EP4638662A1 - Procédé de stabilisation d'huiles riches en azote - Google Patents

Procédé de stabilisation d'huiles riches en azote

Info

Publication number
EP4638662A1
EP4638662A1 EP23836859.1A EP23836859A EP4638662A1 EP 4638662 A1 EP4638662 A1 EP 4638662A1 EP 23836859 A EP23836859 A EP 23836859A EP 4638662 A1 EP4638662 A1 EP 4638662A1
Authority
EP
European Patent Office
Prior art keywords
oil stream
liquid oil
process according
pyrolysis
catalyst
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
EP23836859.1A
Other languages
German (de)
English (en)
Inventor
Magnus Zingler STUMMANN
Christian Ejersbo STREBEL
Jens Anders Hansen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of EP4638662A1 publication Critical patent/EP4638662A1/fr
Pending legal-status Critical Current

Links

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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/002—Apparatus for fixed bed hydrotreatment processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Definitions

  • the present invention relates to a process for hydrotreating a nitrogen rich liquid oil stream by, in a continuous operation in a fixed bed reactor, reacting the nitrogen rich liquid oil stream with hydrogen in the presence of catalyst at a temperature of 80-250°C, a pressure of 10-200 barg, a liquid hourly space velocity (LHSV) of 0.1 - 6 h’ 1 , thereby forming a stabilized liquid oil stream.
  • LHSV liquid hourly space velocity
  • renewable feedstocks have been attracting a great deal of attention, not only in Europe, but also US and China.
  • Using renewable feedstocks enables a sustainable approach to the production of hydrocarbon products for use as transportation fuel, in particular any of marine fuel, diesel, jet fuel and naphtha as well as for use as petrochemical raw materials, such as steam cracker feeds.
  • Oils derived from nitrogen rich feedstocks such as sewage sludge, algae or other nitrogenrich renewable sources have a higher propensity for polymerization than oils derived from wood or straw.
  • oils derived from nitrogen rich feedstocks are not stabilized they may quickly coke and plug catalyst bed. If they are stabilized using the same method as used for pyrolysis oil derived from woody biomass, then an unnecessary high pressure, low LHSV and very expensive catalyst is used, leading to a very high CAPEX.
  • WO 2022/152900 describes a method for low temperature stabilization of liquid oils.
  • the present technology provides the discovery of a new problem - that for feeds with low carbonyl numbers, such as above the detection limit, but below 1.13 mmol/g, but high concentrations of nitrogen, plugging of the reactor is a risk. It is an object to provide a stable renewable crude, and a process for the formation thereof, that can be further hydroprocessed using more traditional hydroprocessing conditions.
  • the present invention relates to a process for hydrotreating a nitrogen rich liquid oil stream by, in a continuous operation in a fixed bed reactor, reacting the nitrogen rich liquid oil stream with hydrogen in the presence of catalyst at a temperature of 80-250°C, a pressure of 10-200 barg, a liquid hourly space velocity (LHSV) of 0.1 - 6 h’ 1 , thereby forming a stabilized liquid oil stream.
  • LHSV liquid hourly space velocity
  • barg denotes pressure above atmospheric (atmospheric pressure: about 1 bar).
  • a process for hydrotreating a nitrogen rich liquid oil stream comprising at least 0.5 wt% nitrogen and a carbonyl content from 0.5 mmol/g to 1.13 mmol/g by, in a continuous operation in a fixed bed reactor, reacting the nitrogen rich liquid oil stream with hydrogen in the presence of catalyst at a temperature of 80-250°C, a pressure of 10-200 barg, a liquid hourly space velocity (LHSV) of 0.1 - 6 h’ 1 , thereby forming a stabilized liquid oil stream.
  • LHSV liquid hourly space velocity
  • the temperature is in the range 180 - 220°C, e.g. 190-200°C.
  • the pressure is 80-175 barg, e.g. 150 barg.
  • LHSV is 0.2- 4.0 h’ 1 , such as 0.2-0.2 h’ 1 , or 0.8-1.0 h’ 1 , e.g. 0.9 h -1 .
  • the temperature is in the range 180 - 220°C, e.g. 190-200°C.
  • the pressure is 15-80 barg, e.g. 50 barg.
  • LHSV is 0.2- 4.0 h’ 1 , such as 0.2-0.2 h’ 1 , or 0.8-1.0 h’ 1 , e.g. 0.9 h -1 .
  • the temperature range 80-250°C encompasses the inlet temperature of the liquid oil stream and the outlet temperature of stabilized liquid oil stream.
  • Preferred temperature ranges include 100-250°C, 120-250°C, and 150-250°C.
  • the process is exothermic thus a raise in temperature of about 100°C or more may occur.
  • the outlet temperature can for instance be 150 or 200 or 240°C. More generally, the temperature in a given step or reactor (unit) thereof, means the inlet temperature in an adiabatic step, or the reaction temperature in an isothermal step.
  • continuous operation means that the incoming stream of liquid oil during a given production cycle is continuous, as also is the stabilized liquid oil stream being withdrawn as the outcoming product.
  • discontinuous operation as is also well known in the art, in which the total amount of liquid oil and catalyst is introduced at the beginning of the process, and the outcoming product is withdrawn after a certain period of time.
  • the process suitably has a hydrogen to liquid oil ratio, defined as the volume ratio of hydrogen to the flow of the liquid oil stream, of 100-8000 NL/L, such as 2000-5000 NL/L.
  • the process is also conducted at a hydrogen to liquid oil ratio of 1000- 6000 NL/L, such as 2000-5000 NL/L, for instance 2500, 3000, 3500, 4000 or 4500 NL/L.
  • hydrogen to liquid oil ratio or "H2/Oil ratio” means the volume ratio of hydrogen to the flow of the liquid oil stream.
  • unit NL means "normal" liter, i.e. the amount of gas taken up this volume at 0°C and 1 atmosphere.
  • the volume of liquid oil is in line with the practice in the field determined at 15°C and 1 atmosphere.
  • the liquid oil stream contains at least 2 wt% N, or at least 5 wt% N.
  • the liquid oil stream may contain 10 wt% nitrogen (N), such as at least 2 wt% N, or at least 5 wt% N.
  • the nitrogen content is suitably determined by standard elemental analysis.
  • the liquid oil stream contains at least 0.5 wt% oxygen (O), such as at least 2 wt% O, or at least 4 wt% O.
  • O wt% oxygen
  • the micro carbon residue (MCR) of the liquid oil stream, before hydrotreating, as determined by ASTM D 4530 is between 5-20 wt%, such as between 5-15wt%, as such elevated MCR values indicate an inclination for coke depositing.
  • the micro carbon residue (MCR) of the stabilized liquid oil stream, as determined by ASTM D 4530 is suitably below 5 wt%, such as below 4.5 wt%, which indicates lower inclination for coke depositing.
  • the liquid oil stream is a pyrolysis oil stream or a hydrothermal liquefaction oil (HTL oil) stream.
  • the liquid oil stream is a stream of oil originating from a thermochemical decomposition process, such as pyrolysis or hydrothermal liquefaction, being part of the same process plant or a separate process plant.
  • the liquid oil stream is a pyrolysis oil stream which comprises at least 0.5 mol/kg of one or more of: aldehyde compounds, ketones, alcohols, furfural, as determined by ASTM E3146-20.
  • the liquid oil stream may be characterized by it's elemental composition being from 50 wt% to 70 wt%, 80 wt% or 85 wt% C and from 2 wt% 3 wt% 5 wt% or 10 wt% to 50wt% O, which an exemplary elemental composition range of a liquid, non-aqueous thermochemical decomposition product such as a pyrolysis oil stream or a hydrothermal liquefaction oil (HTL oil) stream.
  • HTL oil hydrothermal liquefaction oil
  • the catalyst is Ni-based, Mo-based, CoMo-based, NiMo-based, W-based, NiW- based or Ru-based, optionally in sulfided or reduced form.
  • a catalyst is "based" on a particular metal (e.g. Ni-based), this means that that the listed metal Ni, Mo,... is at least 90wt%, 99% or 100% of the Group 1-12 materials in the catalyst.
  • the catalyst is a supported catalyst having a Mo content of 2-30 wt%, and optionally also a P content of 0-3 wt%, based on the total weight of the catalyst.
  • the support may be selected from alumina, silica, titania and combinations thereof; optionally in combination with a solid acid such as silica-alumina or a molecular sieve having topology MFI, BEA or FAU.
  • topology MFI means a structure as 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.
  • the process may further comprise a prior step of thermal decomposition of a solid renewable feedstock, for producing said liquid oil stream.
  • thermal decomposition shall for convenience be used broadly for any decomposition process, in which a material is partially decomposed at elevated temperature (typically 250°C to 800°C or even 1000°C), in the presence of sub-stoichiometric amount of oxygen (including no oxygen).
  • the product will typically be a combined liquid and gaseous stream, as well as an amount of solid char.
  • the term shall be construed to include processes known as pyrolysis and hydrothermal liquefaction, both in the presence and absence of a catalyst.
  • the thermal decomposition is pyrolysis, such as fast pyrolysis, thereby producing said pyrolysis oil stream.
  • the thermal decomposition is conducted in a thermal decomposition section.
  • the pyrolysis is conducted in a pyrolysis section
  • the hydrothermal liquefaction is conducted in a hydrothermal liquefaction section.
  • section means a physical section comprising a unit or combination of units for conducting one or more steps and/or sub-steps.
  • Fast pyrolysis means the thermal decomposition of a solid renewable feedstock in the absence of oxygen, at temperatures in the range 350-650°C e.g. about 500°C and reaction times of 10 seconds or less, such as 5 seconds or less, e.g. about 2 sec.
  • Fast pyrolysis may for instance be conducted by autothermal operation e.g. in a fluidized bed reactor.
  • the latter is also referred as autothermal pyrolysis and is characterized by employing air, optionally with an inert gas or recycle gas, as the fluidizing gas, or by using a mixture of air and inert gas or recycle gas.
  • the partial oxidation of pyrolysis compounds being produced in the pyrolysis reactor provides the energy for pyrolysis while at the same time improving heat transfer.
  • autothermal pyrolysis For details about autothermal pyrolysis, reference is given to e.g "Heterodoxy in Fast Pyrolysis of Biomass" by Robert Brown: https://dx.doi.Qrq/10.1021/acs. enerqyfuels.0c03512.
  • the pyrolysis is fast pyrolysis, wherein said fast pyrolysis is suitably conducted in the absence of a catalyst and hydrogen.
  • "Intermediate" or “slow” pyrolysis are also suitable for high N feedstocks, and may be even more suitable than fast pyrolysis. One reason is that high N containing feedstocks tend to comprise more alkaline metals, which increases the risk of agglomeration and defluidization.
  • the pyrolysis step is intermediate pyrolysis, in which the vapor residence time is in the range of 10 seconds - 5 minutes, such as 11 seconds - 3 minutes.
  • the temperature is also in the range 350-650°C e.g. about 500°C.
  • this pyrolysis is conducted in pyrolysis reactors handling different types of waste, where the vapor is burned after the pyrolysis reactor. Typical reactors are: Herreshoff furnace, rotary drums, amaron, CHOREN paddle pyrolysis kiln, auger reactor, and vacuum pyrolysis reactor.
  • the pyrolysis step is slow pyrolysis, in which the solid residence time is in the range of 5 minutes - 2 hours, such as 10 min - 1 hour.
  • the temperature is suitably about 300°C.
  • This pyrolysis gives a high char yield and the char can be used as a fertilizer or as char coal; the pyrolysis still produces some gas and renewable crude and if the carbon is used a fertilizer the final bio-oil can have a GHG above 100 %, thus being carbon negative.
  • Typical reactors are auger reactor (yet with a different residence time than for intermediate pyrolysis), fixed bed reactor, kiln, lambiotte SIFIC/CISR retort, Lurgi process, wagon reactor, and carbo twin resort.
  • Hydrothermal liquefaction involves the reaction of biomass or organic material in the presence of water or other solvents at hydrothermal conditions, effectively in the range of temperatures from 250 °C to 450 °C, and pressures from approximately 100-350 bar. At these conditions, water remains in a liquid or relatively dense supercritical state. Due to the requirement of a wet reaction environment, HTL is especially suited to wet feedstocks as the need for drying is alleviated.
  • organic material undergoes a number of depolymerization reactions including hydrolysis, dehydration and decarboxylation to form water-soluble intermediates, and repolymerization reactions including various condensation mechanisms to form water insoluble products including renewable crude and char.
  • gases typically dominated by CO 2 but, depending on biomass and reaction conditions, with varying contents of H 2 , CH 4 and CO, as well as an aqueous phase with soluble organics, mostly in the form of alcohols, acids and phenols (for lignocellulosics).
  • the thermal decomposition step may be:
  • - pyrolysis such as fast, intermediate or slow pyrolysis, thereby producing a pyrolysis oil stream; or - hydrothermal liquefaction (HTL), thereby producing a HTL oil stream.
  • HTL hydrothermal liquefaction
  • the solid renewable feedstock is:
  • lignocellulosic biomass including : wood products, forestry waste, and agricultural residue;
  • municipal waste in particular the organic portion thereof, where the municipal waste is defined as a feedstock containing materials of items discarded by the public, such as mixed municipal waste given in EU Directive 2018/2001 (RED II), Annex IX, part A.
  • renewable shall be construed to exclude fossil crudes, but to include recycled waste of fossil origin, such as plastic waste.
  • 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 lignocellulosic biomass is suitably 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. wheat straw, oats, rye, reed grass, bamboo, sugar cane or sugar cane derivatives such as bagasse, maize and other cereals.
  • the process further comprises passing the stabilized liquid oil stream through a hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), or hydrodesulfurisation (HDS) step, suitably wherein the HDO is conducted at a higher temperature than the prior step for forming said stabilized liquid oil stream.
  • HDO hydrodeoxygenation
  • HDN hydrodenitrogenation
  • HDS hydrodesulfurisation
  • any organic nitrogen present in the stabilized pyrolysis oil stream is removed and a hydrotreated stream is produced, which can be further treated for producing hydrocarbon products boiling in the transportation fuel range, such as diesel, jet fuel and naphtha.
  • oxygen is mainly removed as H2O, which gives a paraffinic fuel consisting of paraffins with the same number for carbon atoms as in the backbone of the triglycerides. This is called the hydrodeoxygenation (HDO) pathway.
  • HDO hydrodeoxygenation
  • the material catalytically active in hydrotreating e.g. HDO, typically comprises an active metal (sulfided base metals such as nickel, cobalt, tungsten and/or molybdenum, but possibly also either elemental noble metals such as platinum and/or palladium) and a refractory support (such as alumina, silica or titania, or combinations thereof).
  • the process further comprises passing the stabilized liquid oil stream through one or more metal guards active in hydrometallation (HDM) and/or hydrodeoxygenation (HDO), prior to said HDO step.
  • a suitably guard bed for at least removing P and Fe is a porous material comprising alumina, the alumina comprising alphaalumina, with the porous material comprising one or more metals selected from Co, Mo, Ni, W and combinations thereof, and said porous material having a BET-surface area of 1-110 m2 /g, suitably also having a total pore volume of 0.50-0.80 ml/g, as measured by mercury intrusion porosimetry, and a pore size distribution (PSD) with at least 30 vol% of the total pore volume being in pores with a radius > 400 A, suitably pores with a radius > 500 A, such as pores with a radius up to 5000 A; as for instance disclosed in co-pending patent application PCT/EP2021/068656.
  • Another suitable guard bed is a catalyst comprising molybdenum supported on alumina, i.e. a Mo/AI 2 O 3 catalyst.
  • a catalyst having demetallization activity and moderate hydrodesulfurization activity such as a NiMo catalyst, e.g. in which the metal content is Mo: 6.0 wt %, Ni: 1.8 wt %.
  • Hydrodemetallation as is well known in the art, means a pretreatment, by which organically bound metals are deposited as sulfides or oxides. It would be understood, that while the reaction is similar for hydrodesulfurization (HDS) the heteroatom (S) is removed as H 2 S in gas form.
  • HDS hydrodesulfurization
  • Oils derived from sewage sludge and other nitrogen rich feedstocks have a high nitrogen content (>1 wt%). These oils are more thermally stable than fast pyrolysis oil, but a stabilization step is still necessary before it can be heated to 300°C.
  • an oil with 9 wt% nitrogen has been stabilized using a a NiMoS/AI 2 O 3 (Mo: 6.0 wt %, Ni: 1.8 wt %) catalyst operating at LHSV: 0.25- 0.5 h-1, 20-120 barg and 190-220°C.
  • the oil was successfully stabilized and further hydrotreated, which decreased the nitrogen content to 0.17 wt%.
  • the oil composition is shown in Table 1.
  • the oil was produced from sewage sludge, which is the reason for its high nitrogen content (9.0 wt%).
  • Catalyst A is a guard catalyst with medium HDS/HDO/HDN activity.
  • Catalyst B is a guard catalyst with medium HDS/HDO/HDN activity.
  • Catalyst C is a high activity HDO/HDN/HDS catalyst. Mo: 19.7 wt%, Ni: 3.6 wt%, P : 2.0 wt%.
  • the first test the first test it was assumed that the oil was thermally stable and the first reactor was therefore loaded with HDM catalyst, but the inlet to R1 plugged after 167 hours.
  • the liquid product from the first test contained 2.6 wt% nitrogen as shown in Table 3.
  • the purpose of the second test was to investigate if the oil could be stabilized at 20 bar at 190 and 220°C.
  • the test ran for 431 hours without any observed pressure drop over the reactors and as shown in Table 3 the MCR was decreased to between 3.80 and 3.96 wt% compared to 9.81 wt for the feed, hence indicating that the product is more thermally stable than the feed.
  • the nitrogen, sulfur and oxygen content was also decreased to between 8.3 and 8.8 wt%, 0.49 and 0.60 wt%, and 4.4 and 4.9 wt%, respectively, while the hydrogen content was increased to between 8.85 and 9.00 wt% hence indicating that an additional feature of the stabilization reactor is that it removes some heteroatoms while hydrogenating the oil.
  • the pressure was increased to 120 bar and in the first condition the temperature in the first reactor 220°C while the temperature in the second reactor was 100°C, hence the catalyst in the second reactor was considered to be inactive at this temperature.
  • the product had a Micro Carbon Residue (MCR) according to ASTM D4530 of 2.36 wt% while the nitrogen was reduced to 7.6 wt%.
  • MCR Micro Carbon Residue
  • Increasing the temperature in condition 2 to 340 °C and in 3 to 360°C decreased nitrogen content to 1.3 and 0.17 wt%, respectively, while the MCR decreased to below ⁇ 0.05 wt% and the oxygen content decreased to below 1 wt%.

Landscapes

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

Abstract

La présente invention concerne un procédé d'hydrotraitement d'un flux d'huile liquide riche en azote, dans une opération continue dans un réacteur à lit fixe, par mise en réaction du flux d'huile liquide riche en azote avec de l'hydrogène en présence d'un catalyseur à une température de 80 à 250°C, une pression de 10 à 200 barg, une vitesse spatiale horaire de liquide (LHSV) de 0,1 à 6 h- 1 , formant ainsi un flux d'huile liquide stabilisé.
EP23836859.1A 2022-12-22 2023-12-21 Procédé de stabilisation d'huiles riches en azote Pending EP4638662A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22216003 2022-12-22
PCT/EP2023/087208 WO2024133640A1 (fr) 2022-12-22 2023-12-21 Procédé de stabilisation d'huiles riches en azote

Publications (1)

Publication Number Publication Date
EP4638662A1 true EP4638662A1 (fr) 2025-10-29

Family

ID=84569441

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23836859.1A Pending EP4638662A1 (fr) 2022-12-22 2023-12-21 Procédé de stabilisation d'huiles riches en azote

Country Status (6)

Country Link
EP (1) EP4638662A1 (fr)
JP (1) JP2025542311A (fr)
KR (1) KR20250126015A (fr)
CN (1) CN120380113A (fr)
AU (1) AU2023413815A1 (fr)
WO (1) WO2024133640A1 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5904838A (en) * 1998-04-17 1999-05-18 Uop Llc Process for the simultaneous conversion of waste lubricating oil and pyrolysis oil derived from organic waste to produce a synthetic crude oil
FR2953854B1 (fr) * 2009-12-16 2012-12-28 Inst Francais Du Petrole Procede de conversion de charges issues de sources renouvelables avec pretraitement des charges par dephosphatation a chaud
US20120285079A1 (en) * 2011-05-10 2012-11-15 Battelle Memorial Institute Process for stabilizing fast pyrolysis oil, and stabilized fast pyrolysis oil
US20150057475A1 (en) * 2013-08-23 2015-02-26 Battelle Memorial Institute Bi-functional catalyst and processes for conversion of biomass to fuel-range hydrocarbons
SI3921387T1 (sl) * 2019-02-08 2023-02-28 Steeper Energy Aps Proces za nadgradnjo obnovljivih tekočih ogljikovodikov
EP4133037B1 (fr) * 2020-04-07 2024-07-17 TotalEnergies OneTech Belgium Valorisation d'huile à base de déchets plastiques en produits chimiques de haute valeur par craquage catalytique direct
EP4277962A1 (fr) 2021-01-18 2023-11-22 Topsoe A/S Stabilisation à basse température d'huiles liquides

Also Published As

Publication number Publication date
WO2024133640A1 (fr) 2024-06-27
AU2023413815A1 (en) 2025-07-10
JP2025542311A (ja) 2025-12-25
KR20250126015A (ko) 2025-08-22
CN120380113A (zh) 2025-07-25

Similar Documents

Publication Publication Date Title
EP4277962A1 (fr) Stabilisation à basse température d'huiles liquides
CN104411802B (zh) 用于将生物油提质成烃燃料的优化方法
AU2022375041A1 (en) A process for hydrotreatment of aromatic nitrogen compounds
US20260008965A1 (en) Hydroprocessing of bio-crude oil with vegetable and/or fatty material
WO2023134973A1 (fr) Procédé d'hydrotraitement d'une charge d'alimentation en huile liquide
WO2024133640A1 (fr) Procédé de stabilisation d'huiles riches en azote
WO2024188884A1 (fr) Procédé pour traiter des matériaux liquéfiés
US20250382531A1 (en) A process for stabilization of an unstable raw hydrocarbonaceous product
WO2023134974A1 (fr) Procédé d'hydrotraitement d'une charge d'alimentation en huile liquide
RU2852920C1 (ru) Низкотемпературная стабилизация жидких масел
RU2858134C2 (ru) Способ и установка для получения углеводородов из твердого возобновляемого исходного сырья с пониженным выбросом co2
WO2024175793A1 (fr) Procédé de traitement de matériau liquéfié
WO2024194422A1 (fr) Élimination du fluor dans la production de combustible renouvelable
AU2024214927A1 (en) Removal of arsenic in renewable fuel production
EP4662293A1 (fr) Stabilisation à basse température d'huiles liquides
Ahmadi Upgrading of Fast Pyrolysis Oil via HDO Using Nano-Structured Catalysts

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20250627

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)