EP4256007A1 - Production sélective et flexible d'essence synthétique - Google Patents

Production sélective et flexible d'essence synthétique

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Publication number
EP4256007A1
EP4256007A1 EP21816105.7A EP21816105A EP4256007A1 EP 4256007 A1 EP4256007 A1 EP 4256007A1 EP 21816105 A EP21816105 A EP 21816105A EP 4256007 A1 EP4256007 A1 EP 4256007A1
Authority
EP
European Patent Office
Prior art keywords
synthetic
hydrocarbon
gasoline
hydrocracking
hydrocarbon mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21816105.7A
Other languages
German (de)
English (en)
Inventor
Angelica HIDALGO VIVAS
Nghia Pham PHU
Rickard Vannby
Ole Frej ALKILDE
Thoa Thi Minh NGUYEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of EP4256007A1 publication Critical patent/EP4256007A1/fr
Pending 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
    • 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
    • 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
    • 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
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • 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
    • C10G45/60—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 characterised by the catalyst used
    • C10G45/64—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 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1025—Natural gas
    • 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
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines

Definitions

  • the present invention relates to a method and a process plant for flexible production of a gasoline product with a low amount of high boiling hydrocarbons and olefins from methanol and other oxygenates, which optionally may be produced from synthesis gas.
  • Production of synthetic gasoline from methanol and other easily convertible oxygenates either produced via synthesis gas of fossil or renewable origin or of other origins results in a product having many characteristics highly suitable for gasoline, but having a distillation curve, which compared to typical fractionated fossil feedstock, comprises a distillation tail rich in diaromatic hydrocarbons, e.g., substituted naphthalenes, and other two-ring structures, e.g., substituted indenes, which have a tendency to formation of deposits and/or particle emissions during combustion in a vehicle engine.
  • the synthetic gasoline comprises an amount of olefins and aromatics.
  • This product distribution from the MTG process is dictated by kinetics and equilibrium, and may be close to or in conflict with regulations on boiling points and concentrations of regulated constituents in gasoline, and the nature of the MTG process only provides few possibilities for adjusting the product distribution.
  • the heaviest product fraction could be removed by fractionation and used for fuel oil in the process, however, this option is associated with a loss of profit, so instead there is a need for a chemical solution to this problem.
  • Recent regulations for gasoline specifications in various jurisdictions include upper limits for Tgo of 152°C (305°F) and less than 6 vol% olefins in strict specifications or Tgo of 168°C (335°F) and less than 10 vol% olefins in intermediate specifications in contrast to commonly Tgo of 190°C (375°F) and less than 18 vol% olefins in prior specifications.
  • Some such specifications are indirect, by specifying properties after blending, e.g. with ethanol.
  • the examples of specifications will be referred to throughout the present application under the terms strict specifications and intermediate specifications, without implying any legal compliance with specific regulations, unless expressly stated. Since synthetic gasoline from a production plant may be distributed to different markets, with different gasoline specifications, there is a need for a production process which provides flexibility for the production plant.
  • ppmw shall be used to signify weight parts per million.
  • vol% this shall be used to signify vol/vol %.
  • Cn shall be used to signify hydrocarbons with exactly n carbon atoms, e.g. C10 signifies hydrocarbons with exactly 10 carbon atoms.
  • Cn+ shall be used to signify hydrocarbons with at least n carbon atoms, e.g. C10+ signifies hydrocarbons with at least 10 carbon atoms
  • T n shall be used to signify the temperature at which n vol% has been distilled in the equipment defined by ASTM D86, e.g. Tgo is the temperature at which 90 vol% of the hydrocarbon mixture has been distilled.
  • a synthetic hydrocarbon mixture produced from a mixture of reactive oxygenates may be understood as a hydrocarbonaceous mixture wherein at least 50% of the C9 aromatics present in said hydrocarbonaceous mixture are tri-methyl benzenes.
  • a broad aspect of the present disclosure relates to a method for providing a synthetic gasoline product comprising less than a specified concentration of olefins, such as 6 vol% or 11 vol% from a first synthetic hydrocarbon mixture produced from a mixture of reactive oxygenates, said first synthetic hydrocarbon mixture having T90 of less than 140°C and comprising at least said specified concentration of olefins and a second synthetic hydrocarbon mixture, produced from a mixture of reactive oxygenates, said second synthetic hydrocarbon mixture having T90 of more than 150°C said method comprising the steps of a. directing the second synthetic hydrocarbon mixture to contact a material catalytically active in hydrocracking under effective hydrocracking conditions, to provide a hydrocracked second synthetic hydrocarbon mixture, b.
  • a specified concentration of olefins such as 6 vol% or 11 vol%
  • a first synthetic hydrocarbon mixture produced from a mixture of reactive oxygenates
  • said first synthetic hydrocarbon mixture having T90 of less than 140°C and comprising at least said specified concentration of olefin
  • said hydrocracked second synthetic hydrocarbon mixture is either added to the first synthetic hydrocarbon mixture upstream contacting said material catalytically active in olefin hydrogenation or it is added to hydrogenated hydrocarbon mixture, downstream contacting said material catalytically active in olefin hydrogenation to provide said synthetic gasoline product.
  • effective hydrocracking conditions involve a temperature in the interval 250-425°C, a pressure in the interval 30-150 Bar, and a liquid hourly space velocity (LHSV) in the interval 0.5-4, optionally together with intermediate cooling by quenching with hydrogen, feed or product and wherein the material catalytically active in hydrocracking comprises (a) one or more active metals taken from the group platinum, palladium, nickel, cobalt, tungsten and molybdenum, (b) an acidic support showing cracking activity, such as amorphous acidic oxides and molecular sieves and (c) a refractory support such as alumina, silica or titania, or combinations thereof.
  • active metals taken from the group platinum, palladium, nickel, cobalt, tungsten and molybdenum
  • an acidic support showing cracking activity such as amorphous acidic oxides and molecular sieves
  • a refractory support such as alumina, silica or titania, or combinations
  • the conditions are chosen such that the amount of material boiling above 190°C in said hydrocracked hydrocarbon stream fraction is reduced by at least 20%wt, 50%wt or 80%wt or more compared to said hydrocracker feed stream.
  • effective hydrogenation conditions involve a temperature in the interval 220-350°C, a pressure in the interval 30-150 Bar, and a liquid hourly space velocity (LHSV) in the interval 0.5-4, optionally together with intermediate cooling by quenching with hydrogen, feed or product and wherein the material catalytically active in hydrocracking comprises 0.1% to 30% of one or more active metals taken from the group platinum, palladium, nickel, cobalt, tungsten and molybdenum and a refractory support such as alumina, silica or titania, or combinations thereof, such as 5-20 wt% sulfided molybdenum or tungsten and 1-10 wt% sulfided nickel or cobalt on an alumina support.
  • active metals taken from the group platinum, palladium, nickel, cobalt, tungsten and molybdenum and a refractory support such as alumina, silica or titania, or combinations thereof, such as 5-20 wt% s
  • the conditions are chosen such that the amount of olefins is reduced by from 20%wt to 80%wt or more compared to the feed stream to the hydrogenation unit.
  • said one or more active metals of said material catalytically active in hydrocracking are taken from the group consisting of nickel, cobalt, tungsten and molybdenum and the hydrocracking feedstock contacting the material catalytically active in hydrocracking comprises at least 50 ppmw sulfur. This has the associated benefit of such a material catalytically active in hydrocracking having a low cost.
  • said one or more active metals of said material catalytically active in hydrocracking are taken from the group consisting of platinum and palladium and the hydrocracking feedstock contacting the material catalytically active in hydrocracking comprises at less than 50 ppmw sulfur. This has the associated benefit of such a material catalytically active in hydrocracking having a high selectivity.
  • said one or more active metals of said material catalytically active in isomerization are taken from the group consisting of nickel, cobalt, tungsten and molybdenum and the hydrocracking feedstock comprises at least 50 ppmw sulfur. This has the associated benefit of such a material catalytically active in isomerization having a low cost.
  • said one or more active metals of said material catalytically active in isomerization are taken from the group consisting of nickel, platinum and palladium and the hydrocracking feedstock comprises at less than 50 ppmw sulfur. This has the associated benefit of such a material catalytically active in isomerization having a high selectivity.
  • said first synthetic hydrocarbon mixture and said second synthetic hydrocarbon mixture are provided by fractionation of a synthetic hydrocarbon mixture produced from a mixture of reactive oxygenates, optionally after one or both synthetic hydrocarbon mixtures having contacted a material catalytically active in a hydroprocessing process under active hydroprocessing conditions.
  • said fractionation provides a third synthetic hydrocarbon mixture, having a T90 above that of said second synthetic hydrocarbon mixture and wherein said third synthetic hydrocarbon mixture is directed to contact a material catalytically active in hydrocracking under active hydrocracking conditions, to provide a hydrocracked third synthetic hydrocarbon mixture, which is included in said synthetic gasoline product, either by addition upstream said fractionation or by addition in a position downstream said fractionation.
  • This has the associated benefit of further hydrocracking an amount of synthetic gasoline under mild conditions, ensuring a product adhering to strict specifications or intermediate specifications, while minimizing the yield loss.
  • said hydrocracking process conditions for the hydrocracking feedstock are chosen, such that the molar ratio between hydrocarbons comprising exactly 10 carbon atoms in the hydrocracked hydrocarbon stream and the hydrocracking feedstock is less than 20%. This has the associated benefit of such a high hydrocracking conversion simplifying the process by avoiding operation with recycle.
  • the conditions of the hydrocracking step for the hydrocracking feedstock and the amount of recycled hydrocarbon stream are such that the ratio of the mass of hydrocarbons comprising at least 11 carbon atoms in the synthetic gasoline to the mass of hydrocarbons comprising at least 11 carbon atoms in the synthetic hydrocarbon mixture is less than 5%. This has the associated benefit of a recycle process being able to obtain high overall hydrocracking conversion but maintaining moderate conditions and thus moderate conversion per pass.
  • a further aspect of the present disclosure relates to a method for production of a synthetic gasoline product from a synthetic hydrocarbon mixture produced from a mixture of reactive oxygenates comprising the steps of i. fractionating the synthetic hydrocarbon mixture in at least a low boiling hydrocarbon fraction and an intermediate boiling hydrocarbon fraction, ii. directing at least an amount of said intermediate boiling hydrocarbon fraction to contact a material catalytically active in isomerization under effective isomerization conditions to provide an isomerized intermediate boiling hydrocarbon fraction, iii. directing at least an amount of said isomerized intermediate boiling hydrocarbon fraction to contact a material catalytically active in hydrocracking under effective hydrocracking conditions to provide a hydrocracked intermediate boiling hydrocarbon fraction, iv.
  • the method further comprises the steps of v. further separating the synthetic hydrocarbon mixture in a higher boiling fraction comprising at least 70% of the molecules comprising 10 or more carbon atoms present in the hydrocarbon mixture, vi. directing at least an amount of said higher boiling hydrocarbon fraction as a hydrocracking feedstock to contact a material catalytically active in hydrocracking under effective hydrocracking conditions providing a hydrocracked hydrocarbon stream and vii.
  • effective hydrocracking conditions involve a temperature in the interval 250-425°C, a pressure in the interval 30-150 Bar, and a liquid hourly space velocity (LHSV) in the interval 0.5-4, optionally together with intermediate cooling by quenching with hydrogen, feed or product and wherein the material catalytically active in hydrocracking comprises (a) one or more active metals taken from the group platinum, palladium, nickel, cobalt, tungsten and molybdenum, (b) an acidic support showing cracking activity, such as amorphous acidic oxides and molecular sieves and (c) a refractory support such as alumina, silica or titania, or combinations thereof.
  • active metals taken from the group platinum, palladium, nickel, cobalt, tungsten and molybdenum
  • an acidic support showing cracking activity such as amorphous acidic oxides and molecular sieves
  • a refractory support such as alumina, silica or titania, or combinations
  • the conditions are chosen such that the amount of material boiling above 190°C in said hydrocracked hydrocarbon stream fraction is reduced by at least 20%wt, 50%wt or 80%wt or more compared to said hydrocracker feed stream.
  • effective isomerization conditions involves a temperature in the interval 250-350°C, a pressure in the interval 30-150 Bar, and a liquid hourly space velocity (LHSV) in the interval 0.5-8 and wherein the material catalytically active in isomerization comprises one or more active metals in their active form taken from the group elemental platinum, elemental palladium, elemental nickel, sulfided nickel, sulfided cobalt, sulfided tungsten and sulfided molybdenum, one or more acidic supports, preferably molecular sieves, such as those having a topology taken from the group comprising MFI, FAU, BEA, MOR, FER, MRE, MWW, AEL, TON and MTT and an amorphous refractory support comprising one or more oxides taken from the group comprising alumina, silica and titania.
  • LHSV liquid hourly space velocity
  • the amount the amount of psedocumene in said isomerized hydrocarbon stream is reduced by at least 20%wt, 50%wt or 80%wt or more compared to said intermediate boiling hydrocarbon fraction.
  • a further aspect of the present disclosure relates to a process for production of a synthetic gasoline product from a feedstock comprising methanol, said process comprising the steps of;
  • a further aspect of the present disclosure relates to a gasoline post-treatment unit for combining and post-treating two streams of synthetic hydrocarbons, a low boiling hydrocarbon inlet, comprising an intermediate boiling hydrocarbon inlet and an upgraded synthetic gasoline product outlet, an post-treatment hydrocracking unit, having an inlet and an outlet and a hydrogenation unit having an inlet and an outlet, wherein the intermediate boiling hydrocarbon inlet is in fluid communication with said post-treatment hydrocracking unit inlet and said post-treatment hydrocracking unit outlet is in fluid communication with either said hydrogenation unit inlet or said upgraded synthetic gasoline product outlet, and said low boiling hydrocarbon inlet is in fluid communication with said hydrogenation unit inlet and the hydrogenation unit outlet is in fluid communication with the upgraded synthetic gasoline product outlet.
  • This has the associated benefit of such a gasoline upgrading unit being flexible and efficient for provision of a synthetic gasoline in compliance with the strict or intermediate specifications as required.
  • a further aspect of the present disclosure relates to a process plant for production of a synthetic gasoline product
  • a gasoline post-treatment unit according to the previous aspect, and a hydrocarbon synthesis section having an oxygenate inlet and a synthetic hydrocarbon outlet, a gasoline splitter section, having an inlet and at least a low boiling hydrocarbon outlet, an intermediate boiling hydrocarbon outlet and a high boiling hydrocarbon outlet and a hydrocracking section having an inlet and an outlet, and an optional isomerization section having an inlet and an outlet, wherein the gasoline splitter section inlet is in fluid communication with the synthetic hydrocarbon outlet, wherein if the optional isomerization section is absent, the intermediate boiling hydrocarbon outlet is in fluid communication with the low boiling hydrocarbon inlet of the gasoline post-treatment unit or wherein if the optional isomerization section is present, the intermediate boiling hydrocarbon outlet is in fluid communication with the inlet of the optional isomerization section and the outlet of the optional isomerization section is in fluid communication with the low boiling hydrocarbon inlet of the gasoline post-treatment unit, where
  • an intermediate boiling fraction being an amount of the synthetic hydrocarbon mixture, is directed to contact a material catalytically active in isomerization under effective isomerization conditions, and wherein the intermediate boiling hydrocarbon fraction contains at least 80% of the molecules comprising exactly 9 carbon atoms of the synthetic hydrocarbon mixture with the associated benefit of such a process increasing the octane number of the synthetic hydrocarbon mixture, by conversion of pseudocumene to mesitylene.
  • the aromatics comprising 10 or more carbon atoms in the intermediate boiling fraction accounts for less than 5%, 10% or 20% of the aromatics comprising 10 or more carbon atoms in the synthetic hydrocarbon mixture, with the associated benefit that when a minimum of C10+ aromatics are present in the intermediate boiling fraction, a majority is present in the high boiling hydrocarbon fraction such that the selective separation maximizes the amount of high boiling hydrocarbons to undergo hydrocracking.
  • Methanol-to-Gasoline The conversion of methanol or methanol/dimethyl ether mixtures into gasoline is generally referred to as the Methanol-to-Gasoline (MTG) process.
  • MMG Methanol-to-Gasoline
  • the methanol reactant is typically synthetized from a synthesis gas, which may be made by gasification of solid carbonaceous material or by reforming liquid or gaseous hydrocarbons, typically natural gas.
  • the gasoline synthesis takes place in well-known fixed bed and/or fluidized bed reactors and is typically carried out at a pressure of 10-40 bar and a temperature of 280-450°C, preferably 300-430°C.
  • the effluent from the gasoline synthesis section which is enriched in gasoline components and water, low boiling olefinic hydrocarbons, methane and paraffins, is cooled and passed to a three phase separating unit where a non-polar phase comprising C3+ hydrocarbons (including paraffins, naphthenes, aromatics and olefins), a polar phase comprising water, oxygenated hydrocarbon by-products and unconverted oxygenates, and a gaseous phase comprising uncondensables (H2, CO, CO2 etc.), light ends (CH4, C2H6) and low boiling olefins are separated.
  • the gaseous phase is normally split in a purge stream and a recycle stream directed for the production of synthesis gas.
  • Raw synthetic gasoline is typically fed to a degassing unit to remove fuel gas and LPG fraction and volatile by-products dissolved in the raw synthetic gasoline, to provide a stabilized synthetic gasoline.
  • This degassing unit may be either independent or integrated into other means of separation for the synthetic gasoline.
  • oxygen-containing hydrocarbons (oxygenates) other than methanol are also easily converted in the MTG process.
  • gasoline synthesis results in some by-production of olefins, paraffins, methane and products from thermal cracking (hydrogen, CO, CO2). Subsequent separation and/or distillation ensures the upgrading of the raw hydrocarbon product mixture to useful gasoline.
  • a high yield of the useful gasoline products is desirable for obtaining proper process economy.
  • the synthesis gas for reacting to form the reactive oxygenates for the MTG process may be made any by synthesis gas production processes well known to the skilled person. These processes may involve gasification of carbonaceous materials, such as coal, (typically high boiling) hydrocarbons, solid waste and biomass; from reforming of liquid or gaseous hydrocarbons, typically natural gas; from coke oven waste gas; from biogas or from combination of streams rich in carbon oxides and hydrogen - e.g. of electrolytic origin.
  • the oxygenates originates from biomass they may be created by synthesis or fermentation and they may be characterized by having a 14C-isotope content above 0.5 parts per trillion of the total carbon content. Oxygenates originating from biomass will be beneficial due to a reduced CO2 emission.
  • the synthesis section for the production of easily convertible oxygenates may consist of a one-step methanol synthesis, a two-step methanol synthesis, a two-step methanol synthesis followed by a DME synthesis, or a methanol synthesis step followed by a combined methanol and DME synthesis step and a DME synthesis step or a one-step combined methanol and DME synthesis. It would be understood that the number of possible combinations of means of co-feeding into the methanol/DME synthesis loop and the layouts of the methanol or methanol/dimethyl ether synthesis is large. Any combinations deductible is therefore to be regarded as embodiments of present invention.
  • a catalytically active material comprising a zeolite is used for the conversion of oxygenates to gasoline products.
  • This may be any zeolite type being known as useful for the conversion of oxygenates to gasoline range boiling hydrocarbons.
  • Preferred types are those with a silica to alumina mole ratio of at least 12 and pore sizes formed by up to 12 membered rings, preferably 10 membered.
  • Examples of such zeolites are those having one of the topologies MFI, MEL, MTW, MTT, FER such as ZSM-5, ZSM-11 , ZSM-12, ZSM-23, ZSM-35 and ZSM-38. The manufacture of these is well known in the art and the catalysts are commercially available.
  • a common catalytically active material is the ZSM-5 zeolite in its hydrogen form, i.e. HZSM-5.
  • the synthesis of gasoline from oxygenates is in simple terms based on conversion of some methanol (a C1 compound) to dimethylether (a C2 compound).
  • Methanol (C1) and dimethylether (C2) react to form olefins (C2-C5), and the olefins react to form aromatics and naphthenics (C6-C11+) as well as longer olefins and paraffins (C6-C11).
  • the gaseous compounds (C1-C3) are recycled to synthesis gas production and the high boiling compounds constitute a mixture corresponding qualitatively to fossil naphtha.
  • synthesis temperature is increased and as a result the relative activity of side reactions towards forming longer olefins is increased.
  • the synthetic gasoline While functionally equivalent, to naphtha obtained by hydroprocessing of fossil hydrocarbons, the synthetic gasoline has a different carbon distribution, resulting into a slightly higher boiling range of products, typically with a lower amount of C6 and C7 hydrocarbons, a higher amount of C8, C9 and C10 hydrocarbons as well as a presence of C11 + hydrocarbons in the 2-5wt% range, which would be substantially absent in fractionated fossil hydrocarbons.
  • a further difference between the nature of fossil gasoline and synthetic gasoline is the fact that fossil gasoline is a mixture of hundreds of different molecules, whereas synthetic gasoline is dominated by as few as 10 different molecules that account for approximately 50 wt% of the total composition.
  • the nature of the synthetic gasoline is illustrated in Table 1.
  • a common C10 hydrocarbon in the synthetic gasoline product is durene (1 ,2,4,5- tetramethylbenzene), which has a melting point of 79.2°C and a boiling point of 196°C.
  • the high melting point is problematic for the final gasoline product, especially in cold climates.
  • the other tetramethylbenzenes have a much lower melting point and a slightly higher boiling point.
  • pseudocumene (1 ,2,4- trimethylbenzene) is the most abundant, whereas the isomer mesitylene (1 ,3,5-trime- thylbenzene) is less common.
  • the octane number of mesitylene is 171 , i.e.
  • the C11+ hydrocarbons are often diaromatics and are undesired in gasoline due to the potential formation of particulate matter during combustion.
  • olefins an inherent product group in the synthesis of gasoline from methanol is olefins.
  • the majority of olefins will be C7 and C8 compounds.
  • olefins typically, around 6-15 wt% olefins are produced, which is in compliance with typical intermediate specification, but not in compliance with strict specifications.
  • a synthetic gasoline product with lower content of C8+ compounds would thereforebe preferable, as the resulting boiling point distribution would be in compliance with strict specifications, and a simple solution ensuring compliance with all current gasoline standards would be a separation of C8+ products and directing these to other uses.
  • the chemical nature of the C8+ fraction is not favorable for alternative valuable use, and therefore the use would typically to direct this fraction for use in fired heaters or for recycle to be used in the synthesis gas. Since this would constitute a yield loss of at least 20% this is not a desirable solution.
  • Isomerization is the conversion of constituents into other constituent having the same molecular formula.
  • the objective of isomerization is to convert undesired constituents to desired constituent, e.g. conversion of pseudocumene to mesitylene and durene to isodurene
  • the material catalytically active in isomerization of synthetic gasoline typically comprises an active metal (which according to the present disclosure is preferred to be either sulfided base metals such as nickel, cobalt, tungsten and/or molybdenum alone or in combination or one or more elemental reduced metals such as nickel, platinum and/or palladium), an acidic support (typically a molecular sieve showing high shape selectivity, and having a topology such as MFI, FAU, BEA, MOR, FER, MRE, MWW, AEL, TON and MTT) and a typically amorphous refractory support (such as alumina, silica or titania, or combinations thereof).
  • an active metal which according to the present disclosure is preferred to be either sulfided base metals such as nickel, cobalt, tungsten and/or molybdenum alone or in combination or one or more elemental reduced metals such as nickel, platinum and/or palladium
  • an acidic support typically a mo
  • material catalytically active in isomerization comprising sulfided or reduced Ni in combination with ZSM-5, reduced Ni in combination with silica-alumina, sulfided NiW in combination with y-alumina, reduced Pt in combination with ZSM-5, reduced Pt in combination with zeolite Y, all supported on an amorphous material, such as alumina.
  • the catalytically active material may comprise further components, such as boron or phosphorous.
  • Effective isomerization conditions typically involve directing the intermediate synthetic gasoline fraction to contact a material catalytically active in isomerization under effective isomerization conditions.
  • the conditions are typically a temperature in the interval 250- 430°C, a pressure in the interval 50-100 Bar, and a liquid hourly space velocity (LHSV) in the interval 0.3-8.
  • LHSV liquid hourly space velocity
  • Increasing temperature or decreasing LHSV will, as it is known to the skilled person, increase the process severity and thus the isomerization conversion.
  • Isomerization is substantially thermally neutral and consumes only hydrogen in hydrocracking side reactions so only a moderate amount of hydrogen is added in the isomerization reactor.
  • the isomerization feedstock must only comprise potential catalyst poisons in low levels such as levels of sulfur below 50 ppmw or even 1-10 ppmw, which may require purification. If the active metal is in sulfided form, a level of sulfur above 50 ppmw is required.
  • the Tgo requirements may be met by converting the high boiling fraction of synthetic gasoline to a lower boiling fraction by catalytic hydrocracking. Such a process will convert at least an amount of the di-aromatics to mono-aromatics and dealkylate multi-substituted monoaromatics to lower boiling compounds, thus reducing the intermediate boiling point and high boiling point of the product distillation curve.
  • the initial boiling point (IBP) of the high boiling fraction that will be selectively hydrocracked is selected/determined according to an optimization of the conversion required to meet distillation points specifications whilst minimizing octane rating loss incurred by dealkylation and hydrogenation reactions.
  • Hydrocracking involves directing high boiling synthetic gasoline fraction to contact a material catalytically active in hydrocracking.
  • the material catalytically active in hydrocracking typically comprises an active metal (which may be one or more sulfided base metals such as nickel, cobalt, tungsten and/or molybdenum or reduced noble metals such as Pt, Pd or PdPt), an acidic support (typically a molecular sieve showing high cracking activity, and having a topology such as MFI, BEA, FAU and MOR, but amorphous acidic oxides such as silica-alumina may also be used) and a refractory support (such as alumina, silica or titania, or combinations thereof).
  • the catalytically active material may comprise further components, such as boron or phosphorous.
  • Effective hydrocracking conditions are typically a temperature in the interval 250-430°C, a pressure in the interval 20-100 Bar, and a liquid hourly space velocity (LHSV) in the interval 0.3-10.
  • LHSV liquid hourly space velocity
  • Increasing temperature or decreasing LHSV will, as it is known to the skilled person, increase the process severity and thus the hydrocracking conversion, i.e. the amount of product having a lower molecular weight than the feedstock.
  • the process may involve intermediate cooling e.g. by quenching with cold hydrogen, feed or product.
  • a high boiling synthetic gasoline fraction, including the treat gas, is typically directed to contact the material catalytically active in hydrocracking without further purification.
  • this mixture of hydrocarbons and treat gas should preferably contain at least 50 ppmw sulfur and when it is a noble metal the sulfur level should preferably be below 10 ppmw sulfur.
  • olefins may be present in too high concentration in the raw synthetic gasoline. They may be removed by a catalytic hydrogenation process, where hydrogen reacts with the olefin to saturate olefinic double bonds.
  • the material catalytically active in hydrogenation of olefins typically comprises an active metal (sulfided base metals such as nickel, cobalt, tungsten and/or molybdenum, but possibly also either elemental noble metals such as platinum and/or palladium) and a refractory support (such as alumina, silica or titania, or combinations thereof).
  • active metal sulfided base metals such as nickel, cobalt, tungsten and/or molybdenum, but possibly also either elemental noble metals such as platinum and/or palladium
  • a refractory support such as alumina, silica or titania, or combinations thereof.
  • the most common catalytically active materials will be sulfided molybdenum (5-20 wt%) and nickel (1-10 wt%) on an alumina support.
  • Effective hydrogenation conditions are typically a temperature in the interval 220-350°C, a pressure in the interval 10-150 Bar, and a liquid hourly space velocity (LHSV) in the interval 0.1-10, optionally together with intermediate cooling by quenching with cold hydrogen, feed or product. Hydrogenation of olefins will typically also occur in contact with materials catalytically active in other hydroprocessing reactions such as hydrocracking and isomerization, under the conditions for these processes.
  • LHSV liquid hourly space velocity
  • Some embodiments of the present disclosure may involve the use of a catalytically active material comprising a sulfided base metal.
  • a sulfur donor is required to maintain sulfidation, and thus activity, of the sulfided active metal, since the synthetic gasoline is inherently sulfur free.
  • embodiments may be envisioned in which such added sulfur must be removed upstream a catalytically active material based on noble metals. Typically sulfur removal will occur in relation to stabilization of intermediate products.
  • a process plant for upgrading of synthetic gasoline to comply with intermediate specifications for Tgo and olefin content will, as mentioned above, beneficially involve a single intermediate product fractionation distributing product between the different treatments, such that C10+ will be directed to hydrocracking and C9 to isomerization, in order to adjust boiling point and boost the octane number, while lower boiling hydrocarbons will be by-passed such reactions to ensure a minimal yield loss.
  • a process for providing a product which is compatible with strict specifications would also require hydrocracking and isomerization as well as some olefin hydrogenation of the synthetic gasoline. As mentioned hydrogenation of olefins will also occur under the reaction conditions for isomerization.
  • the C9+ fraction would require hydrocracking and the C7 fraction (or at least a part of it) and the C8 fraction would contain a high amount of olefins to be saturated, and therefore a simple process for compliance with strict specifications with a low number of reactors would involve splitting the synthetic gasoline in a C3-C6/C7 fraction which is passed untreated as product, a C7/C8- C9 fraction for isomerization and hydrogenation and a C10+ fraction for hydrocracking with recycle of the product.
  • the synthetic gasoline is split in a C3-C8 fraction which is passed untreated as product, a C9+ fraction for isomerization and a C10+ fraction for hydrocracking with recycle of the product.
  • the isomerized C9+ fraction is then further hydrocracked and combined with the C3-C8 fraction, the combined stream is subsequently directed for olefin saturation. While such a process has the added cost of two reactors, the total volume of reactors and the total volume of catalyst required is reduced, with substantial savings as the result.
  • Figure 1 shows a process for producing a synthetic gasoline product comprising a gasoline upgrade unit according to the present disclosure
  • Figure 2 shows a process for producing a synthetic gasoline, in which gasoline is upgraded without a separate gasoline upgrade unit by a process integrated in the gasoline stabilization unit.
  • Figure 1 shows an embodiment of the present disclosure, which is configured for providing a synthetic gasoline complying with strict specifications for boiling point and olefin content, while also minimizing loss of octane number rating by inclusion of an isomerization unit, and for maximizing the gasoline yield by a low extent of hydrocracking per pass in combination with recycling the hydrocracked higher boiling hydrocarbon fraction.
  • a carbonaceous feed stream (2) typically natural gas, but optionally a solid feedstock such as coal or renewable feedstock, is directed to a methanol front-end process unit (MFP).
  • MFP methanol front-end process unit
  • a gasifier will produce a synthesis gas, whereas natural gas is converted to synthesis gas in a reformer.
  • the synthesis gas is cleaned, and the composition may be adjusted to match the requirements of a downstream methanol synthesis unit, in which synthesis gas is catalytically converted to methanol.
  • the produced methanol (4) is directed to a hydrocarbon synthesis unit (MTG) in which methanol (4) is converted to a raw synthesized hydrocarbon mixture (6).
  • the raw synthesized hydrocarbon mixture (6) is directed to gasoline treatment unit (GTU) comprising a gasoline splitter section (GSS), which may comprise several sub-units, typically including a three-phase separator, separating incondensable gases, water and raw synthetic gasoline.
  • GTU gasoline treatment unit
  • GSS gasoline splitter section
  • the raw hydrocarbon mixture (6) is typically stabilized in a de-ethanizer and an LPG splitter, to provide one or more gaseous hydrocarbon streams and a synthesized hydrocarbon mixture.
  • a de-ethanizer and an LPG splitter For simplicity the figure does not show withdrawal of one or more gas streams comprising H2, CO, CH4, C2H6, C3H8, C4H10, and to some extent, C5H12, but in practice it is typically split in multiple fractions as described.
  • the gasoline splitter section (GSS) further splits the synthesized hydrocarbon mixture in a low boiling hydrocarbon fraction (10) boiling in the gasoline range, and typically comprising C4-C8 hydrocarbons, an intermediate boiling hydrocarbon fraction (12), typically dominated by C9 hydrocarbons and a higher boiling hydrocarbon fraction (14) comprising C10+ hydrocarbons.
  • the intermediate boiling hydrocarbon fraction (12) is directed to a hydroisomerization unit (ISOM), in which pseudocumene is converted to mesitylene, resulting in increased octane number providing an isomerized intermediate boiling hydrocarbon fraction (16).
  • the higher boiling hydrocarbon fraction (14) is directed to a hydrocracking unit (HDC), in which the C10+ hydrocarbons are converted mainly to C8-C9 hydrocarbons by hydrocracking, providing a hydrocracked higher boiling hydrocarbon fraction (18).
  • the hydrocracked higher boiling hydrocarbon fraction (18) is directed to feed the gasoline splitter section (GSS), such that light and intermediate boiling hydrocracked products are directed to the low boiling hydrocarbon fraction (10) and intermediate boiling hydrocarbon fraction (12), whereas the higher boiling hydrocracked products are directed to the higher boiling hydrocarbon fraction (14), and thus recycled to the inlet of the hydrocracking unit (HDC), allowing milder hydrocracking conditions per pass, as any unconverted high boiling hydrocarbons will be recycled.
  • GSS gasoline splitter section
  • HDC hydrocracking unit
  • the low boiling hydrocarbon fraction (10) and the isomerized intermediate boiling hydrocarbon fraction (16) will be directed to a gasoline post-treatment unit (GPT) which may be integrated into the gasoline treatment unit (GTU) or be positioned separately, and possibly receive additional feed streams.
  • the gasoline post-treatment unit (GPT) will contain an post-treat hydrocracker unit (PHC) containing a material catalytically active in hydrocracking, which may be the same or different from the material catalytically active in hydrocracking in the hydrocracker unit (HDC) and a hydrogenation unit (HYD) containing a material catalytically active in hydrogenation of olefins.
  • PLC post-treat hydrocracker unit
  • HDC hydrocracker unit
  • HID hydrogenation unit
  • the post-treat hydrocracker unit will receive the stream of isomerized intermediate boiling hydrocarbon fraction (16), and be configured for an appropriate conversion, resulting in the boiling point being reduced to the extent required for compliance with specifications, to provide a hydrocracked isomerized hydrocarbon fraction (20), which without removal of gas phase including hydrogen is combined with the low boiling hydrocarbon fraction (10) and directed to the hydrogenation unit (HYD) for partial or complete saturation of olefins.
  • the low boiling hydrocarbon fraction (10) and the isomerized intermediate boiling hydrocarbon fraction (16) may be combined, to provide a synthetic gasoline product (24), to reduce process complexity and operating cost.
  • Hydrogen is added to the hydrocracking, isomerization and hydrogenation units, and the products therefrom are typically stabilized in a separator, by withdrawing light gases but for simplicity this is not shown.
  • Figure 2 shows a process, which is configured for providing a synthetic gasoline complying with strict specifications for boiling point and olefin content, while also minimizing loss of octane number rating, by inclusion of an isomerization unit, and for maximizing the gasoline yield by a low extent of hydrocracking per pass in combination with recycling the hydrocracked higher boiling hydrocarbon fraction.
  • a carbonaceous feed stream (2) typically natural gas, but optionally a solid feedstock such as coal or renewable feedstock, is directed to a methanol front-end process unit (MFP).
  • MFP methanol front-end process unit
  • a gasifier will produce a synthesis gas, whereas natural gas is converted to synthesis gas in a reformer.
  • the synthesis gas is cleaned, and the composition may be adjusted to match the requirements of a downstream methanol synthesis unit, in which synthesis gas is catalytically converted to methanol.
  • the produced methanol (4) is directed to a hydro- carbon synthesis unit (MTG) in which methanol is converted to a raw synthesized hydrocarbon mixture (6).
  • the raw synthesized hydrocarbon mixture (6) is directed to gasoline treatment unit (GTU) comprising a gasoline splitter section (GSS), which may comprise several sub-units, typically including a three-phase separator, separating incondensable gases, water and raw synthetic gasoline.
  • GTU gasoline treatment unit
  • GSS gasoline splitter section
  • the raw hydrocarbon mixture is typically stabilized in a de-ethanizer and an LPG splitter, to provide one or more gaseous hydrocarbon streams and a synthesized hydrocarbon mixture.
  • a de-ethanizer and an LPG splitter For simplicity the figure does not show withdrawal of a gas stream comprising H2, CO, CH4, C2H6, C3H8, and C4H10, but in practice it is typically split in multiple fractions as described.
  • the gasoline splitter section further splits the synthesized hydrocarbon mixture in three fractions, although a higher number of fractions may be provided.
  • the split When producing synthetic gasoline (24) according to intermediate specifications, the split will be in a low boiling hydrocarbon fraction (10) typically comprising C4-C8 hydrocarbons, an intermediate boiling hydrocarbon fraction (12), typically dominated by C9 hydrocarbons and a higher boiling hydrocarbon fraction (14) comprising C10+ hydrocarbons.
  • the gasoline splitter section may also be configured such that the low boiling hydrocarbon fraction (10) comprises C4-C7 hydrocarbons, the intermediate boiling hydrocarbon fraction (12), comprises some C7 and C10 as well as the majority of C8 and C9 hydrocarbons and a higher boiling hydrocarbon fraction (14) comprising C10+ hydrocarbons, which would be the gasoline split configuration chosen for compliance with strict specifications.
  • the intermediate boiling hydrocarbon fraction (12) is directed to a hydroisomerization unit (ISOM), in which pseudocumene is converted to mesitylene and olefins are partially hydrogenated, resulting in minimization of loss of octane number and providing an isomerized intermediate boiling hydrocarbon fraction (16).
  • the higher boiling hydrocarbon fraction (14) is directed to a hydrocracking unit (HDC), in which the C10+ hydrocarbons are converted mainly to C8-C9 hydrocarbons by hydrocracking, providing a hydrocracked higher boiling hydrocarbon fraction (18).
  • the hydrocracked higher boiling hydrocarbon fraction (18) is directed to feed the gasoline splitter section (GSS), such that low boiling and intermediate boiling hydrocracked products are directed to the low boiling hydrocarbon fraction (10) and intermediate boiling hydrocarbon fraction (12), whereas the higher boiling hydrocracked products are directed to the higher boiling hydrocarbon fraction (14), and thus recycled to the inlet of the hydrocracking unit (HDC), allowing milder hydrocracking conditions per pass, as any unconverted high boiling hydrocarbons will be recycled.
  • the low boiling hydrocarbon fraction (10), the isomerized intermediate boiling hydrocarbon fraction (16) and the hydrocracked higher boiling hydrocarbon fraction (18) are combined, to provide a synthetic gasoline product (24).
  • the hydrocracking unit contains a material catalytically active in hydrocracking and is operated under hydrocracking conditions. If the material catalytically active in hydrocracking comprises sulfided base metals, a source of sulfur must be present, typically by addition of a sulfur containing hydrocarbon. If the material catalytically active in hydrocracking comprises reduced metals, the fractions of the synthetic gasoline are inherently sulfur-free, and thus, do not require any sulfur removal process. If no recycle is applied, the process may typically be configured for a high hydrocracking conversion of higher boiling hydrocarbon to ensure that the product complies with the relevant requirements, whereas the process may be configured for low or moderate hydrocracking conversion if recycle is applied.
  • the hydroisomerization unit if present, contains a material catalytically active in hydroisomerization and is operated under hydroisomerization conditions. If the material catalytically active in hydroisomerization comprises sulfided base metals, a source of sulfide must be present in the intermediate boiling hydrocarbon fraction, typically by addition of a sulfur containing hydrocarbon. If the material catalytically active in hydroisomerization comprises reduced metals, the process must be designed to remove sulfides from the intermediate boiling hydrocarbon fraction, at least to a level below 50 ppmw, which may be accomplished during the stabilization of the synthetic gasoline in the hydrocracker section (HDC) or in the gasoline splitting section (GSS).
  • HDC hydrocracker section
  • GSS gasoline splitting section
  • a process for production of synthetic gasoline via a methanol route was evaluated by experimental testing of stabilized synthetic gasoline having the composition and charac- teristics shown in Table 1.
  • This product is neither in compliance with the strict specifications or intermediate specifications considered, which for the examples are an upper limit for Tgo of 152°C (305°F) and less than 6 vol% olefins after blending with 10% ethanol (which before blending corresponds to 6.6 vol%, or 6 wt% in the synthetic gasoline) in strict specifications and Tgo of 168°C (335°F) and less than 10 vol% olefins after blending with 10% ethanol (which before blending corresponds to 11 vol%, or 10 wt% in the synthetic gasoline) in intermediate specifications.
  • Example 1 is an example according to Figure 2.
  • a synthetic gasoline is produced, which in a gasoline splitter is split in a low boiling fraction (C3-C8, boiling below 150°C), an intermediate fraction (C9-C10, boiling between 150°C and 180°C) and a high boiling fraction (C9+, boiling above 180°C).
  • the high boiling fraction is hydrocracked and directed to the gasoline splitter.
  • the intermediate boiling fraction is isomerized and directed to be combined with the low boiling fraction.
  • the concentration of olefins is 10 wt% and T90 is 168°C, which is in compliance with intermediate specifications but not in compliance with strict specifications.
  • Example 2 is also an example according to the process layout Figure 2 of the present disclosure, but with different fractionation temperatures.
  • a synthetic gasoline is produced, which in a gasoline splitter is split in a low boiling fraction (41 t/h, C3-C7, boiling below 90°C), an intermediate fraction (59 t/h, C8-C9, boiling between 90°C and 150°C) and a high boiling fraction (13 t/h, C10+, boiling above 150°C).
  • the high boiling fraction is hydrocracked and directed to the gasoline splitter.
  • the intermediate boiling fraction is isomerized and directed to be combined with the low boiling fraction.
  • the volume of the intermediate stream is increased from 22 t/h to 59 t/h, i.e. a factor 2.7 compared to example 1 and the volume directed for hydrocracking is increased from 10 t/h to 14 t/h, i.e. by 40%.
  • similar reaction conditions are required, including reactor space velocity. Therefore, an increase of the isomerization reactor size by a factor 2.7 is necessary for sufficient isomerization. It is not assumed that additional reactor volume or catalyst is required due to the olefin saturation.
  • the volume directed for hydrocracking will also be increased by 40%.
  • reactor size must be increased and the volume of make-up hydrogen consumed will be increased, which will add to capital cost as well as operational cost.
  • the concentration of olefins is 6 wt% and T90 is 152°C, which is in compliance with strict specifications.
  • Example 3 is an example according to Figure 1 of the present disclosure.
  • a synthetic gasoline is produced, which is split in a low boiling fraction (C3-C8, boiling below 150°C), an intermediate fraction (C9-C10, boiling between 150°C and 180°C) and a high boiling fraction (C9+, boiling above 180°C), in a similar manner as Example 1 (78 t/h, 22 t/h and 10 t/h respectively).
  • Example 3 requires two extra reactors; a post-treat hydrocracking unit and a hydrogenation unit; but the related capital cost is secondary to the cost related to the extra reacting volumes of Example 2.
  • the concentration of olefins is 4 wt% and T90 is 152°C, which is in compliance with strict specifications.
  • Example 2 is conceptually similar to Example 1 , and appears simpler, and requires 2 reactors less, and therefore appears the immediate choice.
  • Example 3 is however able to demonstrate the same performance as Example 2, and although apparently more complex, Example 3 is also less expensive to implement, as the total volume of reacting streams will be lower, and provides the flexibility of producing products adhering to strict or intermediate specifications.

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente divulgation concerne une usine de production et un procédé de production d'un produit à base d'essence synthétique à partir d'un mélange d'hydrocarbures synthétiques produit par post-traitement d'un produit à base d'essence synthétique comprenant moins d'une concentration spécifiée en oléfines, tel que 6 % en volume ou 11 % en volume à partir d'un premier mélange d'hydrocarbures synthétiques produit à partir d'un mélange de composés oxygénés réactifs, ledit premier mélange d'hydrocarbures synthétiques ayant T90 inférieur à 140 °C et comprenant au moins ladite concentration spécifiée en oléfines et un second mélange d'hydrocarbures synthétiques, produit à partir d'un mélange de composés oxygénés re-actifs, ledit second mélange d'hydrocarbures synthétiques ayant T90 supérieur à 150 °C. Ledit procédé comprend les étapes consistant à a. orienter le second mélange d'hydrocarbures synthétiques pour entrer en contact avec un matériau catalytiquement actif en hydrocraquage dans des conditions d'hydrocraquage efficaces, pour fournir un second mélange d'hydrocarbures synthétiques hydrocraqués, b. diriger ledit premier mélange d'hydrocarbures synthétiques pour entrer en contact avec un matériau catalytiquement actif dans l'hydrogénation d'oléfines, pour obtenir un mélange d'hydrocarbures hydrogéné, ledit second mélange d'hydrocarbures synthétiques hydrocraqués étant soit ajouté au premier mélange d'hydrocarbures synthétiques en amont de la mise en contact dudit matériau catalytiquement actif dans l'hydrogénation d'oléfines, soit ajouté à un mélange d'hydrocarbures hydrogéné, en contact en aval dudit matériau catalytiquement actif dans l'hydrogénation d'oléfines pour obtenir ledit produit à base d'essence synthétique. Cela présente l'avantage associé de permettre une production flexible d'essence synthétique respectant des spécifications strictes ou des spécifications intermédiaires pour le point d'ébullition et la concentration d'oléfines selon les besoins.
EP21816105.7A 2020-12-01 2021-12-01 Production sélective et flexible d'essence synthétique Pending EP4256007A1 (fr)

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EP20210941 2020-12-01
PCT/EP2021/083760 WO2022117644A1 (fr) 2020-12-01 2021-12-01 Production sélective et flexible d'essence synthétique

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US11939283B1 (en) * 2022-09-30 2024-03-26 Uop Llc Process for the hydrogenation of olefins

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GB9109747D0 (en) * 1991-05-07 1991-06-26 Shell Int Research A process for the production of isoparaffins
JP3824489B2 (ja) * 1998-10-05 2006-09-20 セイソル テクノロジー （プロプライエタリー） リミテッド 生分解性の中間留出物
ITMI20031361A1 (it) * 2003-07-03 2005-01-04 Enitecnologie Spa Processo per la preparazione di distillati medi e basi lube a partire da cariche idrocarburiche sintetiche.
AU2005207842A1 (en) * 2004-01-16 2005-08-11 Syntroleum Corporation Process to produce synthetic fuels and lubricants
CN104334693B (zh) 2012-05-29 2016-06-29 赫多特普索化工设备公司 用于改质汽油的方法和催化剂
DE102018103552B4 (de) * 2018-02-16 2024-01-25 Cac Engineering Gmbh Verfahren und Anlage zur Herstellung eines synthetischen Benzins

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