EP3230411A1 - A method for diesel production - Google Patents
A method for diesel productionInfo
- Publication number
- EP3230411A1 EP3230411A1 EP14835732.0A EP14835732A EP3230411A1 EP 3230411 A1 EP3230411 A1 EP 3230411A1 EP 14835732 A EP14835732 A EP 14835732A EP 3230411 A1 EP3230411 A1 EP 3230411A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrocarbon mixture
- range
- diesel
- reactor system
- zone
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 104
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 104
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 49
- 238000004821 distillation Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000009835 boiling Methods 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 229910003294 NiMo Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 238000005336 cracking Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
-
- 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
- C10G45/04—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 characterised by the catalyst used
- C10G45/06—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- 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
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
- C10G2300/802—Diluents
-
- 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
- C10G2400/04—Diesel oil
Definitions
- the present invention relates to a method for production of diesel from a hydrocarbon mixture having an initial T95 distillation temperature within the range between 360°C and 420°C.
- ultra-low sulfur diesel ULSD
- ULSD ultra-low sulfur diesel
- the 95% distillation temperature of diesel (ASTM D86) is required to be less than 360°C and reduction in the 95% distillation temperature (T95) of diesel represents the decrease in the volume of diesel produced.
- middle distillate hydrocarbon streams from crude distillation units must be treated in hydrodesulfurization units.
- the feedstock is processed with a suitable desulfurization catalyst under a temperature ranging between 350°C and 450°C and a hydrogen partial pressure ranging between 60 bars and 80 bars.
- the requirement that the T95 of diesel is to be maximum 360°C (ASTM D86) determines a maximum boiling range for the feedstock.
- a limited extent of T95 reduction can be achieved in hydrodesulfurization processes, which is generally around 5 to 10°C. Accordingly, maximum T95 of the feedstock is limited to the range between 360°C and 365°C.
- diesel boiling range hydrocarbon mixtures are processed with suitable desulfurization catalyst(s) under temperatures ranging between 350°C and 450°C and with hydrogen partial pressures within the range of 60 bars to 80 bars.
- desulfurization catalyst(s) under temperatures ranging between 350°C and 450°C and with hydrogen partial pressures within the range of 60 bars to 80 bars.
- sulfur content of said hydrocarbon mixtures is reduced to a maximum value lower than 10 wppm.
- dewaxing catalysts are employed prior to reactor outlets, to improve cold filter plugging properties especially in winter seasons. Similar with that by hydrodesulfurization units mentioned above, only a limited T95 reduction can be achieved at deep hydrodesulfurization units.
- hydrodesulfurization processes are in conventional use and they are very well known by refining industry. At these processes, feedstocks involving heavier hydrocarbons are to be converted into lighter products like diesel using further conversion units, e.g. hydrocracking reactors.
- the amount of middle distillate produced from a crude distillation unit can generally be considered to be insufficient for supplying the demand for diesel and jet fuel. Therefore conversion processes like hydrocracking are employed in petroleum refineries.
- hydrocracking reactors heavy feedstocks such as vacuum gas oils are processed with suitable hydrocracking catalysts under elevated temperatures ranging between 400°C and 500°C and pressures ranging between 160 bars and 200 bars in presence of hydrogen.
- the operating conditions and choice of hydrocracking catalysts in a hydrocracking reactor affect respective product yields.
- Partial or full conversion hydrocracking is used to produce diesel with lower yield of unconverted oil that is fed to other units such as fluid catalytic cracking (FCC) units. Additionally, the conversion level might be reduced in the hydrocracking and unconverted oil with improved quality can be utilized in lube production.
- FCC fluid catalytic cracking
- Mild hydrocracking is also used in petroleum refineries in order to improve the properties of unconverted oil that is fed to other downstream units while partially converting heavy feedstocks such as vacuum gas into lighter products like diesel.
- Mild hydrocracker units are operated under less severe conditions, i.e. lower temperatures and pressures with respect to abovem . entioned hydrocracking processes. Accordingly, conversion levels achieved with mild hydrocracker units are relatively low compared to conventional hydrocracking processes.
- a typical diesel boiling range feedstock hydrodesulfurization unit having a 100 tonnes of feed capacity outputs 95 tonnes of diesel product in average throughout the catalyst cycle length with a density of 839 kg/m 3 (which corresponds to about 113.2 m 3 diesel production per day), and 5 tonnes of lighter hydrocarbon mixture with a lower T95 distillation temperature with regard to diesel. Additionally, heavier hydrocarbon fractions with higher T95 distillation temperatures in comparison with diesel boiling range fraction have lower economical value with regard to diesel.
- Primary object of the present invention is to eliminate the above-mentioned shortcomings in the prior art.
- a further object of the present invention is to provide a method to increase the volumetric production capacity for diesel boiling range hydrocarbons in refineries.
- a further object of the present invention is to provide a method to increase the mass production capacity of diesel boiling range hydrocarbons in refineries.
- a further object of the present invention is to provide a method which increases the added value production. at petroleum refineries.
- a further object of the present invention is to provide a method which reduces the T95 distillation point of a feedstock by converting heavier hydrocarbon fractions into diesel boiling range hydrocarbons under less severe conditions in comparison with conventional hydrocracking processes for hydrocracking of such heavier hydrocarbon fractions.
- the present invention proposes a method for production of diesel from a hydrocarbon mixture having an initial T95 distillation temperature within the range between 360°C and 420°C, using a continuous reactor system wherein the reactor system temperature is within the range of 350°C and 450°C, the hydrogen partial pressure within the reactor system is within the range of 60 bar and 80 bar, the reactor system comprises a hydrodesulfurization zone comprising hydrodesulfurization ' catalyst, and the reactor system further comprises a hydrocracking zone comprising a hydrocracking catalyst; and wherein said method comprises the sequential steps of preparation of a hydrocarbon mixture by admixing a diesel range stream having a T95 distillation temperature of maximum 360°C with a heavy stream having a T95 distillation temperature higher than 360°C, feeding the hydrocarbon mixture into the reactor system, forwarding the hydrocarbon mixture such that the hydrocarbon mixture flows through the hydrodesulfurization zone, forwarding the hydrocarbon mixture such that said hydrocarbon mixture flows through a hydrocracking zone.
- the present invention proposes a method for production of diesel from a hydrocarbon mixture having an initial T95 distillation temperature within the range between 360°C and 420°C,
- the reactor system temperature is within the range of 350°C and 450°C
- the hydrogen partial pressure within the reactor system is within the range of 60 bar and 80 bar,
- the reactor system comprises a hydrodesulfurization zone comprising hydrodesulfurization catalyst
- the reactor system further comprises a hydrocracking zone comprising a hydrocracking catalyst
- said method comprises the following sequential steps: a) preparation of a hydrocarbon mixture by admixing a diesel range stream having a T95 distillation temperature of maximum 360°C with a heavy stream having a T95 distillation temperature higher than 360°C,
- the method according to the present invention preferably further comprises a step of forwarding the hydrocarbon mixture from the reactor system into a fractionator, subsequent to the above step 3 ⁇ 4 d)', such that diesel boiling range hydrocarbons are separated from lighter hydrocarbons such as naphtha and LPG.
- the initial T95 distillation temperature of the hydrocarbon mixture is within the range between 375°C and 395°C, and more preferably within the range between 380°C and 390°C.
- an optimum heavy fraction ratio in the hydrocarbon mixture can be supplied by obtaining suitable conversion of large molecules into molecules having boiling points within the diesel-range.
- the space velocity of the hydrocarbon mixture within the reactor system is within the range of 0.5 h "1 and 3 h "1 , and more preferably within the range of 1 h "1 and 2 h "1 .
- an optimum residence time can be obtained for suitable conversion of large molecules into molecules having boiling points within the diesel-range.
- gas to oil ratio is within the range of 300 Nm 3 /m 3 and 1000 Nm 3 /m 3 , and more preferably within the range of 600 Nm 3 /m 3 and 850 Nm 3 /m 3 .
- This provides an optimum density within the reactor system for obtaining diesel boiling range hydrocarbons with desired reaction rates throughout the reactor system.
- the reactor system having hydrodesulfurization zone and the hydrocracking zone could be a single reactor or a series of several reactors.
- the reactor system further comprises a quench zone between the hydrodesulfurization zone and the hydrocracking zone; for cooling the hydrocarbon mixture with a hydrogen-rich gas stream.
- hydrodesulfurization zone and/or hydrocracker zone comprises one or more inter-quench zones, for prevention of superheating of hydrocarbons flowing through the reactor system; since there might be more than one catalytic bed in each catalytic zone.
- the present invention enables low cost production of ultra-low sulfur diesel within required specifications by hydrodesulfurization of diesel boiling range hydrocarbon feed and more importantly T95 reduction of hydrocarbon feeds having a boiling range higher than that of diesel, by performing a less severe hydrocracking than those which are performed in conventional processes.
- hydrodesulfurization and/or dewaxing catalysts in subsequent bed(s) of an existing hydrodesulfurization unit or in an already existing reactor of an existing hydrodesulfurization unit can be replaced with hydrocracking catalyst which operates in line with hydrodesulfurization zone, i.e. under less severe conditions compared to conventional hydrocracking process.
- hydrocracking catalyst which operates in line with hydrodesulfurization zone, i.e. under less severe conditions compared to conventional hydrocracking process.
- T95 limitation of a maximum value of 365°C of the hydrocarbon mixtures used as diesel production reactor feed in the prior art is rised up to 400°C, and preferably up to 385°C.
- the hydrocarbon mixture used as reactor feed in the method according to the present invention is prepared by admixtion of a heavy stream (i.e. a hydrocarbon mixture having a higher T95 distillation temperature compared to that of a diesel range stream which has a T95 distillation temperature of maximum 360°C in accordance with ASTM D86) with a diesel range stream.
- Said heavy stream is preferably selected from the list consisting of a heavy fraction of atmospheric gas oil (AGO), light vacuum gas oil (LVGO), a light fraction of the heavy vacuum gas oil (HVGO), visbreaker gas oil (VBGO) and FCC light cycle oil (LCO) and a mixture thereof.
- AGO atmospheric gas oil
- LVGO light vacuum gas oil
- HVGO heavy vacuum gas oil
- VBGO visbreaker gas oil
- LCO FCC light cycle oil
- the hydrodesulfurization zone employed in the method according to the present invention preferably involves conventional catalysts in appropriate amounts, activity, etc. which can be decided/chosen/calculated by a skilled person in the art, to achieve deep hydrodesulphurization for complying with relevant legislations such that reducing the sulfur content of the hydrocarbon mixture to a value less than 10 wppm.
- the hydrodesulphurization catalyst can be selected from the list consisting of NiMo on alumina, CoMo on alumina, and a mixture thereof.
- the catalyst is NiMo on alumina due to its high hydrogenation and hydrodenitrogenation activity.
- the hydrocracking zone employed in the method according to the present invention preferably involves conventional catalysts in appropriate amounts, activity, etc. which can be decided/chosen/calculated by a skilled person in the art, to obtain both hydrocracking and hydrogenation.
- Cracking occurs by an acidic site which is e.g. a silica-alumina based zeolitic structure; and hydrogenation occurs by a metal site which is e.g. Ni, W, Co etc.
- the hydrocracking catalyst according to the present invention preferably comprises a silica or alumina-based catalyst having metallic sites selected from the list consisting of Nickel, Wolfram, Cobalt and a mixture thereof.
- the hydrocracker catalyst plays an important role on the yields obtained using the method according to the present invention.
- the activity of the hydrocracking catalyst shall be compatible with hydrodesulfurization catalyst so that the cracking level to lighter products such as naphtha and LPG is controlled, thereby maintaining higher concentrations of desired diesel boiling range substances in the product stream.
- an already-set-up diesel desulfurization unit can be utilized to perform the method according to the present invention. Since the diesel boiling range fraction production capacity is almost constant depending on the crude oil processing capacity, , the entire diesel boiling range fraction is to be processed run down in order to avoid extra storage costs.
- the method can be easily applied if the capacity of the desulfurization unit is not fully utilized. But if the unit is at its design capacity, the method can be also applied by operating the desulfurization unit at higher capacity than its design capacity without exceeding the hydraulic and safety limits.
- heavier fractions are partly included into diesel boiling range fractions and a more economical use of heavier fractions is achieved.
- the heavier fraction having lower economical value with regard to diesel is directed to increase the overall diesel production in a refinery, and a greater added value is provided in such refinery.
- the weight ratio of diesel range stream in the feedstock to the heavy stream in the feedstock is preferably within the range between 0.5:10 and 1.5:10; and more preferably within the range between 0.5:10 and 1:10.
- This provides prevention of heavier hydrocarbons in the product and further costs arising due to separation requirement of heavier hydrocarbons and diesel boiling range hydrocarbons is avoided by setting upper limits to heavy stream content in the feedstock (i.e. the hydrocarbon mixture).
- the operating temperature of the reactor system is to be increased in order to produce diesel without heavy hydrocarbons, thereby the cracking level of lighter products increases. This results in reducing diesel production.
- the reactor system to be employed for the method according to the present invention can be arranged by including hydrocracking catalyst into latter stage(s) of a multistage hydrodesulfurization reactor system which can comprise reactor plurality of reactors, or prior to the product outlet of a hydrodesulfurization reactor.
- a single-volume hydrodesulfurization reactor comprises hydrodesulfurization catalysts and successive hydrocracking catalysts with regard to the flow direction of the hydrocarbon mixture in process.
- the reactor system comprises a hydrodesulfurization zone and a successive hydrocracking zone.
- the diesel obtained with the method according to the present invention has a density of 828 kg/m 3 . This corresponds to about 116.9 m 3 diesel production per day, which is about 3.3% volumetric increase in diesel production with regard to a conventional process.
- hydrodesulfurization unit having a normal capacity designed in accordance with diesel boiling range fraction capacity of 100 tonnes per day, and an operational period of 1 day.
- 10 tonnes of a 100 tonnes diesel boiling range fraction is directed to an existing medium pressure and relatively old hydrodesulfurization unit which is designed in accordance with conventional design concept.
- said 10 tonnes of diesel boiling range hydrocarbons which is preferably light portion of diesel boiling range hydrocarbons is processed in said hydrodesulfurization unit; with smaller setup and operational costs.
- 9.5 tonnes of diesel and 0.5 tonnes of lighter hydrocarbons are obtained using this process.
- the capacity of the hydrodesulfurization unit is already fully utilized, it does not mean that the process of the invention can not be applied. If said capacity is fully utilized, then lighter feed components of the feedstock can be transferred to a lower pressure hydrodesulfurization units, i.e. conventional hydrodesulfurization units, thus extra capacity can be generated in the hydrodesulfurization zone. Thus, heavy fractions can be processed in the mentioned reactor system, thereby increasing the total hydrodesulfurization capacity and diesel production.
- the resulting effluent of the hydrocracking zone which is a product including diesel boiling range hydrocarbons and lighter hydrocarbons like naphtha and LPG is sent to a fractionator to obtain the different ranges of products.
- a fractionator In contrast to conventional hydrocracking and mild hydrocracking processes, there is no residual or unconverted heavier components in the product stream such that the T95 distillation temperature of the product stream is within the diesel boiling range. In other words, the conversion of the above mentioned heavy stream is 100% and they are completely converted into diesel boiling range hydrocarbons.
- the increase in T95 distillation temperature of the combined feedstock may vary depending on the type and amount of the heavy fraction admixed with the diesel boiling range fraction.
- the aromatic content of the hydrocarbon mixture and the types of the hydrodesulfurization and hydrocracking catalysts also determine the hydrogenation level which affects the yield distribution and diesel density.
- heavier fractions i.e. heavy stream
- diesel boiling range hydrocarbons under less severe conditions, i.e. under 60 bars to 80 bars and 350°C to 450°C, instead of 160 bars to -200 bar and 400°C to 500°C which conditions are employed for hydrocracking in conventional hydrocracking processes for heavy fractions.
- the product stream of the reactor system can be further directed to a subsequent dewaxing unit for use in winter seasons.
- T95 distillation temperature of a feed stock is reduced by converting heavier hydrocarbon fractions into diesel boiling range hydrocarbons under less severe conditions in comparison with conventional hydrocracking processes for hydrocracking of such heavier hydrocarbon fractions.
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)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
Claims
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/TR2014/000503 WO2016093777A1 (en) | 2014-12-11 | 2014-12-11 | A method for diesel production |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3230411A1 true EP3230411A1 (en) | 2017-10-18 |
EP3230411B1 EP3230411B1 (en) | 2023-01-11 |
Family
ID=52469277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14835732.0A Active EP3230411B1 (en) | 2014-12-11 | 2014-12-11 | A method for diesel production |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP3230411B1 (en) |
WO (1) | WO2016093777A1 (en) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6261441B1 (en) * | 1998-09-24 | 2001-07-17 | Mobil Oil Corporation | Integrated hydroprocessing scheme with segregated recycle |
SI1741768T2 (en) * | 2005-07-04 | 2023-05-31 | Neste Oil Oyj | Process for the manufacture of diesel range hydrocarbons |
CA2657780C (en) * | 2006-07-19 | 2012-02-07 | Uop Llc | A hydrocarbon desulfurization process |
US8980081B2 (en) * | 2007-10-22 | 2015-03-17 | Chevron U.S.A. Inc. | Method of making high energy distillate fuels |
US8343334B2 (en) * | 2009-10-06 | 2013-01-01 | Saudi Arabian Oil Company | Pressure cascaded two-stage hydrocracking unit |
US9212323B2 (en) * | 2011-02-11 | 2015-12-15 | E I Du Pont De Nemours And Company | Liquid-full hydrotreating and selective ring opening processes |
US8721871B1 (en) * | 2012-11-06 | 2014-05-13 | E I Du Pont De Nemours And Company | Hydroprocessing light cycle oil in liquid-full reactors |
-
2014
- 2014-12-11 EP EP14835732.0A patent/EP3230411B1/en active Active
- 2014-12-11 WO PCT/TR2014/000503 patent/WO2016093777A1/en active Application Filing
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2016093777A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP3230411B1 (en) | 2023-01-11 |
WO2016093777A1 (en) | 2016-06-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102447300B1 (en) | A conversion process comprising fixed bed hydrotreating for the manufacture of marine fuels, separation of the hydrotreated resid fraction and catalytic cracking steps | |
US8404103B2 (en) | Combination of mild hydrotreating and hydrocracking for making low sulfur diesel and high octane naphtha | |
TWI617661B (en) | Process with separation for treating petroleum feedstocks for the production of fuel oils with a low sulfur content | |
KR102447843B1 (en) | Process for converting petroleum feedstocks comprising a stage of fixed-bed hydrotreatment, a stage of ebullating-bed hydrocracking, a stage of maturation and a stage of separation of the sediments for the production of fuel oils with a low sediment content | |
US20140299515A1 (en) | Process for conversion of petroleum feed comprising an ebullated bed hydroconversion step in a fixed bed hydrotreatment step for the production of low sulphur content fuel | |
EP2951272B1 (en) | Intergration of residue hydrocracking and solvent deasphalting | |
CA2902355C (en) | Increased production of fuels by integration of vacuum distillation with solvent deasphalting | |
US20080093262A1 (en) | Process and installation for conversion of heavy petroleum fractions in a fixed bed with integrated production of middle distillates with a very low sulfur content | |
US20120189505A1 (en) | Pressure cascaded two-stage hydrocracking unit | |
US10760015B2 (en) | Installation and integrated hydrotreatment and hydroconversion process with common fractionation section | |
US9920264B2 (en) | Process of hydroconversion-distillation of heavy and/or extra-heavy crude oils | |
KR20180014775A (en) | Method for converting feedstocks comprising a hydrotreatment step, a hydrocracking step, a precipitation step and a sediment separation step, in order to produce fuel oils | |
JP2015059220A (en) | Method of producing ship fuel of low sulfur content from hco produced by catalytic decomposition or slurry-type hydrocarbon-containing fraction using hydrogenation treatment stage | |
US20160122662A1 (en) | Process for converting petroleum feedstocks comprising a visbreaking stage, a maturation stage and a stage of separating the sediments for the production of fuel oils with a low sediment content | |
MX2014011112A (en) | Integration of solvent deasphalting with resin hydroprocessing and with delayed coking. | |
US11261387B2 (en) | Fuel oil conversion | |
US11866654B2 (en) | Production of high quality diesel by supercritical water process | |
EP2154225B1 (en) | An integrated process for the conversion of heavy hydrocarbons to a light distillate and/or mid-distillate | |
EP2553054B1 (en) | Hydroprocessing of gas oil boiling range feeds | |
WO2010093732A2 (en) | Selective staging hydrocracking | |
US8608947B2 (en) | Two-stage hydrotreating process | |
CN101434867A (en) | Suspension bed residual oil hydrogenation-catalytic cracking combined technological process | |
KR102405154B1 (en) | Process for producing a heavy hydrocarbon fraction with a low sulfur content comprising a demettalation section and a hydrocracking section with reactors exchangeable between the two sections | |
EP3230411B1 (en) | A method for diesel production | |
CN107532093B (en) | Method for producing oil-based components |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
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: 20170711 |
|
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 MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20180619 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20220916 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 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 MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602014086082 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1543440 Country of ref document: AT Kind code of ref document: T Effective date: 20230215 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20230111 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1543440 Country of ref document: AT Kind code of ref document: T Effective date: 20230111 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230602 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230511 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230411 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230511 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230412 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602014086082 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 |
|
26N | No opposition filed |
Effective date: 20231012 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602014086082 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231211 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20231211 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20231231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230111 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231211 |