EP4341363A1 - Procédé de conversion de charges d'alimentation biologiques en distillats moyens avec élimination d'inhibiteur catalytique - Google Patents

Procédé de conversion de charges d'alimentation biologiques en distillats moyens avec élimination d'inhibiteur catalytique

Info

Publication number
EP4341363A1
EP4341363A1 EP22729522.7A EP22729522A EP4341363A1 EP 4341363 A1 EP4341363 A1 EP 4341363A1 EP 22729522 A EP22729522 A EP 22729522A EP 4341363 A1 EP4341363 A1 EP 4341363A1
Authority
EP
European Patent Office
Prior art keywords
oil
isomerization
stream
hydrogen
hydroprocessing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22729522.7A
Other languages
German (de)
English (en)
Inventor
Dominic DEBONIS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Axens SA
Original Assignee
Axens SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Axens SA filed Critical Axens SA
Publication of EP4341363A1 publication Critical patent/EP4341363A1/fr
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/229Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2256/00Main component in the product gas stream after treatment
    • B01D2256/16Hydrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/50Carbon oxides
    • B01D2257/504Carbon dioxide
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to an improved apparatus and methods for removing carbon dioxide during the hydrotreatment and/or hydroprocessing of biological feedstocks in the making of middle distillates.
  • Recent years have been marked by the rapid growth in need of fuels, in particular diesel fuel bases in the European community and also by the importance of the problems related to global warming and the emission of greenhouse gases. The result is a desire to reduce energy dependence on fossil- based raw materials and on reducing C02 emissions.
  • the search for new methods to manufacture fuels from renewable sources that can be easily integrated into the traditional pattern of refining and fuel production is an issue of increasing importance.
  • the integration into the refining process of new products of plant origin resulting from the conversion of lignocellulosic biomass or from the production of vegetable oils or animal fats, has in recent years experienced a growing interest due to the rising cost of fossil fuels.
  • the transesterification reaction utilizes an alcohol such as methanol leading to methyl esters of vegetable oils (VOME) commonly called biodiesel.
  • VOME methyl esters of vegetable oils
  • This path is now widely used in Europe since the production of VOME has increased dramatically in the last ten years, reaching 1.5 Mt in 2003 (the average annual growth rate was 35% between 1992 and 2003).
  • This production is supported in particular by the European directive on the promotion of biofuels (2003/30 / EC), which sets increasing targets for biofuel consumption in the transport sector. These consumptions will have to represent at least 20/0 in 2005, 5,750 / 0 in 2010 and 8% (percentages measured in energy) in 2015 of the global consumption of gasoline and diesel fuel used in transport.
  • Hydrotreating has been used more frequently commercially due to its ability to produce hydrocarbon product with greater stability and ease of blending with hydrocarbons derived from mineral oil.
  • the triglycerides are converted into mainly paraffinic and saturated derivatives, thus constituting excellent hydrocarbon bases for the diesel fuel pool because of their high cetane numbers.
  • hydrogen from a hydrogen plant is fed along with pretreated biological feedstock for hydroprocessing, including a hydrotreatment step and an isomerization step.
  • the biological feedstock generally needs to be pretreated because, contaminants contributing to the presence of trace elements in animal fats and/or plant oils, hinder the ability to catalytically convert these feedstocks to hydrocarbons during hydroprocessing.
  • certain elements and compounds containing these elements e.g., phosphorous, phosphorous-containing compounds, and metals such as calcium and magnesium
  • poison or reduce the activity of hydroprocessing catalysts thereby shortening their useful life and consequently increasing the overall cost of biofuel production.
  • a wide variety of different pretreatment schemes have been reported, each offering different advantages and disadvantages.
  • the hydrotreatment of triglycerides includes several different reactions. In the first reaction, hydrogen is added to saturate the double bonds of the unsaturated vegetable oil triglycerides. In the second reaction, hydrogen is added to remove the propane backbone, hereby converting the saturated vegetable oil triglycerides to fatty acids.
  • the fatty acids either undergo hydrodeoxygenation (by addition of more hydrogen the oxygen leaves as FbO) or decarboxylation (oxygen leaves as CO2 without further addition of hydrogen), or a combination of these two.
  • the result is a mixture of straight chain paraffinic hydrocarbons. Shown below is the reaction pathway for the hydrotreatment process.
  • Decarboxylation The alkane isomerisation and cracking step thereafter brings the biofuel to a quality that equals or surpasses specifications for conventional petroleum fuels.
  • a major drawback of the hydrotreating pathway however is that it requires multiple auxiliary processes to support it; these additional processes increase not only the cost of constructing such a facility, but also increase the energy intensity and by extension the carbon footprint required to make the renewable fuel.
  • One such example is the amine regeneration unit.
  • Amine is often used in current state of the art processes for hydrotreating triglycerides and fatty acids to remove carbon dioxide.
  • a specialty amine is required; most conventional amines either do not readily remove carbon dioxide or result in other operational issues such as severe fouling.
  • the amine regeneration itself also represents an additional investment cost and requires significant energy input.
  • Prior art also suggests conventional pressure-driven membranes can be used to remove carbon dioxide from the hydrotreating section. For these membranes however, the hydrogen rich side is the permeate, resulting in significant pressure losses that require additional compression to be recovered. Pressure-driven membranes then effectively separate hydrogen from hydrocarbon gasses and carbon monoxide, but they do not effectively separate hydrogen gas from carbon dioxide.
  • the present invention provides a method and apparatus for efficiently and effectively removing carbon dioxide from the hydroprocessing reactor section of a biomass feedstock processing facility comprising: a) contacting a biological feedstock with hydrogen gas and a solid catalyst in a hydroprocessing reactor to produce a vapor hydroprocessing effluent stream and a liquid hydroprocessing effluent stream; and b) feeding said vapor hydroprocessing effluent stream to a membrane separator of which the permeability of carbon dioxide is greater than the permeability of hydrogen wherein a substantial portion of the carbon dioxide in said vapor hydroprocessing effluent stream diffuses through said membrane separator to create a permeate stream and wherein a substantial portion of the hydrogen in said vapor hydroprocessing effluent stream remains on the other side of said membrane separator
  • FIG. 1 shows a particular embodiment of Applicant’s scheme for removal of carbon dioxide using a membrane in a renewable middle distillate and/or diesel processing plant.
  • Figure 1 shows a particular embodiment of Applicant’s scheme for removal of carbon dioxide using a membrane in a renewable middle distillate and/or diesel processing plant.
  • the carbon dioxide removal step allows to remove at least 50% of the initial carbon dioxide (in volume), preferably between 50% and 90% of the initial carbon dioxide (in volume), depending on the sizes of the membrane.
  • hydrotreating or hydrotreatment means chemical reactions between the hydrocarbon feedstock and hydrogen including hydrodenitrification, hydrodesulfurization, hydrodeoxygenation, hydrogenolysis, alkene saturation, and olefin saturation; this term will also be used herein to include decarboxylation and decarbonylation, as these reactions occur simultaneously as a competing reaction to hydrogenolysis under the given reaction conditions.
  • hydroprocessing means a process in which the hydrotreatment reactions occur between the hydrocarbon feedstock and hydrogen when contacted with the catalyst bed.
  • the hydroprocessing process may also include, in addition to the catalyst bed(s), one or more of the following: separation of liquid stream(s) and vapor stream(s) downstream of the catalyst bed(s), a recycle gas loop, recycle liquid loop(s). Further, the hydroprocessing process may also include an isomerization and/or hydrocracking step with different catalyst(s) to facilitate isomerization/hydrocracking of paraffinic hydrocarbons.
  • middle distillates means hydrocarbon fuels generally comprising primarily of hydrocarbon components boiling above 150°C including, for example, kerosene, diesel, or gasoil.
  • biological feedstocks means vegetable oils, animal fats, tall oil, and derived material such as fatty acid alkyl esters, or combinations thereof.
  • Vegetable oils include, but are not limited to, rapeseed oil, soybean oil, corn oil, coconut oil, olive oil, linseed oil, sunflower oil, palm oil, jatropha oil, mustard oil, peanut oil, hemp oil, and cottonseed oil.
  • Animal fats include, but are not limited to, pork fat, poultry fat, lard, butter and tallow.
  • light ends or light hydrocarbons means chemical compounds lighter than pentane including methane, ethane, propane, n-butane, or isobutane. Such light hydrocarbons or “light ends” are often used in some hydrocarbon processing schemes as a feedstock and/or as a fuel.
  • LHSV is the liquid hourly space velocity, which is the ratio of liquid volume flow per hour to catalyst volume.
  • LHSV is the liquid hourly space velocity, which is the ratio of liquid volume flow per hour to catalyst volume.
  • a system with a flow rate 2 m 3 /h and lm 3 of catalyst would have an LHSV of 2. (The units are 1/hr).
  • LHSV is inversely proportional to residence time.
  • a biological feedstock (preferably pretreated) 10 is fed along with a hydrogen treat gas 15 to a hydroprocessing reactor section 12 for hydrotreating.
  • the hydrogen treat gas 15 may include a hydrogen feed stream 11 and/or a recycle hydrogen stream 31 from the membrane separation section 30.
  • the hydrogen feed stream 11 and the recycle feed stream 31 may be separately sent to the hy droproces sing reactor section 12 in lieu of being combined and sent as a treat gas stream 15.
  • the hydrogen feed stream 11 may come from any number of sources including Steam Methane Reforming (SMR), Autothermal Reforming, Partial Oxidation or any other hydrogen production technology known to those skilled in the art.
  • SMR Steam Methane Reforming
  • Autothermal Reforming Partial Oxidation
  • any other hydrogen production technology known to those skilled in the art.
  • hydrogen from the treat gas stream 15 is added to saturate the double bonds of the unsaturated vegetable oil triglycerides from the biological feedstock 10 and remove the propane backbone, thereby converting the saturated vegetable oil triglycerides to fatty acids.
  • the fatty acids either undergo hydrodeoxygenation (by addition of more hydrogen the oxygen leaves as FhO) or decarboxylation (oxygen leaves as CO2 without further addition of hydrogen), or a combination of these two.
  • liquid hydroprocessing effluent stream 14 comprising a mixture of paraffinic hydrocarbons and light ends and a vapor hydroprocessing effluent stream 13 comprising carbon dioxide, carbon monoxide, water vapor, hydrogen, and hydrocarbon lightends.
  • This hydroprocessing reactor section 12 utilizes a solid catalyst to catalyze the hydrotreatment reactions.
  • Catalysts known in the art often use metals from group VIII such as nickel or cobalt alone or in combination with metals from group VIB such as molybdenum or tungsten.
  • Catalyst types well known in the art are sulfided forms of NiMo, C0M0, and NiW on an alumina support as well as reduced nickel.
  • the reaction typically operates at reaction temperatures generally between 180 °C and 400 °C, a pressure between 10 bar to 150 bar, and a LHSV of between 0.1 to 10 h "1 .
  • the hydroprocessing reactor section 12 may also include catalyst that allow the straight chain paraffinic hydrocarbons to undergo alkane isomerization and cracking after the hydrotreatment reactions have taken place.
  • the isomerization/cracking catalyst may be present in stage independent of the hydrotreatment reactions or share a common stage with the hydrotreatment reactions.
  • the liquid hydroprocessing effluent stream 14 comprising a mixture of paraffinic hydrocarbons may thereafter be fed to a separation section 20.
  • the optional separation section 20 typically may use a single vessel with multiple stages, such as a distillation column, but may use multiple vessels, particularly if it is desirable to achieve production of multiple hydrocarbon liquid products of varying boiling ranges.
  • the optional separation section 20 is operated at low pressure, and separates the liquid hydroprocessing effluent stream 14 into a hydrocarbon liquid product stream 22 and a vent gas stream 21.
  • the hydrocarbon liquid product stream 22 typically comprises paraffinic hydrocarbons and is thereafter suitable for further processing by any number of methods known to those skilled in the art into saleable products including diesel fuel, kerosene, jet fuel, gas oil, and/or naphtha.
  • the vapor hydroprocessing effluent stream 13 which comprises carbon dioxide, carbon monoxide, water vapor, hydrogen, and hydrocarbon lightends, is thereafter sent to a membrane separation section 30.
  • Carbon dioxide from the vapor hydroprocessing effluent stream 13 then diffuses through the membrane separation section 30 and is concentrated on the permeate side 30a.
  • the permeate stream 32 is then removed from the membrane separation section 30 and may be routed to a fuel gas system to be burned; alternatively, the permeate stream may be sent to a destination wherein any hydrogen gas in the permeate stream 32 may be recovered, such as a PSA. Hydrogen is more favorably kept on the residue side 30b of the membrane separation section 30, to obtain a residue stream 31.
  • the residue stream which comprises hydrogen is sent to the suction of a recycle compressor (not shown); the recycle compressor routs the hydrogen-rich residue stream 31 back to the hydroprocessing reactor section 12 either by itself or in combination with the hydrogen feed stream 11 , wherein the hydrogen is used as a reactant for hydrodeoxygenation, hydrogenation, hydrodesulfurization, and hydrodenitrification.
  • make-up hydrogen may optionally be mixed into the recycle compressor suction if additional compression is required for the stream.
  • the membrane separation section 30 may operate between -20°F and 150°F (i.e. between -29°C and 66°C).
  • the pressure at the process inlet of the feed side may operate between 1,500 psig and 300 psig (i.e. between 10,4 MPa and 2,2 MPa); the permeate side may operate from 500 psig to 0 psig (i.e. between 3,5 MPa and 0,1 MPa), but may preferably operate at a lower pressure than that of the membrane process inlet.
  • a significant advantage of this invention over amine absorption is that it does not require an amine supply in order to function.
  • the invention also offers an advantage over conventional membrane separation because the hydrogen rich side is the membrane residue, substantially reducing the required compression required on the hydrogen rich stream as well as the level of pressure required to facilitate the separation thus saving costs as increased amounts of compression required to a system increases costs substantially. Due to the nature of the membrane separation section 30, the permeate stream 32 may still contain appreciable amounts of hydrogen gas. For this reason, it would be practical to send the permeate stream 32 to a hydrogen recovery system such as a PSA.
  • the permeate stream as feedstock to a hydrogen production process such as a Steam Methane Reformer, to both recapture the hydrogen and convert the lightends to hydrogen, thus reducing the required amount of natural gas feed.
  • a hydrogen production process such as a Steam Methane Reformer
  • Figure 1 is one embodiment of the present invention. Although not shown on Figure 1, there are several other possible configurations of Applicants invention. First, while it is possible to recover any hydrogen in the permeate stream 32 as indicated above, it is still desirable to limit the amount of hydrogen in the permeate stream 32 so that the flowrate of hydrogen sent to the hydrogen recovery section is minimized.
  • the invention described herein has been disclosed in terms of a specific embodiment and application. However, these details are not meant to be limiting and other embodiments, in light of this teaching, would be obvious to persons skilled in the art. Accordingly, it is to be understood that the drawings and descriptions are illustrative of the principles of the invention, and should not be construed to limit the scope thereof.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

L'invention concerne un appareil et des procédés améliorés destinés à éliminer le dioxyde de carbone pendant l'hydrotraitement et/ou le traitement par hydrogène de charges d'alimentation biologiques dans la fabrication de distillats moyens. L'appareil et les procédés améliorés éliminent la nécessité de multiples procédés auxiliaires pour les supporter comprenant, par exemple, une unité de régénération d'amine, ce qui permet de réduire ainsi significativement non seulement le coût de construction d'une telle installation, mais également l'intensité énergétique et par extension l'empreinte carbone nécessaire pour fabriquer le combustible renouvelable.
EP22729522.7A 2021-05-18 2022-05-16 Procédé de conversion de charges d'alimentation biologiques en distillats moyens avec élimination d'inhibiteur catalytique Pending EP4341363A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202117322975A 2021-05-18 2021-05-18
PCT/EP2022/063118 WO2022243212A1 (fr) 2021-05-18 2022-05-16 Procédé de conversion de charges d'alimentation biologiques en distillats moyens avec élimination d'inhibiteur catalytique

Publications (1)

Publication Number Publication Date
EP4341363A1 true EP4341363A1 (fr) 2024-03-27

Family

ID=82019636

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22729522.7A Pending EP4341363A1 (fr) 2021-05-18 2022-05-16 Procédé de conversion de charges d'alimentation biologiques en distillats moyens avec élimination d'inhibiteur catalytique

Country Status (4)

Country Link
EP (1) EP4341363A1 (fr)
CN (1) CN117460806A (fr)
BR (1) BR112023023478A2 (fr)
WO (1) WO2022243212A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI20075794L (fi) * 2007-11-09 2009-05-10 Upm Kymmene Oyj Integroitu prosessi diesel-polttoaineen valmistamiseksi biologisesta materiaalista ja prosessiin liittyvät tuotteet, käyttötavat ja laitteisto
US9399739B2 (en) * 2013-06-13 2016-07-26 Syngag Technology Llc Process for producing distillate fuels from syngas

Also Published As

Publication number Publication date
BR112023023478A2 (pt) 2024-01-30
CN117460806A (zh) 2024-01-26
WO2022243212A1 (fr) 2022-11-24

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