON Motor Octane Number
  • AKI Anti Knock Index
  • gasoline stream comprising the C5+ hydrocarbons in step ii-3 is also referred to as stabilized gasoline or stabilized gasoline stream.
  • the vapor pressure of the gasoline being produced needs to be reduced before blending with methanol so that the vapor pres sure of the blend fulfils volatility specifications.
  • the reduction in vapor pres sure of the gasoline can result in RON/MON/AKI loss; therefore, the net octane boost could be much diminished.
  • the increase in vapor pressure is not as pronounced as when blending the upgraded gasoline with only methanol.
  • the present invention thus integrates the use of methanol as a booster in a pro cess/plant where methanol is readily available from upstream methanol synthesis, as it will also become apparent from one or more or the below embodiments, while at the same time off-setting some of the disadvantages in its use e.g., increase in vapor pres sure and need for phase stabilizers.
  • octane booster(s) whilst also fulfilling mandates for use of oxygenates in gasoline in ac cordance with EU EN228 and/or USA ASTM D4814.
  • the invention enables using some methanol for reducing the need for other oxygen ates by using a small portion of the methanol readily available in the plant.
  • the methanol feed stream to the methanol-to-gasoline reactor is suitably free of other oxygenates such as higher alcohols. If the methanol feed stream contains water, in accordance with step iv) it is dried by a water removal step, suitably in a fractionation step e.g. in a distillation column before being directed to blending with oxygenate(s) other than methanol and the upgraded gasoline stream.
  • the methanol stream suitably the dehydrated methanol stream, and the one or more oxygenates other than methanol, are combined into a multi-oxygenate blend prior to blending with the at least a portion of the upgraded gasoline stream.
  • the dehydrated methanol stream, as well as the separate stream of oxygen ates other than methanol, and upgraded gasoline may be blended at a common mixing point
  • a multi-oxygenate blend is produced which may be tailored at will during oper ation of the process/plant for further blending with the upgraded gasoline.
  • the blending of oxygenates is conducted during the process for producing the gasoline, i.e. in-situ, thus as part of the process, and not at a distribution point such as a fuel terminal.
  • the octane rating in the gasoline product is thereby easier to control and produce according to required specifications, in particular according to the standards EU EN228 and/or USA ASTM D4814.
  • the blending of the one or more oxygenates is conducted during the process for producing the gasoline product, i.e. in- situ.
  • multi-oxygenate blend means a mixture of methanol, e.g. dehydrated methanol available in the process/plant, and one or more oxygenates other than methanol.
  • the multi-oxygenate blend does not com prise gasoline e.g. upgraded gasoline.
  • the “gasoline product” refers to a product blend of gasoline (here the upgraded gasoline) with oxy genates.
  • the separate stream comprising one or more oxygenates other than methanol is externally sourced.
  • the term “externally sourced” means outside the bat tery limits of the process/plant according to the present application.
  • the methanol used in the process instead, is internally sourced.
  • separate (individual) streams of the one or more oxygenates other than methanol may be provided.
  • a stream comprising or comprising only one oxygenate other than methanol may be combined with another stream comprising or comprising only yet an additional oxygenate other than methanol, and then combined with e.g. the dehydrated methanol stream for thereby forming the multi-oxygenated blend.
  • a metal-free octane booster such as a N-methyl ani line compound, is further provided, i.e. further added, for forming the multi-oxygenated blend, and the metal-free octane booster is not an oxygenate.
  • the metal-free octane booster is 1 wt% or less, such as 0.5 wt%.
  • the separate stream comprising one or more oxygenates other than methanol is a stream comprising higher alcohols and/or higher ethers, suitably com prising only higher alcohols, such as ethanol and/or isobutanol.
  • higher alcohol means an alcohol other than methanol and having no more than five carbons.
  • the proportion of the methanol stream suitably the dehydrated methanol to the one or more oxygenates other than methanol in the multi-oxygenate- blend is 35 wt% or lower, such as dehydrated methanol/oxygenates other than metha- nol (ratio of methanol to oxygenates-other-than-methanol) of 35/65 wt% or 20/80 wt%.
  • the one or more oxygenates other than methanol is: ethanol and/or iso-butanol.
  • Other higher alcohol(s) such as isopropanol or tertbutanol may also be used.
  • tertbutanol (t-BuOH) instead of, or in addition to, iso-butanol is utilized.
  • the one or more oxygenates other than methanol is an ether as defined above, i.e. ethers with five or more C-atoms, such as methyl tertbutyl ether (MTBE).
  • MTBE methyl tertbutyl ether
  • the multi-oxygenate-blend is 2.7/2.7 vol.% methanol/isobutanol.
  • Table 1 above is for EU specifications, with max O-content of 3.7 wt%.
  • max O-content of 3.7 wt%.
  • the multi-oxygenate blend is 2.7/4.2/2.6 vol.% meth anol/ethanol/isobutanol.
  • a blend of 2.7/4.2/2.6 vol% methanol/ethanol/isobutanol re sults in an oxygenate and oxygen content combination that would be allowed in the EU.
  • the total oxygen content of 2.7 methanol + 4.2 ethanol +2.6 isobutthanol is 3.7 wt%, and, if there was only ethanol, about 10 vol%; more specifically 10.4 vol.% ethanol gives same 3.7 wt% oxygen content.
  • the in crease in vapor pressure that would result from adding only methanol (>3 psi) is at least partly off-set by the ethanol and isobutanol in the multi-oxygenates blend ( ⁇ 2 psi, i.e. vapor pressure range of less than 2 psi).
  • the process of the invention enables in-situ tailoring the composition of the gasoline product in compliance with any of the above specifications.
  • the invention enables also to use the available methanol in the plant for cli ents which will include in their scope the blending of oxygenates.
  • the invention surprisingly enables boosting the gasoline, in-situ, without impairing gas- oline throughput.
  • gasoline throughput gasoline yield from methanol
  • the conversion of methanol to gasoline also gen erates water, whereas the diverted dehydrated methanol for blending is mixed directly with the upgraded gasoline product and thereby fully accounted therein.
  • the raw gasoline stream comprises C2- compounds, such as methane, ethane, eth- ene, and the process thus comprises in step ii-1) using a de-ethanizer (de-ethanizer column e.g. fractionation column) for generating the stream comprising the C2- com pounds
  • de-ethanizer column e.g. fractionation column
  • the gasoline stream comprising the C5+ hydrocarbons in step ii-3 is conducted to a fractionation column for separating light gasoline as overhead stream, fuel oil as bottom stream and an intermediate stream as the gasoline stream comprising the C5+ hydrocarbons in step ii-3 being conducted to said upgrading step, suitably to a HDI and/or HDC step.
  • the material catalytically active in hydroisomerization typically comprises an ac tive metal (either elemental noble metals such as platinum and/or palladium or sulfided base metals such as nickel, cobalt, tungsten and/or molybdenum), an acidic support (typically a molecular sieve showing high shape selectivity, and having a topology such as MFI, MEL, MOR, FER, MRE, MWW, AEL, TON and MTT) and a refractory support (such as alumina, silica or titania, or combinations thereof).
  • an ac tive metal either elemental noble metals such as platinum and/or palladium or sulfided base metals such as nickel, cobalt, tungsten and/or molybdenum
  • an acidic support typically a molecular sieve showing high shape selectivity, and having a topology such as MFI, MEL, MOR, FER, MRE, MWW, AEL
  • HDI conditions involve a temperature in the interval 250-400°C, a pressure in the interval 20-150 bar, and a liq uid hourly space velocity (LHSV) in the interval 0.5-8.
  • the material catalytically active in hydrocracking (HDC) typically comprises an active metal (either elemental noble metals such as platinum and/or palladium or sulfided base metals such as nickel, cobalt, tungsten and/or molybdenum), an acidic support (typically a molecular sieve having a topology such as IZA, FAU, MFI, MEL, MOR,
  • HDC conditions involve a temperature in the in terval 250-400°C, a pressure in the interval 20-150 bar, and a liquid hourly space ve locity (LHSV) in the interval 0.5-8.
  • LHSV liquid hourly space ve locity
  • step ii-2) is conducted in LPG-splitting column (LPG splitter).
  • LPG splitter LPG-splitting column
  • the C3- C4 fraction is thereby separated as LPG as the overhead stream in the LPG-splitting col umn (LPG splitter), while stabilized gasoline is withdrawn as the bottoms product.
  • C3-C4 compounds is also referred to as “LPG”.
  • LPG means liquid/liquified petroleum gas, which is a gas mixture mainly comprising propane and butane, i.e. C3-C4; LPG may also comprise i-C4 and a minor portion of olefins.
  • the MTG process for producing gasoline is well-known, as for instance disclosed in US 4788369, US 4481305 or US 4520216.
  • the LPG fraction typically constitutes between 15 and 20 wt% of the gasoline product slate.
  • LPG has normally a low value and in the MTG process the value is even lower, because it is very far from specifications, for instance also by the presence of up to about 10 wt% olefins.
  • the gasoline product (C5+ hydrocarbons) is a complex hydrocarbon mixture, comprising e.g. C5-C10 hydrocarbons.
  • the catalyst in the methanol-to-gasoline reactor is a zeolitic catalyst having an MFI framework such as ZSM-5, for instance ZSM-5 in its hydrogen form (HZSM-5); and wherein the temperature in the methanol-to-gasoline reactor reactor is
  • the pressure is in the range 15-25 bar abs; and optionally the WHSV is 1-6 , such as 1-2, for instance 1.5 or 1.6.
  • the methanol-to-gasoline reactor has arranged along its length a fixed bed or a plurality of successive fixed beds com prising the catalyst.
  • MFI structure means a structure as assigned and main tained by the International Zeolite Association Structure Commission in the Atlas of Ze olite Framework Types, which is at http:// www.iza-structure.org/databases/ or for in- stance also as defined in “Atlas of Zeolite Framework Types”, by Ch. Baerlocher, L.B. McCuskerand D.H. Olson, Sixth Revised Edition 2007.
  • the process further comprises: prior to step i), producing said meth anol feed stream by methanol synthesis of a methanol synthesis gas, and wherein the methanol synthesis gas is generated by: by steam reforming of a hydrocarbon feed such as natural gas, and/or at least partly by electrolysis of water and/or steam.
  • methanol is readily available in the process/plant, as methanol feed in the MTG reactor or a minor portion such as 10wt% or less, as methanol stream in the blending step iv).
  • the methanol and resulting gasoline product may then be blue or green-stamped.
  • Blue or green stamped gasoline means a gasoline product utilizing blue or green meth anol, respectively. These are much more environmentally friendly gasoline products than when produced from typical fossil feed derived methanol.
  • blue methanol means methanol originating from a fossil fuel source, but with recovery of CO2 and other greenhouse gases in the process.
  • the CO2 is for instance sequestrated.
  • the fossil fuel source e.g. natural gas
  • methanol synthesis gas which is then converted to meth anol, here ‘blue methanol’.
  • Green methanol means methanol originating from a re newable fuel source, such as from solar, wind and hydropower, for producing electricity used in electrolysis of water (steam) for generation of hydrogen and thereby methanol synthesis gas which is then converted to methanol, here ‘green methanol.
  • Black meth- anol means methanol originating from a petroleum/coal source.
  • the steam reforming is conducted by the use of electricity from renewable sources, such as by electrically heated steam reforming (e-SMR), for producing the methanol synthesis gas; and/or where electrolysis is used for producing the methanol synthesis gas
  • the resulting methanol may also be categorized as e-methanol e.g. eMethanolTM.
  • the steam reforming step is conducted in an elec trically heated reformer (e-reformer), i.e. the steam reforming unit is an e-reformer.
  • e-reformer is also referred to as “e-SMR” (electrically heated steam methane re former).
  • the e-reformer is suitably powered by electricity derived from renewable re sources such as wind, hydropower and/or solar energy.
  • renewable re sources such as wind, hydropower and/or solar energy.
  • the methanol feed stream is produced from methanol synthe sis gas which is generated at least partly by electrolysis of water and/or steam.
  • the methanol synthesis gas is generated by: b-1) combining air separation, autothermal reforming or partial oxidation, and electroly sis of water and/or steam, as disclosed in Applicant’s WO 2019/020513 A1.
  • the methanol synthesis gas which as is well-known in the art, is a mixture comprising mainly hydrogen and carbon monoxide tailored for methanol synthesis, may also be generated by: b-2) combining the use of water electrolysis in an alkaline or PEM electrolysis unit, or steam in a solid oxide electrolysis cell (SOEC) unit, thereby generating a hydrogen stream, together with the use, i.e. the provision, of a CC>2-rich stream in a SOEC unit for generating a stream comprising carbon monoxide and carbon dioxide, then combin ing the hydrogen stream and the stream comprising carbon monoxide and carbon diox ide for generating said methanol synthesis gas, as e.g. disclosed in Applicant’s co pending European patent application No. 20216617.9.
  • SOEC solid oxide electrolysis cell
  • the methanol feed stream can be produced from many primary resources (including biomass and waste), particularly in times of low wind and solar electricity costs.
  • the term “process” means a process comprising steps i)-iv) related to the production of the gasoline product including addi tion of an oxygenate other than methanol, and the process may also encompass the prior (front-end) production of the methanol feed from a methanol synthesis generated by said steam reforming and/or at least partly by electrolysis of water and/or steam, as recited above.
  • process/plant means process and/or plant.
  • the invention encompasses also a plant, i.e. process plant, for car rying out the process according to any of the above embodiments.
  • a process/plant 10 is shown for producing a gasoline product from a methanol feed stream according to an embodiment of the present invention.
  • a methanol feed stream 1 is split into separate methanol feed streams 3, 5, here de noted as methanol feed stream 3 and methanol split stream 5,
  • the methanol feed stream 3 is conducted to a methanol-to-gasoline loop section 20 comprising a metha- nol-to-gasoline reactor (not shown), thereby producing a raw gasoline stream 11 com prising C2-compounds, C3-C4 compounds, and C5+ hydrocarbons.
  • the methanol split stream 5 is conducted to a water removal step in fractionation column 30, thereby gen erating a water stream 7 and a dehydrated methanol stream 9.
  • the raw gasoline stream 11 is conducted to a separation (stabilizer) section 40 comprising a de ethanizer 40’ and LPG-splitter 40”, suitably as fractionation columns.
  • a separation (stabilizer) section 40 comprising a de ethanizer 40’ and LPG-splitter 40”, suitably as fractionation columns.
  • an off-gas stream 13 comprising the C2-compounds is separated, while in the LPG-splitter 40” a stream comprising the C3-C4 compounds, e.g. LPG stream 15 is separated.
  • a gasoline stream 17 comprising the C5+ hydrocarbons (stabilized gasoline) is also separated and conducted to upgrading section 50 comprising HDI and/or HDC (not shown), for thereby producing upgraded gasoline stream 19.
  • the dehydrated methanol stream 9 is conducted to a mixing point, suitably in a mixing unit 60, and combined with other oxygenates externally sourced via stream 21.
  • the de hydrated methanol stream 9, and the one or more oxygenates other than methanol in stream 21, are combined into a multi-oxygenate-blend 23 prior to blending with the up graded gasoline stream 19, suitably in mixing unit 70.
  • the mixing point 60 may be omit ted, so that oxygenates externally sourced via 21 are combined directly with the dehy drated methanol stream 9 and the upgraded gasoline stream 19 in mixing unit 70.
  • a gasoline product 25, i.e. product blend of gasoline with oxygenates, of higher octane rating than the upgraded gasoline is thereby withdrawn and transported to distribution points, i.e. fuel terminals.
  • the increase in the octane rating of gasoline being produced in the process/plant is thus conducted in-situ, i.e. during operation of the process/plant 10.
  • Blends of gasoline with methanol/ethanol/isobutanol mixtures were studied in connec tion with a process/plant according the accompanying figure described above.
  • Methanol is one the options considered to boost octane that fulfills European specifica tions, as up to 3 vol% methanol and up to 3.7 wt% oxygen is allowed In U.S. plants; an EPA substantially similar ruling has established that methanol and butanol can be used in equal volumes such that the maximum oxygen content of the product blend of gaso line with oxygenates is not higher than 2.7 wt% and the total amount of oxygenates is not higher 5.5 vol%.
  • the base gasoline is oxygenate-free and it is the base gasoline in the examples, thus in this application corresponding to upgraded gasoline.
  • Vapor pressure (VP) and octane numbers for this and below examples are shown in Table .
  • Blend of the base gasoline (Example 1) and 2.7 vol% methanol Blend of the base gasoline (Example 1) and 2.7 vol% methanol.
  • the octane rating im provement by 2.7 vol% methanol is relatively modest (+1 AKI number); however, meth anol is readily available in a TIGAS plant (a methanol to gasoline plant).
  • TIGAS plant a methanol to gasoline plant.
  • One of the possible disadvantages is the significant increase in VP (>3 psi).
  • the blend of the base gasoline with methanol and a higher alcohol achieves a similar modest octane boost.
  • methanol is available in readily available in the TIGAS process and that the increase is VP is not as pronounced as in the blend with only methanol.
  • the oxygenates and oxy gen content in the blend with 2.7 methanol/2.7 isobutanol would be allowed by both EU EN228 and USA D4814. This is the only blend in Table that at present would be al lowed in USA, provided that the rest of the specifications are fulfilled.
  • Example 5 Sample name: Base gasoline_2.7M_4.4E_2.7B_booster (as in Example 4 and a metal- free booster).
  • Vapor pressure ⁇ VP Vapor pressure ⁇ VP
  • Octane number RON, MON, AKI.

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Abstract

L'invention concerne un procédé et une installation de production d'un produit à base d'essence à partir d'un courant d'alimentation en méthanol. Ledit procédé comprend les étapes consistant à : conduire une partie du courant d'alimentation en méthanol vers un réacteur méthanol-essence pour la production d'un courant d'essence brut comprenant des composés en C2, des composés en C3-C4 et des hydrocarbures en C5+ ; séparer à partir du courant d'essence brut : un courant comprenant les composés en C2, un courant comprenant les composés en C3-C4, et un courant d'essence comprenant les hydrocarbures en C5 +, à savoir de l'essence stabilisée ; valoriser l'essence stabilisée, de manière appropriée en la conduisant à une étape d'hydroisomérisation (HDI) et/ou une étape d'hydrocraquage (HOC) ; éventuellement conduire un courant d'alimentation en méthanol, de manière appropriée une autre partie dudit courant d'alimentation en méthanol, vers une étape d'élimination d'eau pour produire un courant de méthanol déshydraté ; et mélanger un courant de méthanol avec un courant séparé comprenant un ou plusieurs composés oxygénés autres que le méthanol, avec au moins une partie du courant d'essence valorisé pour produire ledit produit d'essence, et ledit courant de méthanol est : une partie dudit courant d'alimentation en méthanol, ou un courant de méthanol déshydraté produit à partir de la conduite du courant de méthanol, de manière appropriée une partie de celui-ci, à une étape d'élimination d'eau.
PCT/EP2022/069776 2021-07-21 2022-07-14 Procédé et installation d'amélioration de l'indice d'octane de l'essence Ceased WO2023001695A1 (fr)

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Cited By (1)

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WO2024249094A1 (fr) 2023-05-30 2024-12-05 Arcadia eFuels US Inc. Production d'hydrocarbures synthétiques

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US4520216A (en) 1983-05-11 1985-05-28 Haldor Topsoe Process for the preparation of synthetic hydrocarbons
US4564643A (en) 1982-12-29 1986-01-14 Research Association For Petroleum Alternatives Development Process for the production of mixed alcohols
US4788369A (en) 1985-12-31 1988-11-29 Mobil Oil Corporation Conversion of methanol to gasoline
US20080216391A1 (en) 2007-03-08 2008-09-11 Cortright Randy D Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons
WO2011060116A2 (fr) 2009-11-12 2011-05-19 Range Fuels, Inc. Procédé de production d'essence renouvelable, et compositions de carburant produites avec ce type d'essence
CN102732332A (zh) 2012-07-11 2012-10-17 温志明 一种甲醇与丁醇混合车用燃料的制备方法
WO2016116612A1 (fr) 2015-01-22 2016-07-28 Haldor Topsøe A/S Procédé de conversion de méthanol en hydrocarbures convenant à l'utilisation comme essence ou base de mélange pour essence.
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WO2019020513A1 (fr) 2017-07-25 2019-01-31 Haldor Topsøe A/S Méthode de préparation d'un gaz de synthèse
US20190040331A1 (en) 2016-02-11 2019-02-07 Bp Oil International Limited Additising a Fuel
WO2019228797A1 (fr) 2018-05-31 2019-12-05 Haldor Topsøe A/S Reformage à la vapeur chauffé par chauffage par résistance

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Publication number Priority date Publication date Assignee Title
US4481305A (en) 1982-09-07 1984-11-06 Haldor Topsoe A/S Process for the preparation of hydrocarbons
US4564643A (en) 1982-12-29 1986-01-14 Research Association For Petroleum Alternatives Development Process for the production of mixed alcohols
US4520216A (en) 1983-05-11 1985-05-28 Haldor Topsoe Process for the preparation of synthetic hydrocarbons
US4788369A (en) 1985-12-31 1988-11-29 Mobil Oil Corporation Conversion of methanol to gasoline
US20080216391A1 (en) 2007-03-08 2008-09-11 Cortright Randy D Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons
WO2011060116A2 (fr) 2009-11-12 2011-05-19 Range Fuels, Inc. Procédé de production d'essence renouvelable, et compositions de carburant produites avec ce type d'essence
CN102732332A (zh) 2012-07-11 2012-10-17 温志明 一种甲醇与丁醇混合车用燃料的制备方法
US9964256B2 (en) * 2014-12-22 2018-05-08 Exxonmobil Research And Engineering Company Conversion of organic oxygenates to hydrocarbons
WO2016116612A1 (fr) 2015-01-22 2016-07-28 Haldor Topsøe A/S Procédé de conversion de méthanol en hydrocarbures convenant à l'utilisation comme essence ou base de mélange pour essence.
US20190040331A1 (en) 2016-02-11 2019-02-07 Bp Oil International Limited Additising a Fuel
WO2019020513A1 (fr) 2017-07-25 2019-01-31 Haldor Topsøe A/S Méthode de préparation d'un gaz de synthèse
WO2019228797A1 (fr) 2018-05-31 2019-12-05 Haldor Topsøe A/S Reformage à la vapeur chauffé par chauffage par résistance

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024249094A1 (fr) 2023-05-30 2024-12-05 Arcadia eFuels US Inc. Production d'hydrocarbures synthétiques

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