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WO2024227724A2 - Procédé et installation de production de kérosène paraffinique synthétique en tant que carburéacteur - Google Patents

Procédé et installation de production de kérosène paraffinique synthétique en tant que carburéacteur Download PDF

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Publication number
WO2024227724A2
WO2024227724A2 PCT/EP2024/061722 EP2024061722W WO2024227724A2 WO 2024227724 A2 WO2024227724 A2 WO 2024227724A2 EP 2024061722 W EP2024061722 W EP 2024061722W WO 2024227724 A2 WO2024227724 A2 WO 2024227724A2
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WO
WIPO (PCT)
Prior art keywords
stream
olefins
reactor
oligomerization
catalyst
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PCT/EP2024/061722
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WO2024227724A3 (fr
Inventor
Niels Christian Schjødt
Esben Taarning
Rasmus Yding BROGAARD
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Topsoe AS
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Haldor Topsoe AS
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Priority to CN202480029614.4A priority Critical patent/CN121039255A/zh
Publication of WO2024227724A2 publication Critical patent/WO2024227724A2/fr
Publication of WO2024227724A3 publication Critical patent/WO2024227724A3/fr
Anticipated expiration legal-status Critical
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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • 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
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
    • 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
    • C10G2300/1011—Biomass
    • 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
    • C10G2300/4056—Retrofitting operations
    • 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
    • C10G2400/08—Jet fuel

Definitions

  • the present invention relates to a process and plant for producing hydrocarbons in the transportation fuel range, for instance a jet fuel such as kerosene, more specifically synthetic paraffinic kerosene (SPK), from ethylene.
  • a jet fuel such as kerosene, more specifically synthetic paraffinic kerosene (SPK)
  • SPK synthetic paraffinic kerosene
  • the ethylene is for instance provided by catalytic dehydration of ethanol.
  • the ethanol is for instance provided by the fermentation of biomass.
  • the present invention relates also to a method of retrofitting existing hydroprocessing plants.
  • hydrocarbons in the transportation fuel range such as fuels for aviation (jet fuel, kerosene) from non-fossil sources.
  • This can be accomplished by various technologies such as Fischer-Tropsch (FT) synthesis from non-fossil synthesis gas, or by converting methanol-to-olefins (MTO) from non-fossil methanol combined with oligomerization and hydrogenation.
  • FT Fischer-Tropsch
  • MTO methanol-to-olefins
  • SPK synthetic paraffinic kerosene
  • Ethanol can be converted to ethylene and oligomerized in various ways, followed by hydrogenation and fractionation to produce SPK, as for instance disclosed in US 2022/0396741 , US 11377607, US 11078433 and US 20150299069.
  • dewaxing and/or hydrocracking reactors for the hydroprocessing of hydrocarbon feeds including renewable feeds such as vegetable oils into valuable hydrocarbon products in the transportation fuel range, such as diesel and jet fuel.
  • the dewaxing and/or hydrocracking sections comprising such reactors are normally more expensive in terms of capital and operating expenses (CAPEX and OPEX, respectively) than the section used for oligomerization of ethylene. It would therefore also be desirable to be able to provide a process and plant for producing a hydrocarbon stream which is capable of utilizing such already existing reactors (units).
  • the present invention provides a process and plant to convert ethylene, optionally obtained from EtOH, for example from ethanol which is obtained by fermentation of biomass, i.e. from bio-ethanol, to SPK in high yield and with a low freezing point, while at the same time reducing the risk of fouling and thus plugging in the oligomerization of ethylene or a downstream olefin stream due to formation of wax and polymeric material.
  • the invention provides a process for producing a hydrocarbon from ethylene according to the following steps: a) converting an ethylene stream in a first oligomerization reactor by contacting said ethylene stream with an oligomerization catalyst, said oligomerization catalyst being a homogeneous catalyst comprising:
  • transition metal compound or complex comprising at least one of Ti, Zr, Cr, Ni, together with an alkyl aluminum compound dissolved in a hydrocarbon solvent or an etheral solvent;
  • LAOs linear alfa olefins
  • fourth stream of C8+ olefins such as C8-C20 olefins
  • b-2 recycling at least a portion of the second stream of C2 olefins from step b- 1) to the first oligomerization reactor
  • a trimerization reactor by contacting the third stream of C4-C6 olefins from step b-1) with an oligomerization catalyst, optionally an oligomerization catalyst as defined in step a), for producing a fifth stream of branched C12-C18 olefins having a Branching Index (Bl), defined as the average number of carbon atoms in the side chains divided by the average number of carbon atoms in the main chain, higher than 0.30; c-2) hydrogenating the fifth stream of branched C12-C18 olefins in a hydrogenation reactor into a sixth product stream of branched C12-C18 isoparaffins having a Bl higher than 0.30.
  • Bl Branching Index
  • the fourth stream i.e. the LAO-stream of C8+ olefins, such as C8-C20 olefins
  • a hydroprocessing plant i.e. refinery, comprising a dewaxing section, and further processed therein.
  • the fifth stream of branched C12-C18 olefins from the second oligomerization reactor is suitably transported outside battery limits to the hydroprocessing plant also comprising a hydrogenation section, and further processed therein.
  • the fourth and sixth stream are mixed to form a combined feed for the dewaxing reactor, as recited in a below embodiment.
  • said hydrocarbon is synthetic paraffinic kerosene (SPK), and said process further comprises: d) converting the fourth stream of C8+ olefins, such as C8-C20 olefins, optionally together with a portion of said sixth product stream of branched isoparaffins, in the presence of hydrogen in a dewaxing reactor by contacting said third stream of C8+ olefins with a dewaxing catalyst, the dewaxing catalyst comprising: at least one transition metal selected from Ni, Pd, Pt or combinations thereof, and optionally another transition metal, and a zeolite or zeotype or a silica-alumina; and carrying out a dewaxing reaction comprising hydrogenation and isomerization of the olefins, for producing a seventh product stream of branched C8-C20 isoparaffins having a Bl higher than 0.05; e) separating the sixth product stream from step c-2) and
  • the freezing point is measured according to ASTM D2386.
  • first aspect refers to a process according to the invention.
  • second aspect refers to a plant (system) according to the invention.
  • another aspect of the invention refers to a SPK product according to the invention.
  • second another aspect of the invention refers to a method of retrofitting an existing hydroprocessing plant for producing hydrocarbon products such as any of gasoline, jet fuel, diesel.
  • the reference to specific compounds in a given stream means a stream rich in said compound or compounds.
  • ethylene stream means a stream rich in ethylene.
  • first stream of linear alfa olefins in the C2-C20 range means a stream rich in C2-C20 linear alfa olefins.
  • third stream of C4-C6 olefins means a stream rich in C4-C6 olefins.
  • the term “rich in a compound or compounds”, for instance a stream rich in C2-C6 olefins means more than 50 wt% of the stream, such as 60, 70, 80, 90 or 100 wt% of the stream.
  • the terms “compound” and “component” may be used interchangeably.
  • C8+ means hydrocarbons of up to 8 carbon atoms, optionally more than 8 carbon atoms; for instance C8-C20.
  • C8+ olefins comprise C8-C20 olefins.
  • the term “at least a portion” of a given stream means a portion of the stream or the entire stream.
  • SPK synthetic paraffinic kerosene
  • Branching Index is defined as the average number of carbon atoms in the side chains divided by the average number of carbon atoms in the main chain of hydrocarbons.
  • the term “comprising” includes also “comprising only”, i.e. “consisting of”.
  • a hydrocarbon means one or more hydrocarbons
  • a first oligomerization reactor means one or more oligomerization reactors operating as the first oligomerization reactor; such as one or more oligomerization reactors arranged in parallel.
  • unit or “section” means a physically delimited space.
  • a unit or section may comprise one or more units.
  • a section may comprise one or more units.
  • a unit such a fractionation unit may comprise one or more units, here one or more fractionation units.
  • a reactor such as dewaxing reactor, may also be regarded as a unit.
  • a step may comprise one or more sub-steps. For instance, said step b) comprises step b-1) and b-2).
  • present invention or “invention” may be used interchangeably with the term “present application” or “application”, respectively.
  • step c-1) comprises:
  • an oligomerization catalyst comprising a substituted N, N’, N” trialkyl 1 ,3,5-triazacyclohexane chro- mium(lll) chloride, optionally said substituted N, N’, N” trialkyl 1 ,3,5-triazacyclohexane chromium(lll) chloride being provided as the oligomerization catalyst precursor.
  • the trimerization reaction in step c-1) is thereby carried out with high selectivity by the proper choice of the transition metal catalyst, which is capable of forming intermediary metallacycles with the olefins.
  • An example of said substituted N, N’, N” trialkyl 1 ,3,5- triazacyclohexane chromium(lll) chloride is provided in A. G. N. Coxon & R. D. Kohn “Efficient 1 -Hexene Trimerization with Triazacyclohexane Chromium Catalysts and Detailed Product Analysis by 13C NMR”, ACS Catalysis 6 (2016), 3008-3016.
  • the invention provides a process for converting ethylene, optionally obtained by dehydration of EtOH, to SPK in at least 75% overall yield and with a freezing point of -40°C or below, or even -47°C or below.
  • the overall yield herein also interchangeably referred to as “yield”, is defined as the ratio of the number of carbon atoms in the SPK with respect to the number of carbon atoms in the ethylene being fed to the first oligomerization reactor.
  • the freezing point is of particular importance for jet fuel compositions since airplanes operate at high altitude and therefore at low temperature.
  • the SPK thus obtained may be blended with hydrocarbons from other sources or used alone as jet fuel.
  • the invention enables reduced formation of wax and polymeric material in the oligomerization, due to the relatively low chain propagation probability, i.e. the chain propagation probability defined by: the “alpha-value”, or interchangeably “a-value” of the Schultz-Flory distribution of products being in the range of 0.35-0.60; or the “lambda-value”, or interchangeably, “A-value” of the Poisson distribution of products in the range of 1.0-4.7.
  • the invention provides a high yielding process with an SPK composition particularly rich in branched isomers, where the Bl is unusually high, for instance above 0.10.
  • the process layout allows to maximize yield of SPK in the nineth product stream by tuning the LAO distribution in the first stream from the first oligomerization reactor, which controls the relative magnitude of thefifth stream from the second oligomerization reactor and the seventh product stream from the dewaxing reactor.
  • the freeze point can be tuned to achieve on- spec SPK with varying degrees of dewaxing severity (with concomitant yield loss) needed.
  • the invention comprises the recycle of said second stream of C2 olefins, i.e.
  • step b-2 an ethylene stream, to the first oligomerization reactor (step b-2)), thereby enabling to build up longer LAOs.
  • this solves the problem of the LAOs being too light for SPK, thus for use as jet fuel, and increases the overall SPK yield; there is a higher degree of branching upon recycling, which is normally unwanted, yet as a feedstock for SPK it is desirable; in case a low boiling hydrocarbon solvent is used in the oligomerization reactor, such as benzene, this can also be recycled back without the need to separate it from, e.g. the C8 LAO.
  • a portion of the second stream of C2 olefins is used for making aromatics.
  • the hydrocarbon solvent is benzene.
  • Kappa “k” is the number of monomers in the chain, here denoted as the alfa-olefin carbon number, and alfa “a” which has a value between 0 and 1, measures said chain propagation probability. The lower the alpha value, the more the shorter chains are favored. See for instance appended Fig. 2.
  • x is the number of occurrences
  • lambda “A” is the expected rate of occurrences, here denoted as the alfa-olefin carbon number.
  • lambda measures the chain propagation probability.
  • the molar fraction of the products is suitably described by the Poisson distribution and then converted to the corresponding weight fraction. See for instance appended Fig. 3.
  • said separating step is by fractionation in a fractionation unit, for instance distillation such as flash distillation in a flash distillation column, or in a distillation column.
  • the chain propagation probability is 0.40-0.54, such as 0.45 for a Schulz-Flory distribution; or 2.5-4.0 such as 3.1 for a Poisson distribution.
  • LAOs linear alpha olefins
  • said SPK i.e. the nineth product stream, has a freezing point of - 47°C or below and/or a Bl of up to 0.40.
  • the high degree of branching and the general low symmetry of the isomers has the effect of decreasing the melting point and thereby the freezing point.
  • n-dodecane (Bl 0)
  • C12H26 which has a melting point of -10°C.
  • the isomeric 2-methylundecane (Bl 0.091
  • the process further comprises, prior to said step a), a step of catalytic dehydration of ethanol for producing said ethylene stream; optionally the process further comprising fermentation of biomass for producing at least a portion of said ethanol.
  • the ethanol may be provided by different sources, for instance from the fermentation of biomass, in which carbohydrates are converted to ethanol and carbon dioxide by microorganisms.
  • the biomass is for instance a lignocellulosic biomass or non-lignocellu- losic biomass.
  • lignocellulosic biomass means a biomass containing, cellulose, hemicellulose and optionally also lignin. The lignin or a significant portion thereof may have been removed, for instance by a prior bleaching step.
  • the biomass can be forestry waste and/or agricultural residue and comprises biomass originating from plants including grass such as nature grass (grass originating from natural landscape), wheat e.g.
  • the biomass may thus include starch containing materials such as wheat and corn.
  • the biomass may also include sucrose containing materials such as sugar beet and sugar cane.
  • the process further comprises: supplying at least a portion of said eight stream of light end compounds to a hydrogen producing unit (HPU) or a gasification unit (Gil) for providing a make-up hydrogen stream or a synthesis gas stream; and providing at least a portion of said make-up hydrogen gas as said hydrogen in any of said steps c-2), i.e. hydrogenation, or d) i.e. dewaxing.
  • HPU hydrogen producing unit
  • Gil gasification unit
  • the eighth stream of light end components comprises for instance C3-C4 compounds such as LPG.
  • the light end stream may also comprise naphtha compounds, such as C5-C9 hydrocarbons.
  • the light end stream may comprise one or more side streams generated in the process or plant such as off- gases containing some C1-C2 hydrocarbons.
  • While some of the light end stream(s) may then be withdrawn as an off-gas and used as fuel in the process or plant, for instance in burners of fired heaters or auxiliary boilers for producing steam, at least a portion, suitably a major portion, or the entire portion, is used to generate make-up hydrogen used in the process or plant, thereby enabling high integration in the process as the required hydrogen is internally sourced instead of being externally sourced.
  • a portion of the light end stream is withdrawn as a separate naphtha stream. This can then be sold as a separate product.
  • the HPU comprises a steam reforming unit.
  • the steam reforming unit is for instance an electrically heated steam methane reformer (e-SMR), optionally with a pre-reformer arranged upstream.
  • the steam reforming unit is for instance an autothermal reformer (ATR), optionally with a pre-reformer arranged upstream.
  • the steam reforming unit is for instance a convection reformer, optionally with a pre-reformer arranged upstream. Combinations of the above are also envisaged.
  • the HPU may further comprise a water gas shift (WGS) section as well as a hydrogen purification unit such as a pressure swing adsorption (PSA) unit, for producing said make-up hydrogen gas.
  • the HPU may further comprise a CCh-removal unit, for instance in between the WGS section and the hydrogen purification unit.
  • the removed CO2 rich gas may then be subjected to carbon capture, utilization and storage (CCUS) according to known techniques.
  • the steam reforming unit is: a convection reformer, preferably comprising one or more bayonet reforming tubes such as an HTCR reformer i.e. Topsoe bayonet reformer, where the heat for reforming is transferred by convection along with radiation; a tubular reformer i.e. conventional steam methane reformer (SMR), where the heat for reforming is transferred chiefly by radiation in a radiant furnace; autothermal reformer (ATR), where partial oxidation of the hydrocarbon feed with oxygen and steam followed by catalytic reforming; electrically heated steam methane reformer (e-SMR), where electrical resistance is used for generating the heat for catalytic reforming; or combinations thereof.
  • a convection reformer preferably comprising one or more bayonet reforming tubes such as an HTCR reformer i.e. Topsoe bayonet reformer, where the heat for reforming is transferred by convection along with radiation
  • a tubular reformer i.e. conventional steam methane reformer (S
  • e-SMR electricity from green resources may be utilized, such as from electricity produced by wind power, hydropower, and solar sources, optionally from thermonuclear power, thereby further minimizing the carbon footprint.
  • a convection reformer, a SMR, or an ATR will require the burning of a great portion of e.g. LPG for producing heat for reforming
  • an e-SMR enables full utilization of the LPG or any other off-gas for the reforming and then production of the make-up hydrogen gas.
  • the catalyst in the steam reforming unit is a reforming catalyst, e.g. a nickel based catalyst.
  • the catalyst in the water gas shift reaction is any catalyst active for water gas shift reactions.
  • the said two catalysts can be identical or different.
  • reforming catalysts are Ni/MgAI 2 O4, Ni/AI 2 O 3 , Ni/CaAI 2 O4, Ru/MgAI 2 O 4 , Rh/MgAI 2 O 4 , lr/MgAI 2 O 4 , Mo 2 C, Wo 2 C, CeO 2 , Ni/ZrO 2 , Ni/MgO-AI 2 O 3 , Ni/CaAI 2 O4, Ru/MgO-AI 2 O 3 , or Rh/MgO-AI 2 O 3 , a noble metal on an AI 2 O 3 carrier, but other catalysts suitable for reforming are also conceivable.
  • the catalytically active material may be Ni, Ru, Rh, Ir, or a combination thereof, while the ceramic coating may be AI 2 O 3 , ZrO 2 , MgAI 2 O4, CaAI 2 O4, or a combination therefore and potentially mixed with oxides of Y, Ti, La, or Ce.
  • the maximum temperature of the reactor may be between 850-1300°C.
  • the pressure of the feed gas may be 15-180 bar, preferably about 25 bar.
  • Steam reforming catalyst is also denoted steam methane reforming catalyst or methane reforming catalyst.
  • the HPU may also produce a synthesis gas (syngas) stream, for instance by withdrawing a stream downstream the steam reforming unit, for instance from between the steam reforming unit and the WGS section, or from the WGS section, or from between the WGS section and the hydrogen purification unit, e.g. PSA unit.
  • a synthesis gas syngas
  • the at least a portion of said eighth stream of light end compounds may also be supplied to a gasification unit (GU) for providing the syngas.
  • the Gil as is well-known in the art syngas production, is a unit that converts a carbonaceous material at temperatures above 700°C without combustion with a controlled amount of oxygen and/or steam. It is to be understood, that the Gil may also include a water gas shift (WGS) reactor downstream the gasifier so as to convert CO with water to H2 and CO2, thus increasing the yield of the make-up hydrogen stream.
  • GSS water gas shift
  • syngas is a mixture of CO and H2, often in combination with CO2 and/or H2O.
  • syngas is to be understood in its broadest sense as any mixture of CO, CO2, H2 and H2O, possibly also containing gases which are inert to the reaction conditions such as Ar, N2 and CH4.
  • said step d) is carried out by sequential hydrogenation and dewaxing, by said fourth stream of C8+ olefins, such as C8-C20 olefins, being first hydrogenated in a first hydrogenation zone and subsequently isomerized in a dewaxing zone.
  • said fourth stream of C8+ olefins such as C8-C20 olefins
  • dewaxing and hydroisomerization are used interchangeably.
  • the dewaxing zone is arranged downstream the first hydrogenation zone.
  • the first hydrogenation zone is for instance a hydrogenation reactor.
  • the dewaxing zone is for instance a dewaxing reactor arranged downstream the first hydrogenation reactor.
  • the first hydrogenation zone and the dewaxing zone are for instance provided as different catalytic fixed beds in the same reactor.
  • the dewaxing catalyst comprises at least one transition metal selected from Ni, Pd, Pt and optionally another transition metal, and a zeolite or zeotype or a silica-alumina, to carry out a dewaxing reaction comprising hydrogenation and isomerization of the olefins to yield the seventh product stream of mainly branched C8- C20 isoparaffins.
  • the material catalytically active in dewaxing 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 showing high shape selectivity, and having a topology such as MOR, FER, MRE, MWW, AEL, TON and MTT) and a refractory support (such as alumina, silica or titania, or combinations thereof).
  • 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 showing high shape selectivity, and having a topology such as MOR, FER, MRE, MWW, AEL, TON and MTT
  • a refractory support such as alumina
  • the dewaxing conditions involve typically a temperature in the interval 250-400°C, a pressure in the interval 20-100 bar, and a liquid hourly space velocity (LHSV) in the interval 0.5-8.
  • LHSV liquid hourly space velocity
  • excess hydrogen from any of said dewaxing reactor and hydrogenation reactor downstream the second oligomerization reactor further comprises supplying at least a portion of said excess hydrogen to a hydrogen purification unit, such as a PSA unit, suitably to the PSA unit of said hydrogen producing unit (HPU).
  • a hydrogen purification unit such as a PSA unit
  • make-up hydrogen gas from the HPU is not only produced from the light end stream, but the HPU particularly the hydrogen purification unit therein e.g. PSA unit, serves to purify any excess hydrogen streams produced in the process.
  • the HPU can be made smaller, thus requiring i.a. smaller plot size.
  • the make-up hydrogen gas is recycled to the dewaxing or hydrocracking reactors, thus further enabling the process being self-sufficient with hydrogen.
  • e- SMR is provided in the HPU, a significantly low carbon footprint is also possible, as the e-SMR is powered by electricity produced from renewable sources such as wind and solar, optionally from thermonuclear power.
  • step a) or c-1) in any of step a) or c-1):
  • the oligomerization catalyst is a dissolved metal catalyst, in which the metal is said transition metal, and the transition metal is present in the concentration range 0.01-1.0 wt%; and/or - said alkyl aluminum catalyst is an alkyl aluminum compound such as triethyl aluminum or methyl aluminumoxide (MAO).
  • the oligomerization catalyst is a combination of titanium or zirconium alkoxides or carboxylates with alkyl aluminum compounds such as MAO; or complexes of Or or Ni in combination with alkyl aluminum compounds such as MAO.
  • the alkyl aluminum catalyst acts suitably as a co-catalyst.
  • the oligomerization catalyst is for instance an alkyl aluminum compound such as triethyl aluminum, or a combination of titanium or zirconium alkoxides or carboxylates with alkyl aluminum compounds such as MAO or complexes of Or or Ni in combination with MAO or other alkyl aluminum compounds.
  • alkyl aluminum compounds such as triethyl aluminum
  • a combination of titanium or zirconium alkoxides or carboxylates with alkyl aluminum compounds such as MAO or complexes of Or or Ni in combination with MAO or other alkyl aluminum compounds.
  • the oligomerization is better catalyzed by a transition metal compound in combination with an alkyl aluminum compound.
  • the chain propagation probability in the first oligomerization reaction is suitably controlled by the ratio between these two catalyst components and/or by the process conditions in terms of temperature and pressure, as for instance described in S. A. Svejda and M. Brookhart, Organometallics 18 (1999), 65-74, for a
  • the oligomerization in any of steps a) or c-1) is carried out at a temperature in the range 0-250°C, such as 20-200°C and at a pressure in the range 0.5-30 MPa, such as 1-15 MPa.
  • the temperature is 40, 60, 80, 100, 120, 140, 160, 180°C.
  • the pressure is 5, 10, 15, 20, 25 MPa.
  • the pressure values are absolute pressure.
  • the hydrocarbon solvent of the oligomerization catalyst is any of: said benzene, toluene, a portion of nineth product stream i.e. a portion of the SPK, a portion of the seventh product stream i.e. isoparaffins in the C8-C20 range, a portion of sixth product stream i.e. isoparaffins int the C12-C18 range, a combination of the sixth and seventh product streams. Combinations of any of these streams is also envisaged.
  • the oligomerization is thus carried out in appropriate solvents which can be for example benzene, toluene, an etheral solvent, or product streams produced in the process. Further integration of process streams is thereby provided.
  • the hydrocarbon solvent is benzene.
  • the etheral solvent of the oligomerization catalyst is any of: 1 ,4-bu- tanediol, an ether, or combinations thereof.
  • the ether is any of: diethyl ether, dipropyl ether, tetra hydrofuran, 1 ,4-dioxane or tetrahydropyran, or combinations thereof.
  • any of the first stream of LAOs or the fifth product of branched C12-C18 olefins is quenched by admixture with a solvent capable of neutralizing the dissolved catalyst species and removing them from the hydrocarbon phase of any of said first stream of LAOs or said fifth product of branched C12-C18 olefins, in which the solvent is a polar solvent comprising water, an alcohol, or a combination thereof;
  • the dissolved catalyst or catalysts are separated from the first stream of LAOs and recycled to the first oligomerization reactor;
  • the dissolved catalyst or catalysts are separated from the fifth product of branched C12-C18 olefins, and recycled to the second oligomerization reactor.
  • said SPK i.e. the nineth product stream, comprises less than 1 pppm wt of any of Al, Ni, Or, and combinations thereof.
  • the first product stream of LAOs comprises more Al and/or Cr than said SPK.
  • said SKP i.e. the nineth product stream, further comprises > 65 wt% paraffins, such as > 95 wt%, (with said Bl > 0.10), a specific gravity in the range 0.73- 0.77 g/cm 3 as measured by ASTM D287.
  • the SPK has the required density and is highly paraffinic.
  • a SPK product obtainable by the process as defined in any of the above process embodiments, comprising: > 65 wt% paraffins, such as > 95 wt%, a Bl > 0.10, e.g. Bl > 0.10 and up to 0.40, a specific gravity in the range 0.73-0.77 g/cm 3 as measured by ASTM D287, and a freezing point below -40 °C, e.g. -47°C, as measured by ASTM D2386; optionally wherein the SPK product is in compliance with ASTM D7566- Annex 5.
  • SPK synthetic paraffinic kerosene
  • the high content of paraffins together with Bl > 0.10, particularly in said range up to 0.40, along with the specific gravity (density) enables the provision of a superior SPK product.
  • the SPK product is suitably in accordance with ASTM D7566 - Annex 5 where the ethylene is produced from renewable sources e.g. biomass.
  • the SPK may thus be a sustainable aviation fuel (SAF) in accordance with ASTM D7566 - Annex 5 and it may then be blended with conventional jet fuel to a maximum limit of 50 vol%, thereby in compliance with ASTM D1655 corresponding to conventional Jet A or Jet A1 kerosene.
  • SAF sustainable aviation fuel
  • the first oligomerization rector comprising an oligomerization catalyst, said oligomerization catalyst being a homogeneous catalyst comprising: a transition metal compound or complex comprising at least one of Ti, Zr, Cr, Ni, together with an alkyl aluminum compound dissolved in a hydrocarbon solvent or an etheral solvent; or an alkyl aluminum compound dissolved in a hydrocarbon solvent or an etheral solvent, optionally as a co-catalyst;
  • the first oligomerization reactor further being arranged to provide a first stream of linear alfa olefins (LAOs) in the C2- C20 range of which at least 80 wt% having a Schultz-Flory distribution with a chain propagation probability (al
  • said first separation section arranged to receive: said first stream of LAOs and provide: said second stream of C2 olefins, a third stream of C4-C6 olefins, and a fourth stream of C8+ olefins, such as C8-C20 olefins; said first separation section further comprising a conduit arranged for recycling said at least a portion of second stream of C2 olefins to the first oligomerization reactor;
  • a second oligomerization reactor arranged to operate at conditions for trimerization, i.e. a trimerization reactor, and which is arranged to receive the third stream of C4-C6 olefins and provide a fifth stream of branched C12-C18 olefins having a Branching Index (Bl), defined as the average number of carbon atoms in the side chains divided by the average number of carbon atoms in the main chain, higher than 0.30;
  • Bl Branching Index
  • a hydrogenation reactor arranged to receive said fifth stream of branched C12-C18 olefins and provide a sixth product stream of branched C12-C18 isoparaffins having a Bl higher than 0.30;
  • a dewaxing reactor arranged to receive the fourth stream of C8+ olefins, such as C8-C20 olefins, optionally arranged to receive a portion of said sixth product stream or branched C12-C18 olefins, as well as hydrogen, the dewaxing reactor comprising a dewaxing catalyst, the dewaxing catalyst comprising: at least one transition metal selected from Ni, Pd, Pt or combinations thereof, and optionally another transition metal, and a zeolite or zeotype or a silica-alumina; the dewaxing reactor further being arranged to provide a seventh product stream of branched C8-C20 isoparaffins having a Bl higher than 0.05;
  • a second separation section arranged to receive the sixth product stream of branched C12-C18 isoparaffins from the hydrogenation reactor and the seventh product stream of branched C8-C20 isoparaffins from the dewaxing reactor and to provide: an eight stream of light end components, and a nineth product stream as synthetic paraffinic kerosene (SPK), and suitably wherein said SPK has: i) a Bl higher than 0.10, and ii) a freezing point below -40°C.
  • a dewaxing reactor i.e. an existing dewaxing reactor, a hydrogenation reactor, and a separation section arranged downstream at least said dewaxing reactor, i.e. an existing separation section; the method of retrofitting comprising:
  • a first oligomerization reactor upstream said dewaxing reactor, in which the first oligomerization reactor is arranged to receive an ethylene stream and at least a portion of a second stream of C2 olefins i.e.
  • the first oligomerization reactor comprising an oligomerization catalyst, said oligomerization catalyst being a homogeneous catalyst comprising: a transition metal compound or complex comprising at least one of Ti, Zr, Cr, Ni, together with an alkyl aluminum compound dissolved in a hydrocarbon solvent or an etheral solvent; or an alkyl aluminum compound dissolved in a hydrocarbon solvent or an etheral solvent, optionally as a co-catalyst; the first oligomerization reactor further being arranged to provide a first stream of linear alfa olefins (LAOs) in the C2- C20 range of which at least 80 wt% having a Schultz-Flory distribution with a chain propagation probability (alpha) of 0.35-0.60, or a Poisson distribution with a chain propagation probability (lambda) of 1.0-4.7;
  • LAOs linear alfa olefins
  • first separation section downstream and in direct fluid communication with said first oligomerization reactor, in which the first separation section is arranged to receive: said first stream of LAOs and provide: said second stream of C2 olefins, a third stream of C4-C6 olefins, and a fourth stream of C8+ olefins, such as C8-C20 olefins;
  • a second oligomerization reactor arranged to operate at conditions for tri- merization, i.e. a trimerization reactor, downstream said first separation section; further, installing a conduit in direct fluid communication between the first separation section and the second oligomerization reactor for supplying said third stream of C4-C6 olefins to the second oligomerization reactor, and in which the second oligomerization is further arranged to provide a fifth stream of branched C12-C18 olefins;
  • HPU hydrogen producing unit
  • Gil gasification unit
  • a method of retrofitting an existing hydroprocessing plant comprising: a dewaxing reactor, a hydrogenation reactor, and a separation section arranged downstream at least said dewaxing reactor; the method of retrofitting comprising the provision of a plant as defined in any of the above plant embodiments, by:
  • a first oligomerization reactor upstream said dewaxing reactor, in which the first oligomerization reactor is arranged to receive an ethylene stream and at least a portion of a second stream of 02 olefins i.e.
  • the first oligomerization reactor comprising an oligomerization catalyst, said oligomerization catalyst being a homogeneous catalyst comprising: a transition metal compound or complex comprising at least one of Ti, Zr, Cr, Ni, together with an alkyl aluminum compound dissolved in a hydrocarbon solvent or an etheral solvent; or an alkyl aluminum compound dissolved in a hydrocarbon solvent or an etheral solvent, optionally as a co-catalyst; the first oligomerization reactor further being arranged to provide a first stream of linear alfa olefins (LAOs) in the C2- C20 range of which at least 80 wt% having a Schultz-Flory distribution with a chain propagation probability (alpha) of 0.35-0.60, or a Poisson distribution with a chain propagation probability (lambda) of 1.0-4.7;
  • LAOs linear alfa olefins
  • first separation section downstream and in direct fluid communication with said first oligomerization reactor, in which the first separation section is arranged to receive: said first stream of LAOs and provide: said second stream of C2 olefins, a third stream of C4-C6 olefins, and a fourth stream of C8+ olefins, such as C8-C20 olefins;
  • a second oligomerization reactor arranged to operate at conditions for tri- merization, i.e. a trimerization reactor, downstream said first separation section; further, installing a conduit in direct fluid communication between the first separation section and the second oligomerization reactor for supplying said third stream of C4-C6 olefins to the second oligomerization reactor, and in which the second oligomerization is further arranged to provide a fifth stream of branched C12-C18 olefins;
  • a conduit in direct fluid communication between the first separation section and the dewaxing reactor which is arranged downstream for supplying said a fourth stream of C8+ olefins, such as C8-C20 olefins, to the dewaxing reactor, and in which the dewaxing reactor is further arranged to provide a seventh product stream of branched C8-C20 isoparaffins;
  • HPU hydrogen producing unit
  • Gil gasification unit
  • the hydrogenation reactor is the existing hydrogenation reactor, i.e. the hydrogenation reactor of the existing hydrocarbon plant, suitably arranged immediately downstream the separation section.
  • the dewaxing reactor is the existing dewaxing reactor, i.e. the dewaxing reactor of the existing hydrocarbon plant.
  • the separation section arranged downstream at least said dewaxing reactor i.e. the separation section of the existing hydrocarbon plant. This separation section corresponds to the second separation section of the process and plant according to the invention.
  • in direct fluid communication means that there are no intermediate units or process steps significantly changing the composition of the stream.
  • in indirect fluid communication means that there are intermediate units or process steps significantly changing the composition of the stream.
  • hydroprocessing plant may be used interchangeably with the term “refinery”.
  • refinery By this method, it is possible to benefit from existing infrastructure of a hydroprocessing plant.
  • the dewaxing and hydrogenation reactors as well as downstream separation section are common in hydroprocessing plants, yet these, in particular the dewaxing reactor are the more costly parts of the units and associated equipment required for the producing of SPK from ethylene.
  • the LAO front-end hence the first oligomerization reactor and first separation section, as well as the second oligomerization reactor are for instance installed at or nearby such hydroprocessing plants; or alternatively, a LAO stream (C8-C20 olefins), and/or the fifth stream from the second oligomerization reactor (branched C12-C18 olefins), are transported to the hydroprocessing plant(s).
  • any of the embodiments and associated benefits of the first aspect of the invention may be used in the second aspect of the invention or the another aspect of the invention, or the yet another aspect of the invention, or vice versa.
  • Fig. 1 is a schematic layout of the process and plant according to an embodiment of the invention.
  • Fig. 2 is a graph showing the product distribution obtained in the first oligomerization step, i.e. the first stream of LAOs, for three different values of alfa, given a Schulz-Flory product distribution.
  • Fig. 3 is a graph showing the product distribution obtained in the first oligomerization step, i.e. the first stream of LAOs, for three different values of lambda, given a Poisson product distribution.
  • Fig. 4 is an example of product distribution from the conversion of n-C18 in a Dewaxing reactor, i.e. the seventh product stream.
  • LAOs linear alpha olefins
  • the LAOs have less than 5 wt%, such as 1 wt% C20+ or such as 0.5 wt% C20+.
  • This distribution is a Schulz-Flory distribution with an alfa-value in the range 0.35-0.60, such as 0.40- 0.54, preferably 0.45 (see Fig.
  • This first product stream 1 is separated, e.g.
  • Bl Branching Index
  • the fifth stream 5 from the second oligomerization reactor 50 comprises at least 75% by weight of highly branched (Bl > 0.30) olefins in the C12-C18 range.
  • This fifth stream 5 is hydrogenated in a hydrogenation reactor 60 to a sixth product stream 6 comprising for instance at least 70 wt% of highly branched isoparaffins in the C12-C18 range.
  • the seventh product stream 7 comprises for instance at least 80 wt% of branched (Bl > 0.05) isoparaffins in the C8-C20 range.
  • the seventh product stream 7 and fourth product stream 4 are fractionated in a second separation section 80 to give a high-boiling nineth product stream 9 as SPK product, having a Bl higher than 0.10 and a eight stream of light end compounds 8, i.e. light end stream.
  • This light end steam comprises low-boiling compounds such as LPG and/or naphtha.
  • This light end stream 8 may also comprise other off-gases and may be used as fuel gas in the process.
  • the light end stream 8 is suitably utilized to generate make-up hydrogen gas in a hydrogen producing unit (not shown) used in the process, such as the hydrogen for dewaxing and hydrogenation. Part of light end stream 8 may also be sold as a separate product such as naphtha. Any excess hydrogen from the dewaxing and hydrogenation reactors 70, 60 is optionally purified by for example a PSA unit in the HPU (not shown) and recycled back to the process.
  • FIG. 4 it is shown a gas chromatogram showing the effluent stream from conversion of n-octadecane with H2 at 3.5 MPa at 340°C over a commercially available noble metal loaded ZSM-48 as dewaxing catalyst.
  • the graph shows the peaks corresponding to the formation of dimethyl n-hexadecane and methyl n-heptade- cane.

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Abstract

L'invention concerne un procédé et une installation de production de produits hydrocarbonés à partir d'éthylène, le procédé consistant à : a) convertir un flux d'éthylène dans un premier réacteur d'oligomérisation par mise en contact dudit flux d'éthylène avec un catalyseur d'oligomérisation, ledit catalyseur d'oligomérisation étant un catalyseur homogène comprenant : un composé ou un complexe de métal de transition comprenant au moins l'un parmi Ti, Zr, Cr, Ni, avec un composé d'aluminium alkyle dissous dans un solvant hydrocarboné ou un solvant éthéré ; ou un composé d'aluminium alkyle dissous dans un solvant hydrocarboné ou un solvant éthéré, éventuellement en tant que co-catalyseur ; afin de produire un premier flux alpha-oléfines linéaires (LAO) dans la plage C2-C20 dont au moins 80 % en poids ont une distribution de Schultz-Flory avec une probabilité de propagation de chaîne (alpha) comprise entre 0,35 et 0,60, ou une distribution de Poisson avec une probabilité de propagation de chaîne (lambda) comprise entre 1,0 et 4,7 ; b -1) séparer ledit premier flux d'alpha-oléfines linéaires dans la plage C2-C20 en un deuxième flux d'oléfines C2, c'est-à-dire un flux d'éthylène (C2=) séparé, un troisième flux d'oléfines C4-C6, et un quatrième flux d'oléfines C8+, telles que des oléfines C8-C20 ; et b -2) recycler au moins une partie du deuxième flux d'oléfines C2 de l'étape b-1) dans le premier réacteur d'oligomérisation ; c-1) convertir le troisième flux d'oléfines C4-C6 de l'étape b-1) dans un deuxième réacteur d'oligomérisation dans des conditions de trimérisation, c'est-à-dire un réacteur de trimérisation, en mettant en contact le troisième flux d'oléfines C4-C6 de l'étape b-1) avec un catalyseur d'oligomérisation, éventuellement un catalyseur d'oligomérisation tel que défini à l'étape a), pour produire un cinquième flux d'oléfines C12-C18 ramifiées ayant un indice de ramification (BI) supérieur à 0,30. Le procédé peut en outre consister à convertir des cinquième et quatrième flux de produits en kérosène paraffinique synthétique (SPK). L'invention concerne également un procédé d'adaptation d'installations d'hydrotraitement existantes.
PCT/EP2024/061722 2023-05-02 2024-04-29 Procédé et installation de production de kérosène paraffinique synthétique en tant que carburéacteur Pending WO2024227724A2 (fr)

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