WO2022063995A1 - Procédé de conversion méthanol en oléfine (mto) - Google Patents

Procédé de conversion méthanol en oléfine (mto) Download PDF

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Publication number
WO2022063995A1
WO2022063995A1 PCT/EP2021/076374 EP2021076374W WO2022063995A1 WO 2022063995 A1 WO2022063995 A1 WO 2022063995A1 EP 2021076374 W EP2021076374 W EP 2021076374W WO 2022063995 A1 WO2022063995 A1 WO 2022063995A1
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Prior art keywords
stream
olefins
oxygenates
olefin stream
olefin
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PCT/EP2021/076374
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English (en)
Inventor
Pablo Beato
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Haldor Topsøe A/S
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Publication of WO2022063995A1 publication Critical patent/WO2022063995A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • 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
    • 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
    • C10G2400/22—Higher olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • a feedstock comprising oxygenates such as methanol and/or dimethyl ether
  • SAF sustainable aviation fuel
  • Potential feedstocks for producing SAFs are generally classified as (a) oil-based feedstocks, such as vegetable oils, waste oils, algal oils, and pyrolysis oils; (b) solid-based feedstocks, such as lignocellulosic biomass (including wood products, forestry waste, and agricultural residue) and municipal waste (the organic portion); or (c) gas-based feedstocks, such as biogas and synthesis gas (syngas). Syngas, alcohols, sugars, and bio-oils can be further upgraded to jet fuel via a variety of synthesis, either fermentative or catalytic processes.
  • oil-based feedstocks such as vegetable oils, waste oils, algal oils, and pyrolysis oils
  • solid-based feedstocks such as lignocellulosic biomass (including wood products, forestry waste, and agricultural residue) and municipal waste (the organic portion)
  • gas-based feedstocks such as biogas and synthesis gas (syngas). Syngas, alcohols, sugars, and bio-oils can be further upgraded to
  • US 4,021 ,502, US 4,211 ,640, US 4,22,7992, US 4,433,185, US 4,456,779 disclose process layouts based on classical MTO process conditions, i.e. high temperatures e.g. about 500°C and moderate pressures e.g. about 1-3 bar, in order to obtain efficient conversion of methanol to olefins.
  • high temperatures e.g. about 500°C
  • moderate pressures e.g. about 1-3 bar
  • MOGD Mobil-Olefin-to-Gasoline-Distillates
  • US 9,957,449 discloses a process for the producing hydrocarbons in the jet fuel range by oligomerization of renewable olefins having three to eight carbons.
  • Applicant’s US 20190176136 discloses the use of a ZSM-23 zeolite as catalyst for methanol to olefin conversion in a process step which is conducted at atmospheric pressure (about 1 bar) and 400°C, thereby producing a hydrocarbon stream with, less than 5wt% aromatics.
  • US 2002/0103406 A1 discloses a process for making olefin dimer and oligomer product using a nickel-based oligomerization catalyst and using as feed an olefin containing stream from an oxygenated to olefin process.
  • US 2018155637 A1 discloses a process for producing an olefin stream from an oxygenate feedstock over a ZSM-5 catalyst at a pressure of 10-180 psig (0.7-12.4 barg) and a temperature of 440-550°C.
  • a gas phase portion of the olefin stream is separated as light paraffins and light olefins (C4- compounds) and passed to an oligomerization reactor.
  • This citation relates therefore to MTO operation at high temperatures, i.e. about 450°C with C2+C3 olefin yields of at least 50%.
  • a portion of said gas phase (C4- compounds) may be recycled to the MTO reactor.
  • US 8,524,970 discloses a process for producing diesel of better quality, i.e. diesel with a higher cetane number comprising conversion of oxygenates to olefins, oligomerization of olefins and subsequent hydrogenation. More specifically, this citation discloses a similar process in which methanol is first converted to dimethyl ether and which is passed over a ZSM-5 catalyst at a pressure of 2-10 bar and temperature of 300-600°C. The gas phase portion of the resulting product stream is separated as C6-hydrocar- bons and fed to an oligomerization reactor and finally to a hydrogenation reactor. This citation focus therefore also on C2 to C8 olefins, in particular the higher olefins up to C8-olefins by increasing pressure.
  • MTO methanol to olefins
  • OU means oligomerization
  • Hydro means hydrogenation
  • Hydro/OLI means a single combined step comprising hydrogenation and oligomerization.
  • MTO overall process
  • OLI overall process and plant
  • jet fuel and “hydrocarbons boiling in the jet fuel range” are used interchangeably and have the meaning of a mixture of C8-C16 hydrocarbons boiling in the range of about 130-300° at atmospheric pressure.
  • SAF sustainable aviation fuel or aviation turbine fuel, in compliance with ASTM D7566 and ASTM D4054.
  • olefin stream means a hydrocarbon stream rich in olefins comprising higher and lower olefins, and optionally also aromatics, paraffins, iso-paraffins and naphthenes, and in which the combined content of higher and lower olefins is at least 25 wt%, such as 30 wt% or 50 wt%.
  • the term “high content of higher olefins” means that the weight ratio in the olefin stream of higher olefins to lower olefins is above 1 , for instance 2-4.
  • the term “low content of higher olefins” means that the weight ratio in the olefin stream of higher olefins to lower olefins is 1 or below.
  • selectivity to higher olefins means the weight ratio of higher to lower olefins. “High selectivity to higher olefins” or “higher selectivity to higher olefins” means a weight ratio of higher to lower olefins of above 1.
  • the term is also used interchangeably with the term “light paraffins”.
  • substantially free of aromatics means less than 10 wt% aromatics in an olefin stream, in particular less than 5 wt%, or even less than 1 wt%.
  • partial conversion of the oxygenates or “partly converting the oxygenates” means a conversion of the oxygenates of 20-80%, for instance 40-80%, or 50-70%.
  • the term “full conversion of the oxygenates” or “fully converting the oxygenates” means above 80% conversion of the oxygenates, for instance 90% or 100%.
  • the term “substantial methanol conversion” is used interchangeably with the term “full conversion of the oxygenates”, where the oxygenate is methanol.
  • catalyst comprising a zeolite and “zeolite catalyst” are used interchangeably.
  • MTO methanol to olefins
  • It is yet another object of the present invention to provide a process for the conversion of oxygenates with a low content of C2-light fraction, in particular C2 (ethylene), while at the same time being able to reduce the temperature of the MTO and increase the catalyst lifetime.
  • a process for producing an olefin stream comprising passing a feedstock stream comprising oxygenates over a catalyst active in the conversion of oxygenates, in which the catalyst comprises a zeolite with a framework having a 10-ring pore structure, in which said 10-ring pore structure comprises a three-dimensional (3-D) pore structure, such as MFI, at a pressure of 1-50 bar and a temperature of 150-480°C.
  • a catalyst active in the conversion of oxygenates in which the catalyst comprises a zeolite with a framework having a 10-ring pore structure, in which said 10-ring pore structure comprises a three-dimensional (3-D) pore structure, such as MFI, at a pressure of 1-50 bar and a temperature of 150-480°C.
  • the present invention provides a process for producing an olefin stream, said process comprising passing a feedstock stream comprising oxygenates over a catalyst active in the conversion of oxygenates, in which the catalyst comprises a zeolite with a framework having a 10-ring pore structure, in which said 10-ring pore structure comprises a three-dimensional (3-D) pore structure, such as MFI, wherein the pressure is 2-20 bar for instance 5-10 bar, and the temperature is 150-350°C, for instance 200-300°C, or 250-350°C; or the pressure is 2-30 bar, for instance 2-20 bar or 5-10 bar, and the temperature is 340-400°C, for instance 340-385°C or 360-380°C, and wherein an olefin stream comprising C2-C3 olefins is withdrawn from said olefin stream and used as additional feed stream.
  • the catalyst comprises a zeolite with a framework having a 10-ring pore structure, in which said 10-ring pore structure comprises a three-
  • the pressure may be 2-30 bar and the temperature 150-400°C.
  • the pressure is suitably 2-20 bar, such as 5-10 bar; or 2-30 bar, such as 2-20 bar.
  • the temperature is suitably 150-350°C, such as 200-300°C or 250-350°C; or 340-400°C, for instance 340- 385°C or 360-380°C.
  • a zeolite with a framework having a 10-ring pore structure means a pore circumference defined by 10 oxygens.
  • a 3-D pore structure means zeolites containing intersecting pores that are substantially parallel to all three axes of the crystal.
  • the pores preferably extend through the zeolite crystal.
  • the three letter code, e.g. MFI, for structure types are assigned and maintained by the International Zeolite Association Structure Commission in the Atlas of Zeolite Framework Types, which is at http:// www.iza-structure.org/databases/ or for instance also as defined in “Atlas of Zeolite Framework Types”, by Ch. Baerlocher, L.B. McCusker and D.H. Olson, Sixth Revised Edition 2007.
  • temperature means the MTO reaction temperature in an isothermal process, or the inlet temperature to the MTO in an adiabatic process.
  • the catalyst may be formed by combining the zeolite with a binder, and then forming the catalyst into pellets.
  • the pellets may optionally be treated with a phosphoric reagent to create a zeolite having a phosphorous component between 0.5 and 15 wt % of the treated catalyst.
  • the binder is used to confer hardness and strength on the catalyst. Binders include alumina, aluminum phosphate, silica, silica-alumina, zirconia, titania and combinations of these metal oxides, and other refractory oxides, and clays such as montmorillonite, kaolin, palygorskite, smectite and attapulgite.
  • a preferred binder is an aluminum-based binder, such as alumina, aluminum phosphate, silica-alumina and clays.
  • the catalysts are active in not only suppressing the formation of aromatics, but also in providing a high selectivity for higher olefins as well as full conversion.
  • reaction temperatures i.e. reaction temperatures of 150-480°C, in particular 340-400°C; more particularly 360°C or below, or 350°C or below, as recited above; the catalysts are active in not only suppressing the formation of aromatics, but also in providing a high selectivity for higher olefins as well as full conversion.
  • 340-400°C a significant increase in higher olefins is observed as well as a sharp decrease in aromatics content, while still fully converting the oxygenates, e.g. methanol.
  • the above combination of features enables the production of an olefin stream which is an ideal oligomerization feed for the further conversion to jet fuel, particularly SAF in accordance with ASTM as defined above.
  • a suitable oligomerization feed may have some aromatics, for instance 10-20 wt% aromatics, as well as higher and lower olefins
  • the ideal oligomerization feed is namely substantially free of aromatics and composed of higher olefins, and preferably as little as possible C2- light fraction.
  • the olefin stream may comprise at least 20 wt% C4-C8 olefins, such as above 30 wt% C4-C8 olefins and less than 10 wt% aromatics.
  • the oligomerization feed complies with the above ASTM requirements stipulating the 50% SAF blending part to be almost aromatic-free, more specifically that the content of aromatics be limited to below 0.5 wt%.
  • the olefin stream can be converted into such jet fuel via oligomerization and hydrogenation in a more efficient overall process due to i.a. less recycling and higher oligomerization yields.
  • the higher olefins and low selectivity to aromatics simplifies separation steps and increase overall yields of the jet fuel.
  • the pressure is increased, and the temperature lowered, resulting in that it is still possible to maintain substantial methanol conversion whilst at the same time achieving an olefin stream substantially free of aromatics and having a high content of higher olefins.
  • an olefin stream comprising C2-C3 olefins is withdrawn from said olefin stream and used (recycled) as additional feed stream, e.g. by combining with the feedstock stream comprising oxygenates.
  • concentration of higher olefins in the olefin stream is further increased while also having full utilization of the less desired lower olefins for conversion into higher olefins.
  • Any undesired cracking of higher olefins in the process is contained by recycling products of such cracking, namely C2- C3 olefins, back to the feed.
  • this recycle further provides a dilution effect on the feedstock stream, since light paraffins may be recycled, including methane, thereby enabling better control of the exothermicity during the conversion to olefins.
  • the present invention enables the production of an olefin stream with almost no C2-light fraction, in particular ethylene, and that the C2-light fraction, again particularly ethylene, will be recycled with part of the C3 fraction, particularly C3-olefin, thus said C2-C3 olefins, to the MTO to further reduce the operating temperature therein and with that also reduce the yields of ethylene and increase the lifetime.
  • the feed for the oligomerization step is then virtually free from C2 olefins.
  • the feedstock stream may be combined with a diluent, i. an inert diluent, such as nitrogen or carbon dioxide or a light paraffin such as methane, thereby reducing the exothermicity in the conversion to olefins, which is particularly preferred when the catalyst is arranged as a fixed bed.
  • a diluent i. an inert diluent, such as nitrogen or carbon dioxide or a light paraffin such as methane
  • the feedstock stream is diluted with e.g. nitrogen so that the methanol concentration in the feedstock is 2-20 vol.%, preferably 5-10 vol. %.
  • said 3-D pore structure is MFI, such as MFI modified with an alkaline earth metal, for instance a Ca/Mg-modified ZSM-5, in particular a Ca-modified ZSM-5.
  • Ca/Mg-modified ZSM-5 means a ZSM-5 modified with Ca and/or Mg.
  • the catalysts may be prepared by standard methods in the art. For instance, Ca and/or Mg are loaded in a commercially available ZSM-5 zeolite at concentrations of 1- 10 wt.%, such as 2, 4 or 6 wt.%, by ion-exchange e.g. solid-state ion-exchange; or wet impregnation e.g. incipient wetness impregnation or any other suitable impregnation.
  • ion-exchange e.g. solid-state ion-exchange
  • wet impregnation e.g. incipient wetness impregnation or any other suitable impregnation.
  • impregnation of the final catalyst with binder/matrix such as in a catalyst that contains up to 30-90 wt% zeolite such as 50-80 wt% zeolite in a matrix/binder comprising an alumina component such as a silica-alumina matrix binder.
  • the catalyst is 60 wt% zeolite and 40 wt% alumina.
  • the wt% of zeolite in the binder means the wt% of the zeolite with respect to the catalyst weight, in which the catalyst comprises the zeolite and the binder.
  • the term “binder” is also referred to as “matrix binder” or “matrix/binder” or “binder/matrix”.
  • the weight hour space velocity (WHSV) is 0.5-12 h’ 1 , such as 1.5-10, or 4-10, for instance 6, 8, or 10 h’ 1 .
  • WHSV weight hour space velocity
  • oxygenate conversion e.g. methanol conversion
  • the feedstock stream comprising oxygenates is derived from one or more oxygenates taken from the group consisting of triglycerides, fatty acids, resin acids, ketones, aldehydes or alcohols or ethers, where said oxygenates originate from one or more of a biological source, a gasification process, a pyrolysis process, Fischer- Tropsch synthesis, or methanol-based synthesis.
  • said one or more oxygenates are hydroprocessed oxygenates.
  • hydroprocessed oxygenates is meant oxygenates such as esters and fatty acids derived from hydroprocessing steps such as hydrotreating and hydrocracking.
  • the oxygenates are selected from methanol (MeOH), dimethyl ether (DME), or combinations thereof. These are particularly advantageous oxygenate feedstocks, as these are widely commercially available.
  • DME is more reactive than methanol and thus enables running the MTO step at lower temperatures, thereby increasing the selectivity for higher olefins.
  • conversion of DME releases only half the amount of water (steam) compared to methanol, thereby reducing the rate of (irreversible) deactivation due to steam-dealumination of the zeolite catalyst.
  • the methanol is made from synthesis gas prepared by using electricity from renewable sources such as wind or solar energy, e.g. eMethanolTM.
  • the synthesis gas is prepared by combining air separation, autothermal reforming or partial oxidation, and electrolysis of water, as disclosed in Applicant’s WO 2019/020513 A1, or from a synthesis gas produced via electrically heated reforming as for instance disclosed in Applicant’s WO 2019/228797.
  • methanol can be produced from many primary resources (including biomass and waste), in times of low wind and solar electricity costs, the production of e-methanolTM enables a sustainable front-end solution.
  • the process of the invention further comprises, prior to passing the feedstock stream comprising oxygenates over a catalyst active in the conversion of oxygenates, in which the feedstock comprising oxygenates is a methanol stream i.e. methanol feed stream: producing said methanol feed stream by methanol synthesis of a methanol synthesis gas, wherein the methanol synthesis gas is generated by: steam reforming of a hydrocarbon feed such as natural gas, and/or at least partly by electrolysis of water and/or steam.
  • the methanol feed stream is produced from methanol synthesis gas which is generated by combining the use of water electrolysis in an alkaline or PEM electrolysis unit, or steam in a solid oxide electrolysis cell (SOEC) unit, thereby generating a hydrogen stream, together with the use of a CO2- rich stream in a SOEC unit for generating a stream comprising carbon monoxide and carbon dioxide, then combining the hydrogen stream and the stream comprising carbon monoxide and carbon dioxide for generating said methanol synthesis gas, as e.g. disclosed in Applicant’s co-pending European patent application No. 20216617.9.
  • the methanol synthesis gas is then converted into the methanol feed stream via a methanol synthesis reactor, as is well-known in the art.
  • process may also encompass the prior (front-end) production of the methanol feed stream, as recited above.
  • the process is conducted under the presence of hydrogen.
  • the hydrogen improves the methanol conversion by at least slightly decreasing the rate of deactivation of the catalyst, thereby increasing catalyst lifetime. Yet, when conducting the process, there is no addition of hydrogen, since this conveys a risk of hydrogenating some olefins and thereby decrease the olefin yield.
  • the catalyst is arranged as a fixed bed.
  • the process comprises: using a first reactor set including a single reactor or several reactors, preferably mutually arranged in parallel, for the partial or full conversion of the oxygenates.
  • a first reactor set including a single reactor or several reactors, preferably mutually arranged in parallel, for the partial or full conversion of the oxygenates.
  • the process further comprises using a second reactor set including a single reactor or several reactors, preferably mutually arranged in parallel, for the further conversion of the oxygenates, and a phase separation stage in between the first reactor set and the second reactor set for thereby forming the olefin stream.
  • the term “using a first reactor set” means passing the feedstock comprising oxygenates through the first reactor set.
  • using a second reactor set means passing the feedstock or a portion thereof through the second reactor set after the partial or full conversion of the oxygenates and passage through the separation stage.
  • the entire feedstock stream passes through the first reactor set, i.e. there is no substantial splitting of the feedstock stream.
  • the term “entire feedstock” means at least 90 wt% of the feedstock.
  • the process comprises:
  • the feedstock stream comprising oxygenates through the first reactor set under conditions for partly converting, e.g. 40-80% such as 60-70% conversion, the oxygenates, thereby forming a raw olefin stream comprising unconverted oxygenates and C2-C8 olefins, e.g. the raw olefin stream may comprise water, methanol and C2-C8 olefins;
  • a first olefin stream which is rich in lower olefins, particularly C2-C3 olefins
  • a separated oxygenate stream comprising the unconverted oxygenates, e.g. the separated oxygenate stream may comprise water and methanol
  • a second olefin stream which is rich in higher olefins, particularly C4-C8 olefins
  • the first reactor and second reactor set use a catalyst having a three-dimensional (3-D) pore structure, such as MFI.
  • a catalyst having a three-dimensional (3-D) pore structure such as MFI.
  • the recycle of C2-C3 olefins as a co-feed may also be conducted.
  • the process further comprises recycling a portion of the olefin stream, i.e. the olefin product stream from the second reactor set, to said combined stream comprising lower olefins and the unconverted oxygenates and which is fed to the second reactor set, said portion of the olefin stream preferably being an olefin stream comprising C2- C3 olefins, more preferably a C3-olefin stream, which is withdrawn from said olefin stream.
  • the same associated benefits recited above in connection with the recycling C2-C3 olefins are also obtained.
  • the first reactor set consists of 2-4 reactors, such as 3 reactors
  • the second reactor set consists of 1-3 reactors, such as 2 reactors.
  • the reactors are preferably mutually arranged in parallel.
  • normally several reactors are run in parallel, e.g. five (5) reactors.
  • the present invention it is possible to replace the 5 reactors in parallel by for instance the first reactor set consisting of three reactors, and the second reactor set consisting of two reactors. Thereby it is possible to run at full conversion by operating the first three reactors at e.g. only 70% conversion, and then further convert the unconverted oxygenates, e.g.
  • first reactor set and second reactor set are arranged in series.
  • a reactor in the first reactor set and second reactor set operates at 2-30 bar, such as 5-15 bar, and at 150-480°C such as 150-350°C or 200-300°C.
  • the weight hour space velocity (WHSV) is 0.5-12 h-
  • the weight hour space velocity (WHSV) in the first reactor set is higher than in the second reactor set.
  • the WHSV is suitably 3 IT 1 or 6h' 1 while in the second reactor set where full conversion is intended the WHSV is suitably 2 h’ 1 .
  • the process further comprises: passing at least a portion of the olefin stream trough an oligomerization step over an oligomerization catalyst, and optionally subsequently conducting a separation step, for thereby producing an oligomerized stream.
  • the entire olefin stream passes through the oligomerization step, preferably after said olefin stream comprising C2-C3 olefins is withdrawn from the olefin stream.
  • the term “entire olefin stream” means at least 90 wt% of the stream.
  • the olefin stream e.g. the entire olefin stream
  • the oligomerization step i.e. the olefin stream is in direct fluid communication with the oligomerization step, or combined oligomerization and hydrogen step, as explained farther below.
  • the oligomerization step is preferably conducted by conventional methods including the use of an oligomerization catalyst such as solid phosphoric acid (“SPA”), ion-ex- change resins or a zeolite catalyst, for instance a conventional *MRE, BEA, FAU, MTT, TON, MFI and MTW catalyst, at a pressure of 30-100 bar, such as 50-100 bar, and a temperature of 100-350°C.
  • SPA solid phosphoric acid
  • BEA FAU
  • MTT ion-ex- change resins
  • a zeolite catalyst for instance a conventional *MRE, BEA, FAU, MTT, TON, MFI and MTW catalyst
  • the products from the oligomerization reaction may be subsequently separated in the separation step, such as distillation, thereby withdrawing a lighter hydrocarbon stream such as naphtha, which comprises C5-C7 hydrocarbons, and the oligomerized stream, which comprises C8+ hydrocarbons.
  • the process further comprises: passing at least a portion of the oligomerized stream through a hydrogenation step over a hydrogenation catalyst, and optionally subsequently conducting a separation step, for thereby producing a hydrocarbon stream comprising hydrocarbons boiling in the jet fuel range.
  • the hydrogenation step is preferably conducted by conventional methods, including under the presence of hydrogen the use of a hydrotreating or hydrogenation catalyst, for instance a catalyst comprising one or more metals, e.g. Pd, Rh, Ru, Pt, Ir, Re, Co, Mo, Ni, W or combinations thereof, at a pressure of 60-70 bar and a temperature of 50- 350°C.
  • a hydrotreating or hydrogenation catalyst for instance a catalyst comprising one or more metals, e.g. Pd, Rh, Ru, Pt, Ir, Re, Co, Mo, Ni, W or combinations thereof, at a pressure of 60-70 bar and a temperature of 50- 350°C.
  • the C8+ hydrocarbons of the oligomerized stream are thereby saturated to form the corresponding paraffins.
  • These may be subsequently separated in a separation step, for instance a distillation step, whereby any hydrocarbons boiling in the diesel range are withdrawn and thereby separated from the hydrocarbons boiling in the jet fuel range i.
  • the entire oligomerized stream passes through the hydrogenation step.
  • the term “entire oligomerized stream” means at least 90 wt% of the stream.
  • the hydrocarbon stream comprising hydrocarbons boiling in the jet fuel range is SAF, i.e. a sustainable aviation fuel in compliance with ASTM D7566 and ASTM D4054.
  • the oligomerization step and hydrogenation step are combined in a single hydro-oligomerization step (Hydro-OLI), e.g. by combining the steps in a single reactor.
  • Hydro-OLI hydro-oligomerization step
  • the oligomerization step and hydrogenation step are combined in a single hydro-oligomerization step, e.g. by combining the steps in a single reactor.
  • single hydro-oligomerization step or more generally “single step” or “single stage” means a section of the process in which no stream is withdrawn. Typically, a single stage does not include equipment such as compressors, by which the pressure is increased.
  • the oligomerization step is dimerization, optionally also trimerization, i.e. by conducting the oligomerization at conditions suitable for dimerization and/or trimerization.
  • the single reactor is preferably operated at a relatively low pressure, such as 15-60 bar, for instance 20-40 bar.
  • the oligomerization reaction is very exothermic per oligomerization step and much less heat is produced, ,- since there is only dimerization, optionally also trimerization -, instead of higher oligomerization.
  • the lower heat produced favors approaching equilibrium, i.e. higher conversion of olefins.
  • the oligomerization step converts the olefins to a mixture of mainly dimers, trimers and tetramers; for instance, a C6-olefin will result in a mixture comprising C12, C18, C24 products and probably also higher hydrocarbons.
  • a more selective and direct conversion of the higher olefins (C4-C8 olefins) to the jet fuel relevant hydrocarbons, namely C8-C16 is obtained.
  • the dimerization and optional trimerization step comprises the use of lower pressures than in conventional oligomerization processes, thereby also reducing compression requirements which translates into higher energy efficiency as well as reduced costs, e.g. reduced costs of the oligomerization reactor and attendant equipment, as well as reduced operating costs due to less need of separating C16+ olefins otherwise formed in conventional OLI reactors. Accordingly, the pressure of the Hydro/OLI can be adapted to better match the pressure of the previous oxygenate conversion step.
  • the hydrogenation or ⁇ -addition is conducted in the same reactor, for instance by adjusting the activity of the hydrogenation component e.g. nickel.
  • the single hydro-oligomerization step is conducted in a single reactor having a stacked reactor bed where a first bed comprises an oligomerization catalyst, e.g. zeolite catalyst, and a subsequent bed comprises a hydrogenation catalyst.
  • the hydro-oligomerization step is conducted by reacting, under the presence of hydrogen, the olefin stream over a catalyst comprising a zeolite and a hydrogenation metal, such as a hydrogenation metal selected from Pd, Rh, Ru, Pt, Ir, Re, Co, Cu, Mo, Ni, W and combinations thereof, and preferably at a pressure of 15-60 bar such as 20-40 bar, and a temperature of 50-350°C, such as 100- 250°C.
  • a hydrogenation metal selected from Pd, Rh, Ru, Pt, Ir, Re, Co, Cu, Mo, Ni, W and combinations thereof, and preferably at a pressure of 15-60 bar such as 20-40 bar, and a temperature of 50-350°C, such as 100- 250°C.
  • the catalyst comprises a zeolite having a structure selected from MFI, MEL, SZR, SVR, ITH, IMF, TUN, FER, EUO, MSE, *MRE, MWW, TON, MTT, FAU, AFO, AEL, and combinations thereof, preferably a zeolite with a framework having a 10-ring pore structure i.e. pore circumference defined by 10 oxygens, such as zeolites having a structure selected from TON, MTT, MFI, *MRE, MEL, AFO, AEL, EUO, FER, and combinations thereof.
  • zeolites are particularly suitable due to the restricted space of the zeolite pores, thereby enabling that the dimerization is favored over larger molecules.
  • the weight hour space velocity (WHSV) is 0.5-6 h’ 1 , such as 0.5-4 h’ 1 .
  • Lower pressures corresponding to the operating at conditions for dimerization are in particular 15-50 bar, such as 20-40 bar. This, again, is significantly lower than the pressures normally used in oligomerization, which typically are in the range 50-100 bar.
  • catalysts comprising NiW, for instance sulfide NiW (NiWS), or Ni such as Ni supported on a zeolite having a FAU or MTT structure, for instance a Y-zeolite, or ZSM-23.
  • NiW sulfide NiW
  • Ni such as Ni supported on a zeolite having a FAU or MTT structure, for instance a Y-zeolite, or ZSM-23.
  • the catalyst which is active for oligomerization and hydrogenation may for instance contain up to 50-80 wt% zeolite in a matrix/binder comprising an alumina component.
  • the hydrogenation metal may then be incorporated by impregnation on the catalyst.
  • the hydrogenation metals are selected so as to provide a moderate activity and thereby better control of the exothermicity of the oligomerization step by mainly hydrogenating the dimers being formed as the oligomerization takes place, thereby interrupting the formation of higher oligomers.
  • the present invention enables in a single hydro-oligomerization step the use of less equipment e.g. one single reactor, one type of catalyst, optionally a single separation stage downstream for obtaining the jet fuel.
  • a stream comprising C8-hydrocarbons resulting from cracked COCI 6 hydrocarbons is withdrawn from said hydrocarbon stream comprising hydrocarbons boiling in the jet fuel range and added to other processes.
  • the process according to the first aspect of the invention cooperates with a refinery plant (or process), in particular a bio-refinery, and the stream comprising C8-hydrocarbons is added to the gasoline pool in a separate process for producing gasoline of said refinery.
  • a stream comprising C8- hydrocarbons resulting from cracked C9-C16 hydrocarbons is withdrawn from said hydrocarbon stream comprising hydrocarbons boiling in the jet fuel range and used (recycled) as additional feed stream to the oligomerization step or the single hydro-oligomerization step.
  • Fig. 1 is a simplified figure showing the conversion of oxygenates to olefins and optional further conversion to jet fuel in accordance with an embodiment of the invention.
  • Fig. 2 is a simplified figure showing a particular embodiment of the invention for the conversion a feedstock comprising oxygenates to olefins and optional further conversion to jet fuel.
  • Fig. 3 shows plots of methanol conversion (upper chart) and aromatics content (lower chart) in the olefin stream as a function of the temperature in degrees Celsius.
  • Fig. 4 shows plots of weight ratio of higher olefins to lower olefins (upper chart) and the weight content of higher olefins in the olefin stream as a function of the temperature in degrees Celsius.
  • a feedstock comprising oxygenates 100 such as methanol and/or DME
  • oxygenates 100 such as methanol and/or DME
  • an optional hydrogen stream 102 and an olefin stream 104 comprising C2-C3 olefins which is withdrawn from the olefin stream 106 formed in oxygenate conversion section 200.
  • the oxygenate conversion section 200 for instance a MTO section, converts the oxygenates over a zeolite catalyst such as Ca-modified-ZSM-5 at e.g. 5-15 bar and 150-350°C or 340-400°C.
  • This further conversion is conducted in downstream oligomerization and hydrogenation section 300, which preferably is combined as a single hydro-oligomerization step, for instance in a single reactor.
  • the olefin stream 106 suitably after removing its water content, is mixed with optional oligomerization olefin stream 110 comprising C8- hydrocarbons and resulting from cracked C9-C16 hydrocarbons withdrawn from said hydrocarbon stream 112 comprising hydrocarbons boiling in the jet fuel range.
  • the resulting mixed stream is then directed to section 300 and converted, under the presence of hydrogen being fed as stream 108, over a catalyst such as Ni supported on a zeolite having a FAU or MTT structure, for instance Y-zeolite, or ZSM-23, at e.g.
  • the single reactor in section 300 operates such that the oligomerization is dimerization and at the same time there is hydrogenation activity. Due to the higher olefins and low aromatics of the olefin stream 106, the hydrocarbons in stream 112 boiling in the jet fuel range i.e. jet fuel, can be used as SAF.
  • a feedstock stream 100 comprising oxygenates such as methanol and/or DME passes through a first reactor set 200’, for instance three reactors arranged in parallel, for thereby achieving 50-70% conversion of the methanol and producing a raw olefin stream 105 comprising water, methanol and C2-C8 olefins.
  • the raw olefin stream 105 is subjected to separation in 3-phase separator 200” thereby producing a first olefin stream 105a, which is rich in lower olefins, particularly C2-C3 olefins, a separated oxygenate stream 105b comprising the unconverted oxygenates, e.g.
  • the first olefin stream 105a is combined with the separated oxygenate stream 105b comprising the unconverted oxygenates, thereby forming a combined stream 105d comprising lower olefins, particularly C2-C3 olefins, and the unconverted oxygenates.
  • This combined stream is pressurized and fed to a second reactor set 200”’ arranged downstream, and which may for instance include two reactors arranged in parallel, for thereby achieving full conversion e.g.
  • the first reactor set 200’ and second reactor set 200’” are thereby arranged in series.
  • a third olefin stream 105e is produced which is rich in higher olefins, particularly C4-C8 olefins.
  • the second olefin stream 105c (bypass stream) is combined with the third olefin stream 105e, thereby forming said olefin stream 106 which may have been pressurized.
  • the resulting olefin stream 106 is optionally further converted (as shown by the stippled lines) to the hydrocarbon stream 112 comprising hydrocarbons boiling in the jet fuel range (C8-C16), particularly SAF, as explained in connection with Fig. 1.
  • zeolite catalyst load 250 mg cat/250 mg SiC
  • pressure 10 barg
  • space velocity (WHSV) 4 h’ 1
  • total flow 7.0 NL/h (117 mL/min)
  • the temperature used is in the range 320-480°C, with tests running in the order 480-440-400-360-320°C, and subsequently in reverse order in order to evaluate the effect of any catalyst deactivation.
  • pressures are in barg, i.e. absolute pressure minus atmospheric pressure.
  • Fig. 3 shows in the upper chart the methanol conversion as a function of the temperature. It is observed, that already at 340°C, there is 90% or more conversion, and at 360°C, there is 100% conversion. Aromatics are formed, as shown in the lower chart of Fig. 3, the level of which increases with temperature, yet there is low selectivity towards formation of aromatics, which are maintained at a low level of about 10 wt% and below 10 wt% throughout or even well below 5 wt% at about 350°C or lower temperatures.
  • Fig. 4 shows in the upper chart the selectivity (OH/OL) towards higher olefins as a function of the temperature.
  • the curves, as the temperature is changed from 480°C to 320°C (squares, OH/OL'k) and from 320 to 480°C (triangles, OH/OL ⁇ ) are indistinguishable in the upper chart. It is observed, that there is a significant increase in the ratio of higher to lower olefins as the temperature is decreased and particularly in the range 340-400°C. While at 450 or 500°C the ratio is about 1 or below, at 400°C the ratio is already above 2 and at about 350°C close to 3.
  • the concentration of higher olefins C4+ (04+) is observed to increase as the temperature is lowered.
  • the content of higher olefins is significantly higher than the level achieved at 450°C or 500°C, and at about 360°C or 350°C a maximum is obtained, with a higher olefins C4+ (04+) content close to 25 wt%.

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Abstract

L'invention concerne un procédé de production d'un flux d'oléfine, ledit procédé comprenant le passage d'un flux de charge d'alimentation comprenant des composés oxygénés sur un catalyseur comprenant une zéolite qui a une structure ayant une structure de pores à 10 cycles, ladite structure de pores à 10 cycles comprenant une structure de pores en trois dimensions (3-D), telle que MFI, la pression étant de 2 à 20 bars et la température étant de 150 à 350 °C ; ou la pression est de 2 à 30 bars et la température est de 340 à 400 °C, et un flux d'oléfine comprenant des oléfines en C2-C3 est retiré dudit flux d'oléfine et utilisé en tant que flux d'alimentation supplémentaire. Le flux d'oléfine peut être converti en carburéacteur, en particulier un carburéacteur durable (SAF) par oligomérisation et hydrogénation supplémentaires.
PCT/EP2021/076374 2020-09-25 2021-09-24 Procédé de conversion méthanol en oléfine (mto) WO2022063995A1 (fr)

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