Hydroprocessing of waste tire pyrolysis oil using vegetable and / or fatty substances

Abstract

The present invention is a method and a plant for producing a hydrocarbon feedstock, comprising: providing a biocrude feedstock containing 0.1 to 5% by mass of oxygen (O); providing a vegetable oil and / or fatty substance feedstock; producing the hydrocarbon feedstock by combining the biocrude feedstock containing 0.1 to 5% by mass of oxygen (O) with the vegetable oil and / or fatty substance feedstock, wherein the biocrude feedstock containing 0.1 to 5% by mass of O is a waste tire pyrolysis oil feedstock.

Description

Technical Field

[0001] The present invention relates to a method and a plant for hydroprocessing a bio-crude oil feedstock produced from the pyrolysis of a solid feedstock stream, together with a vegetable feedstock and / or a fatty feedstock. The solid feedstock stream includes waste tires, the pyrolysis is pyrolysis, and the bio-crude oil feedstock is waste tire pyrolysis oil.

Background Art

[0002] The co-processing of hydrocarbon fuel feedstocks by combining fossil fuel feedstocks such as petroleum feedstocks and vegetable oil feedstocks in hydroprocessing is well known. However, crude oils produced by thermal decomposition, for example, pyrolysis of solid renewable feedstocks such as lignocellulosic biomass, hydrothermal liquefaction (HTL) are miscible with fats and oils containing bio, generally vegetable oils and / or fatty acids, so the co-processing of these feedstocks in hydrogenation steps such as hydrodeoxygenation (HDO) has been an important problem to be overcome so far.

[0003] Stummann et al. “Hydrotreatment of Catalytic Fast Pyrolysis Oil to Renewable Fuels”, NAM27, The 27 th North American Catalysis Society Meeting, May 22-27, 2022 New York, NY discloses a study of combining catalytic fast pyrolysis (CFP) oil with vegetable oil (here soybean oil) in a stirred batch reactor.

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Nevertheless, the applicant has found that industrial use is very difficult because vegetable oil does not mix with most untreated catalytic pyrolysis oils. The hydrocracking reactor for treating the co-feed clogs after a few days when operated under industrially appropriate conditions.

[0006] Vegetable oil has been found to be miscible in waste tire pyrolysis oil, even though it is immiscible with catalytic and non-catalytic pyrolysis oils, as well as hydrothermal liquefaction (HTL) biocrude. The latter can be considered to be partially deoxygenated due to its low oxygen (O) content.

Means for Solving the Problems

[0007] Accordingly, in a general embodiment according to a first aspect of the present invention, a method for producing a hydrocarbon feedstock is provided, comprising the following steps: A method for producing a hydrocarbon feedstock comprising the following steps: - providing a biocrude feedstock containing 0.1 to 5% by mass of oxygen (O); - providing a vegetable oil and / or fatty substance feedstock; - combining the biocrude feedstock containing 0.1 to 5% by mass of O with the vegetable oil and / or fatty substance feedstock to produce the hydrocarbon feedstock, wherein the biocrude feedstock containing 0.1 to 5% by mass of O is a waste tire pyrolysis oil feedstock.

[0008] For example, separate waste tire pyrolysis oil feeds can be combined into a single waste tire pyrolysis oil feed containing 0.1 to 5% by mass of O.

[0009] For example, a waste tire pyrolysis oil feed can be combined with a vegetable oil feed or a fatty material feed, such as an animal fat feed.

[0010] For example, a waste tire pyrolysis oil feedstock can first be combined with a vegetable oil feedstock and then with a fatty material feed, such as an animal fat feed. Optionally, additional feeds may be provided.

[0011] The term "waste tire pyrolysis oil feed" will be understood to mean a liquid oil resulting from waste tire pyrolysis.

[0012] A biocrude oil feed containing 0.1 to 5% by mass of oxygen (O) can be regarded as a partially deoxygenated biocrude oil feed.

[0013] Therefore, in the hydrogenation processing in a downstream hydroprocessing reactor, such as a hydrodeoxygenation and / or hydrodeoxygenation (HDO / DO) reactor, or in any associated unit such as a pump or a heat exchanger, it is possible to combine waste pyrolysis oil with a vegetable oil and / or fatty substance feed without the risk of clogging the downstream hydroprocessing reactor. Further, the vegetable oil serves to cool the effluent from the HDO / DO reactor, i.e., the partially deoxygenated biocrude oil feed, or as a coolant between the catalyst beds (catalyst beds) in the first HDO reactor. Further, the formation of the heavy fraction in the downstream separation section is reduced, thereby increasing, for example, the production of diesel fuel as a hydrocarbon fuel. An oxygen (O) content of less than 2% by mass in the biocrude oil feed may contribute to miscibility with the vegetable oil and / or fatty substance, but such a low level of oxygen in the oxygen of the biocrude oil feed tends to be associated with a low aromatic content. In contrast, waste pyrolysis oil having an oxygen content of 0.1 to 5% by mass, for example, about 0.5 to 2% by mass, has been found to not only be miscible with the vegetable oil and / or fatty substance feed but also maintain a high level of aromatic compounds. As will be further described below, the presence of a sufficient amount of aromatic compounds is desirable because it can reduce heavy fraction formation during the production and / or downstream separation of hydrocarbon products such as diesel.

[0014] In certain embodiments, prior to the combining step, the method includes the following: - Supplying the waste tire pyrolysis oil feed to a stabilization step in a stabilization reactor prior to the combining step to produce a stabilized waste tire pyrolysis oil feed.

[0015] The stabilization reactor is here also shown as a selective hydrogenation unit. Waste tire pyrolysis oil has a high concentration of aromatics, so a reduction in heavy end formation in the downstream section for producing hydrocarbon fuels is obtained, preferably obtained by hydrotreating, such as hydrodeoxygenation (HDO / DO), a stabilized tire pyrolysis oil, which is then combined with vegetable oil and / or fat materials.

[0016] In one embodiment, the stabilization step is carried out in a fixed bed reactor in continuous operation mode, in the presence of any of the following; in the presence of a Ni-Mo, Co-Mo, Ni-Cu, Mo, Pt, Pd, Ru, or Ni-based catalyst, at 20 - 240 °C, a pressure of 50 - 150 barg, optionally with a liquid hourly space velocity (LHSV) of 0.1 - 2 h -1 and a hydrogen-to-liquid oil ratio defined as the volume ratio of hydrogen to the flow rate of a liquid oil stream (bio-crude feed), for example 500 - 2500 NL / L, of 250 - 3000 NL / L, wherein the bio-crude feed is fed together with hydrogen, thereby forming a stabilized bio-crude feed.

[0017] For example, the catalyst is a Ni-Mo-based catalyst, or a Co-Mo-based catalyst, or a Ru / TiO2-based catalyst (ruthenium supported on titania), or a Pt / TiO2-based catalyst.

[0018] The terms "Ni-Mo-based catalyst", "Co-Mo-based catalyst", etc. mean that Ni-Mo is the active element of the catalyst.

[0019] Suitably, Ni-Mo, Co-Mo, or Mo is in a sulfided form, such as NiMoS. Optionally, Ni is in a sulfided or reduced form.

[0020] The term "stabilization" means converting the carbonyl groups present in compounds of liquid oils, such as aldehydes, ketones and acids, to alcohols. Other molecules such as sugars and furans may also be converted in the stabilization step. Furthermore, diolefins such as conjugated diolefins are hydrotreated. For example, this stabilization step can be carried out by a NiMo-based catalyst, as disclosed in Shumeico et al. “Efficient one-stage bio-oil upgrading over sulfide catalysts”, ACS Sustainable Chem.Eng.2020, 8, 15149-15167. 2020, 8, 15149-15167. Suitably, stabilization is carried out according to the method disclosed in European patent application 21152117.4 (corresponding to international application PCT / EP2022 / 050877) co-pending with the applicant.

[0021] In one embodiment, the feed of vegetable oil and / or fatty substances is a feed of non-hydroprocessed vegetable oil and / or fatty substances. Thus, this feed has not undergone a prior hydroprocessing step such as hydrodeoxygenation (HDO).

[0022] For the purposes of the present application, the term "the first aspect of the present invention" relates to the present method. The term "the second aspect of the present invention" means a process plant, i.e. a plant. The terms "the present invention" and "the present application" are used interchangeably. The term "consisting of" includes "consisting only of", i.e. "consisting of". The term "suitably" is used interchangeably with the term "optionally", i.e. any embodiment.

[0023] The term "bio-crude oil feed containing 0.1 to 5% by mass of oxygen (O)" can be used interchangeably with the term "partially deoxygenated bio-crude oil feed". The term "bio-crude feedstock" refers to the liquid oil product of the pyrolysis step in a pyrolysis unit. The pyrolysis unit is a pyrolysis reactor. The term "unit" is understood here as a "reactor". The term bio-crude feedstock is specifically waste tire pyrolysis oil and can also be understood as "advanced bio-crude".

[0024] The term "vegetable oil feedstock and / or fatty substances" includes vegetable oils such as soybean oil and fatty substances such as animal fats. Fatty substances include fatty acids.

[0025] The term "section", for example, a "hydroprocessing section", means a physical area that includes a unit or combination of units for performing one step and / or sub-step for producing a hydroprocessed hydrocarbon feedstock or a further hydroprocessed hydrocarbon feedstock.

[0026] The term "hydroprocessing" encompasses hydrotreatment and thus includes hydrodeoxygenation or deoxygenation (HDO / DO). The term "hydroprocessing" also includes hydroisomerization (HDI), or hydrocracking (HCR), or hydrodearomatization (HDA). Hydroprocessing steps such as HDO / DO steps are understood to be carried out in a hydroprocessing reactor such as an HDO / DO reactor or in the catalyst bed of a hydroprocessing reactor such as in the catalyst bed of an HDO / DO reactor. The hydroprocessing reactor may include one or more catalyst beds. Other definitions will be described later in connection with one or more embodiments of the present invention.

[0027] Preferably, in the combination step, the mass ratio (A:B) of bio-crude oil, i.e., waste tire pyrolysis oil feedstock (A) to vegetable oil and / or fatty substance feedstock (B) is in the range of 9:1, i.e., 90:10 mass % ratio to 1:9, i.e., 10:90 mass % ratio; for example, 3:1, i.e., 75:25 mass % ratio, 2:1 i.e., 66.6:33.3 mass ratio, 1:1, i.e., 50:50 mass % ratio, 1:2 i.e., 33.3:66.6 mass %, 1:3, i.e., 25:75 mass %, 1:4, i.e., 20:80 mass % ratio, 1:5, i.e., 17:83 mass %, 1:6, i.e., 15:85 mass % ratio.

[0028] It will be understood that the above weight ratios are also applicable when combining hydrogenation feedstocks, for example, when combining a hydrogenated waste tire pyrolysis oil feedstock and a hydrogenated vegetable oil feedstock.

[0029] In one embodiment, the method further comprises a pyrolysis step in the pyrolysis unit including feeding to the pyrolysis unit: the solid feed stream includes at least 50 mass % of waste tire particles for generating the waste tire pyrolysis oil feedstock.

[0030] In one embodiment, the solid feed stream includes at least 60 mass %, or at least 70 mass % or at least 80 mass % or at least 90 mass % of waste tire particles, and the waste tire pyrolysis oil feedstock includes 0.5 to 2 mass % of O.

[0031] The higher the content of waste tire particles in the solid feed stream, the lower the oxygen content obtainable in the waste pyrolysis oil feedstock. For example, a solid feed stream to a pyrolysis unit including at least 90 mass % of waste tire particles produces a waste tire pyrolysis oil feedstock including 1 mass % or less of O, thereby enabling a milder condition in the stabilization step or in a subsequent hydrogenation step, for example, by using a lower range of temperature.

[0032] In an embodiment, the pyrolysis step is a fast pyrolysis step.

[0033] As is well known in the art, the pyrolysis step can include the use of a pyrolysis unit such as a fluidized bed, a transport bed, or a circulating fluidized bed. For example, the pyrolysis step can include the use of a pyrolysis unit (also referred to herein as a pyrolysis reactor), the use of a cyclone to remove particulate solids such as carbon, and thereby the use of a cooling unit to produce a first offgas stream (i.e., pyrolysis offgas) and a first liquid oil stream, i.e., condensed pyrolysis oil. This first offgas stream contains light hydrocarbons such as C1-C4 hydrocarbons, CO and CO2. The first liquid oil stream, also called pyrolysis oil or bio-oil, is typically a liquid material rich in a mixture of molecules consisting of over 200 different compounds including other compounds such as aldehydes, ketones and / or furfural having a carbonyl group, and results from the depolymerization of the products treated by pyrolysis.

[0034] For the purposes of the present invention, the pyrolysis step is preferably fast pyrolysis, also known as flash pyrolysis. Fast pyrolysis means the thermal decomposition of a solid renewable feedstock in the absence of oxygen, at a temperature in the range of 350 to 650 °C, for example about 500 °C, with a reaction time of less than 10 seconds, for example 5 seconds or less, for example about 2 seconds; that is, the vapor residence time is 10 seconds or less, for example less than 2 seconds, i.e., 2 seconds. Conventionally, fast pyrolysis could also be carried out, for example, by autothermal operation in a fluidized bed reactor. The latter is also called auto-pyrolysis or is characterized by the use of a mixture of air and an inert gas or recycle gas. Thereby, the partial oxidation of the pyrolysis compounds produced in the pyrolysis reactor (autothermal reactor) supplies the energy for the pyrolysis and at the same time improves heat transfer. For details on auto-pyrolysis, see, for example, "Heterodoxy in Fast Pyrolysis of Biomass" by Robert Brown: https: / / dx.doi.org / 10.1021 / acs.energyfuels.0c03512.

[0035] Accordingly, in an embodiment of the present application, as a specific embodiment for performing fast pyrolysis, auto-pyrolysis, i.e., the use of auto-pyrolysis, is provided, i.e., the pyrolysis step is carried out by auto-pyrolysis.

[0036] There are several types of fast pyrolysis in which catalysts are used. In a pyrolysis apparatus (pyrolysis reactor), sometimes an acid catalyst such as a zeolite catalyst is used to upgrade the pyrolysis vapor; this technique is called catalytic fast pyrolysis (CFP), and it can be operated in both an internal mode (in-situ mode) (the catalyst is located inside the pyrolysis apparatus) and an external mode (ex-situ mode) (the catalyst is placed in a separate reactor. That is, the pyrolysis gas is sent to a deoxygenation (DO) reactor to catalytically deoxygenate it before condensing the pyrolysis oil as described above). More specifically, in in-situ catalytic fast pyrolysis, the catalyst is located inside the pyrolysis unit, and deoxygenation is carried out inside the pyrolysis reactor (through decarboxylation, decarboxylation by an acid-based catalyst such as a zeolite catalyst) immediately after the pyrolysis vapor is formed. Suitable catalysts for CFP include alumina and all types of zeolite catalysts commonly used for hydrocracking (HCR) and cracking in purification processes such as HZSM-5. A more extensive list of catalyst materials for HCR is described later in this application.

[0037] Similarly, in internal (in-situ) HDO (also called reaction catalytic fast pyrolysis, RCFP), a hydrodeoxygenation (HDO) catalyst is located in the pyrolysis unit, and hydrodeoxygenation occurs immediately in the pyrolysis reactor after the pyrolysis vapor is formed. Suitable catalysts for HDO are metal-based catalysts, for example, reduced Ni, Mo, Co, Pt, Pd, Re, Ru, Fe, for example, including CoMo or NiMo catalysts, and preferably in sulfide form: CoMoS, NiS, NiMoS, NiWS, NiWS, RuS. The catalyst support is the same as in conventional HDO in the purification step and may typically be a refractory support such as alumina, silica, or titania, or a combination thereof. Note that the HDO conditions are also described further below in this application.

[0038] In the ex-situ mode of deoxygenation (DO), the steam is deoxygenated in a separate DO reactor located downstream of the pyrolysis unit. Thus, in external catalytic fast pyrolysis, the steam is deoxygenated using an acid catalyst such as a zeolite catalyst.

[0039] In external HDO, the pyrolysis steam is hydrodeoxygenated in a separate HDO reactor located downstream of the pyrolysis reactor using a hydrotreating catalyst.

[0040] By using a catalyst in the pyrolysis reactor, the activation energy of the reaction is reduced, thereby having the advantage of significantly reducing the temperature required to perform pyrolysis. In addition, an increase in selectivity for the desired pyrolysis oil compounds can be achieved.

[0041] When hydrogen is added to catalytic fast pyrolysis, it will be understood to be called reactive catalytic fast pyrolysis (RCFP). Furthermore, when catalytic fast pyrolysis is carried out at a high hydrogen pressure (> about 5 barg), it is often called catalytic hydro-pyrolysis (CHP). Hydrolysis (HP) means that hydrogen is added to the pyrolyzate, but at atmospheric pressure.

[0042] The pyrolysis step is also simple fast pyrolysis, which for the purposes of this application means that fast pyrolysis is carried out without the presence of a catalyst and hydrogen in the pyrolysis unit, i.e., fast pyrolysis does not fall under any of catalytic fast pyrolysis (CFP), hydro-pyrolysis (HP), reactive catalytic fast pyrolysis (RCFP) or catalytic hydro-pyrolysis (CHP). The pyrolysis unit can be without an HDO reactor downstream. This enables a much simpler and cheaper process.

[0043] The following table summarizes the various options of fast pyrolysis, apart from auto-pyrolysis:

[0044]

Table 1

[0045] Therefore, in an embodiment, the pyrolysis step is fast pyrolysis, the vapor residence time is 10 seconds or less, for example, 5 seconds or less, for example, about 2 seconds or 1 second, etc., or in the range of 1 to 5 seconds, and is selected from the following: simple fast pyrolysis; in-situ catalytic fast pyrolysis (in-situ CFP); ex-situ catalytic fast pyrolysis (ex-situ CFP); reactive catalytic fast pyrolysis (RCFP); hydrolysis (HP); catalytic hydrolysis (CHP).

[0046] In another embodiment, the pyrolysis step is slow pyrolysis, and the vapor residence time is in the range of 10 seconds to 5 minutes, for example, 11 seconds to 3 minutes. For fast pyrolysis, the temperature is also in the range of 350 to 650 °C, for example, about 500 °C. This pyrolysis is often carried out in a pyrolysis reactor for handling different types of waste, and the vapor is burned after the pyrolysis reactor. Typical reactors are Helerchoff reactors, rotary drums, Amaron, Choren paddle pyrolysis kilns, auger reactors, and vacuum pyrolysis reactors.

[0047] In another embodiment, the pyrolysis step is slow pyrolysis, and the solid residence time is in the range of 5 minutes to 2 hours, for example, 10 minutes to 1 hour. Appropriately, the temperature is about 300 °C. This pyrolysis results in a high carbohydrate yield, and the carbon can be used as fertilizer or as carbon; the pyrolysis still produces a certain amount of gas and bio-crude oil. When the carbon is used as fertilizer, the final bio-oil becomes a GHG exceeding 100%, and thus is carbon-negative. Typical reactors are auger reactors (having a different residence time from intermediate pyrolysis), fixed bed reactors, kilns, Lambiotte SIFIC / CISR retorts, Lurgi processes, wagon reactors, and carbon twins resorts.

[0048] In an embodiment, the pyrolysis step further includes a preliminary step of passing a solid renewable feedstock through a solid renewable feedstock production section and including, for example, drying to remove water and / or grinding for particle size reduction. For example, any water / moisture in the solid renewable feedstock that evaporates in the pyrolysis section is condensed in the pyrolysis oil stream, thereby being carried out during the process but may not be desirable. Further, the heat used for water evaporation removes the heat required for pyrolysis. By removing water and providing a smaller particle size in the solid renewable feedstock, the thermal efficiency of the pyrolysis step is increased.

[0049] The preliminary step may also include performing pickling to remove metals. This is particularly relevant to the pyrolysis process where the catalyst is located within the pyrolysis reactor. Removing metals from the solid renewable feedstock extends the catalyst life.

[0050] In particular, hydrocarbon fuel diesel produced from a waste tire pyrolysis oil feed containing 0.1 to 5% by weight, for example 0.5 to 2% by weight of O, is rich in aromatics, and thus the density and cetane index of the diesel fraction are too high to meet the EN590 diesel specification. Therefore, a significant problem associated with such highly bio-crude oil (i.e., waste tire pyrolysis oil) is that it has a very large number of aromatics such that the cyclic alkanes also do not have the best cetane index and are thus not necessarily sufficient for hydrodearomatization (HDA) in an HDA reactor, and thus ring opening by hydrocracking is required. However, by co-processing with, for example, vegetable oils, it is now possible to minimize the hydrocracking and / or isomerization required to obtain a good cetane index such as the cetane index (CCI according to standard ASTM D4737), which is also simply called CCI, for example higher than 40, for example 45 - 60, and at the same time increase the diesel yield.

[0051] For example, hydrotreated vegetable oil (HVO), or hydrotreated cooking oil (hydrotreated used cooking oil), has a very high cetane index (CCI) and low density, but poor low-temperature flow properties. The low-temperature flow properties are appropriately measured by the cloud point (CP according to ASTM D57773), hereinafter simply also referred to as CP. A combination of a waste tire pyrolysis oil feed from waste tire pyrolysis and HVO or hydrotreated cooking oil, optionally with subsequent hydroisomerization (HDI), results in a particularly good diesel fuel compliant with the EN590 standard, including adaptation to desirable low-temperature flow properties, for example with respect to the cloud point (CP).

[0052] Thereby, a significant synergistic effect is achieved, at least with respect to the reduction of CP and / or the reduction of heavy end formation.

[0053] For example, the CP of hydrotreated waste pyrolysis oil (H-WTP oil) is 6°C, while the CP of HVO is 22°C. By combining H-WTP oil with HVO, the CP can be significantly reduced to a value significantly lower than either H-WTP or HVO, for example, down to -4°C.

[0054] Accordingly, in an embodiment, the feed of the vegetable oil and / or fatty substance is hydrotreated, for example, a feed of hydrotreated vegetable oil and / or fatty substance (for example, a feed of hydrotreated vegetable oil and / or a feed of hydrotreated fatty substance). Suitably, this feed is supplied from the outside.

[0055] In one embodiment, the method further comprises feeding a feed of vegetable oil and / or fatty substance to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor before combining with the waste tire pyrolysis oil feed to produce a hydrogenated, i.e., hydrotreated, feed of vegetable oil and / or fatty substance. Thereby, hydrotreated vegetable oil, such as HVO or hydrotreated cooked oil, is supplied internally and integrated into the process.

[0056] In one embodiment, the method further comprises supplying a waste tire pyrolysis oil feed or a stabilized waste tire pyrolysis oil feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor before combining with a vegetable oil and / or a fatty substance or before combining with a hydrogenated vegetable oil and / or a fatty substance feed, to produce a hydrogenated tire pyrolysis oil feed or a hydrogenated stabilized waste tire pyrolysis oil feed.

[0057] Despite the low oxygen content, waste tire pyrolysis oil is rich in aromatics, resulting in a reduction in heavy end formation by hydrogenation, i.e., a reduction in heavy end formation by hydrogenation treatment with, for example, a waste tire pyrolysis oil feed or a stabilized waste tire pyrolysis oil feed accompanied by a vegetable oil and / or a fatty substance.

[0058] In one embodiment, the waste tire pyrolysis oil feed can contain a significant amount of aromatic compounds. Thus, the waste tire pyrolysis oil feed, measured according to ASTM D6591, may contain 35 - 65 wt% aromatics (total), for example 45 - 55 wt% aromatics (total).

[0059] The hydrogen-treated stabilized waste tire pyrolysis oil feed, measured according to ASTM D6591, may contain 25 - 55 wt% aromatics (total), for example 35 - 50 wt% aromatics (total).

[0060] In certain embodiments, the HDO / DO step of the waste pyrolysis oil feed or the stabilized waste tire pyrolysis oil feed is carried out in the same HDO / DO reactor used to carry out the HDO / DO step of the vegetable oil and / or fatty substance feed.

[0061] Thereby, simplification by integration in the method and the plant is achieved, along with a reduction in plot size, and consequently, a reduction in capital and operating costs. For example, in the same HDO / DO reactor, vegetable oil is hydrogenated in the first catalyst bed and then combined with a waste tire pyrolysis oil feed or a stabilized waste tire pyrolysis oil feed before entering a second downstream catalyst bed in the HDO / DO reactor.

[0062] Strictly speaking, deoxygenation (DO) does not exist for the purposes of this application, for example, by the addition of hydrogen, but it is understood that it is still considered a hydrogen treatment step.

[0063] The hydrocarbon feed is a combination of A) a waste tire pyrolysis oil feed and B) a vegetable oil and / or fatty substance, and is produced from: A) a waste tire pyrolysis oil feed, or a stabilized waste tire pyrolysis oil feed, or a hydroprocessed waste tire pyrolysis oil feed, or a hydrogenated stabilized waste tire pyrolysis oil feed; and B) a vegetable oil and / or fatty substance, or a hydrogenated vegetable oil and / or fatty substance.

[0064] Furthermore, as described further below, additional feeds may be combined.

[0065] Thus, the waste tire pyrolysis oil may or may not be hydroprocessed, for example, and may or may not be hydrogenated, and the vegetable oil and / or fatty substance may or may not be hydroprocessed, for example, before being mixed into the hydrocarbon feed, and may or may not be hydrogenated.

[0066] In one embodiment, the method further comprises, optionally in a subsequent HDO / DO reactor, feeding the hydrocarbon feed to a subsequent HDO / DO step to produce a hydroprocessed hydrocarbon feed.

[0067] Therefore, several layouts have been proposed, for example: - Providing at least two HDO / DO reactors. For example, vegetable oil is hydrogenated to produce hydrogenated vegetable oil, which is then mixed with the waste tire pyrolysis oil feed or the stabilized waste tire pyrolysis oil feed, and the mixture, i.e., the hydrocarbon feed, is then sent to a subsequent (second) HDO / DO reactor. - Feeding only one HDO / DO reactor and co-processing vegetable oil or hydrogenated vegetable oil in the first catalyst bed, then mixing with the waste tire pyrolysis oil feed or the stabilized waste tire pyrolysis oil feed, and feeding the mixture to the (downstream) catalyst bed below the HDO / DO reactor.

[0068] The present application enables the co-processing of fatty substances such as vegetable oil and / or fatty acids with waste tire pyrolysis oil, which is not possible by other methods. Further, for example, vegetable oil is used to cool the product from the HDO / DO reactor or as a coolant between the beds in the HDO reactor.

[0069] In one embodiment, the method further includes: Feeding the hydrocarbon feed or the hydrogenated hydrocarbon feed to subsequent hydrogenation steps in a downstream hydrogenation section, such as a hydroisomerization (HDI) step in an HDI reactor, and / or a hydrocracking (HCR) step in an HCR reactor, and / or a hydrodearomatization (HDA) step in an HDA reactor to produce a further hydrogenated hydrocarbon feed.

[0070] Thus, the subsequent hydrogenation step involves treating the combined feed in one or more additional catalytic hydrogenation units under the addition of hydrogen, such as a third catalytic hydrogenation unit or a cracking section. For example, if hydrocarbon products boiling in the jet fuel range are desired, it is understood that, for example, a hydrocracking (HCR) unit is suitably used before passing the thus-treated stream to the HDI.

[0071] This embodiment is understood to include a method that does not include a hydrocarbon feed for the waste tire pyrolysis feed subjected to the HDO / DO step and / or the vegetable oil and / or fatty substance feed subjected to the HDO / DO step.

[0072] Typically, pyrolysis oil contains a large amount of oxygen compounds and unsaturated hydrocarbons. During the hydrogenation treatment of this feed, oxygen is mainly removed as H2O, and a fuel mainly composed of naphthenes and aromatic compounds is obtained. This is called the hydrodeoxygenation (HDO) pathway. Oxygen is also removed by the decarboxylation pathway that produces CO2 instead of H2O:

Chemical formula

[0073] Materials having catalytic activity during HDO (interchangeable with the term hydrogenation treatment as used herein) typically include active metals (sulfided base metals such as nickel, cobalt, tungsten, and / or molybdenum, and also include elemental noble metals such as platinum and / or palladium if possible) and refractory supports (such as alumina, silica, or titania, or combinations thereof).

[0074] The HDO conditions include a temperature between 250 and 400 °C, a pressure between 30 and 150 bar, and a liquid hourly space velocity (LHSV) between 0.1 and 2, optionally including intermediate cooling by cold hydrogen, quenching of the feed or product.

[0075] Materials having catalytic activity in hydroisomerization HDI typically include an active metal (elemental noble metal such as platinum and / or palladium, or sulfided base metal such as nickel, cobalt, tungsten and / or molybdenum), an acidic support (typically a molecular sieve having high shape selectivity and a topology such as MOR, FER, MRE, MWW, AEL, TON and MTT), and a refractory support (alumina, silica or titania, or a combination thereof).

[0076] The HDI conditions include a temperature between 250 and 400 °C, a pressure between 20 and 100 bar and a liquid hourly space velocity (LHSV) in the range of 0.5 to 8.

[0077] Materials having catalytic activity in hydrocracking (HCR) have properties similar to those of materials having catalytic activity in isomerization, which typically include an active metal (elemental noble metal such as platinum and / or palladium, or sulfided base metal such as nickel, cobalt, tungsten and / or molybdenum), an acidic support (typically a molecular sieve having high cracking activity and a topology such as MFI, BEA and FAU) and a refractory support (such as alumina, silica or titania, or a combination thereof). The difference from materials having catalytic activity in isomerization is typically the nature of the acidic support, which may be of a different structure (even amorphous silica-alumina) and may have different acidity, such as by the silica:alumina ratio.

[0078] The HCR conditions include a temperature between 250 and 400 °C, a pressure between 30 and 150 bar, and a liquid hourly space velocity (LHSV) between 0.5 and 8, optionally including intermediate cooling by cold hydrogen, quenching of the feed or product.

[0079] Materials having catalytic activity in HDA typically include an active metal (which is a noble metal element, such as platinum and / or palladium, but may also include sulfide-based metals such as nickel, cobalt, tungsten and / or molybdenum) and a refractory support (including, for example, amorphous silica-alumina, alumina, silica or titania).

[0080] The HDA conditions include a temperature between 200 and 350 °C, a pressure between 20 and 100 bar or between 20 and 200 bar, and a liquid hourly space velocity (LHSV) between 0.5 and 8.

[0081] In one embodiment, the method includes the following: - Further supplying the further hydroprocessed feed to a separation step in a separation section to produce a hydrocarbon product, The hydrocarbon product is any of naphtha, diesel, jet fuel, marine (ship) fuel as a heavy fraction, or a combination thereof.

[0082] Thus, the marine (ship) fuel is suitably taken out as a heavy fraction.

[0083] According to one embodiment, the mass ratio (A:B) of the waste tire pyrolysis oil feed (A) to the vegetable oil and / or fatty substance feed (B) is in the range of 50:50 mass% to 10:90 mass%, for example, 60:40, 70:30, 75:25, 80:20, or 85:15 mass%, and optionally, the subsequent HDO / DO step is carried out in continuous mode under conditions of 250 to 400 °C, for example 350 to 380 °C, a pressure of 50 to 150 bar, for example 100 bar, and a fixed bed catalyst where the catalyst is NiMoS and / or MoS.

[0084] At the above mass ratio (A:B), for example, by combining the hydrotreated waste tire pyrolysis oil with a hydrotreated vegetable oil, such as HVO, the obtained diesel oil shows desirable results regarding the cetane index and compliance with the specifications (EN590 standard), which also includes improved low-temperature flow properties regarding the cloud point. At least, a high synergistic effect is obtained due to the obtained diesel having a lower cloud point than A or B, and further, for example, when a MoS catalyst is provided by introducing it to the upper part of the HDO / DO reactor, the formation of heavy ends is further reduced.

[0085] It will be understood that the temperature of a given reactor refers to the inlet temperature in an adiabatic fixed-bed reactor or the reaction temperature in an isothermal reactor.

[0086] Suitably, either the stabilization reactor and a hydroprocessing reactor such as an HDO / DO reactor or an HDI reactor or an HCR reactor or an HDA reactor is an adiabatic fixed-bed reactor.

[0087] A specific combination of co-processing, at these mass ratios, and, as described above, the provision of NiMoS and / or MoS catalysts in the subsequent HDO / DO step enables a further reduction of the heavy fraction (C18+ formation). Thus, the yield of diesel, which is in the range of C15 - C18, increases.

[0088] Downstream of the desirable hydrocarbon product is, in an embodiment, diesel as the hydrocarbon product boiling in the transport fuel range, which is suitably represented by C15 - C18 hydrocarbons. Hydrocarbons having more than 18 carbon atoms (C18+) may be taken downstream of the separation section as the heavy fraction (also referred to herein as the heavy ends), but it would be desirable to reduce this heavy fraction in order to increase the yield of the C15 - C18 fraction and thus the yield of diesel fuel. The present invention has been found to enable lower production of the heavy end fraction while maintaining proper miscibility of the feed. Without being bound by any theory, the aromatics in the waste tire pyrolysis oil feed are thought to act as hydrogen donors and thereby reduce heavy end formation, despite the low O content as previously described. A conventional approach when dealing with heavy ends is to hydrocrack the heavy portion of the product and thereby remove the heavy ends. However, hydrocracking results in yield losses. Thus, minimizing heavy end formation increases the overall yield of the process, particularly the diesel yield. Further, as explained, the low temperature flow properties regarding cloud point are significantly improved.

[0089] In one embodiment, the feed of the vegetable oil and / or fatty substance is any of the following: Soybean oil, such as, soybean oil, rapeseed oil, corn oil, castor oil, cooking oil, animal fats, such as, beef, pork, milk, chicken fat; and combinations thereof.

[0090] For example, the fatty substance feed contains fatty acids and the fatty substance feed is suitably any of triglycerides, diglycerides, monoglycerides, and free fatty acids.

[0091] As further described above, in one embodiment, the hydrogenated vegetable oil and / or fatty substance is selected from hydrogenated vegetable oil (HVO) or hydrogenated cooking oil.

[0092] This special co-feed results in a diesel fuel compliant with the EN590 standard, including improved low-temperature flow properties, including a high cetane index of diesel produced in the range of, for example, 40 to 60 and a low heavy-end fraction. Furthermore, the cloud point can be significantly reduced by providing a cloud point that is much lower than either waste tire pyrolysis oil alone or, for example, vegetable oil alone, as already explained.

[0093] When combining a bio-crude oil containing 0.1 to 5% by mass of O, i.e., waste tire pyrolysis oil, with a vegetable oil and / or fatty substance feed, an additional feed can be provided for manufacturing the hydrocarbon feed. Thus, in one embodiment, the step of combining waste tire pyrolysis oil with a vegetable oil and / or fatty substance feed is further combined with an additional feed; the additional feed is suitably the following: A feed derived from a fossil feed, i.e., a feed derived from a fossil fuel source such as diesel, kerosene, naphtha, vacuum gas oil (VGO), etc., and / or An intermediate hydrocarbon product, for example, a recycled oil by recycling the intermediate hydrocarbon product produced in this method, i.e., a part of the hydroprocessed hydrocarbon feed produced downstream, the hydroprocessed hydrocarbon feed or the further hydroprocessed hydrocarbon feed.

[0094] Thus, suitably, the intermediate hydrocarbon product produced by this method is a part of the hydroprocessed hydrocarbon feed or the further hydroprocessed hydrocarbon feed.

[0095] According to one embodiment, the method further includes supplying, as heavy fractions, diesel fuel and marine (ship) fuel, or a combination thereof, to a hydroisomerization (HDI) step in an HDI reactor and / or a hydrocracking (HCR) step in an HCR reactor to produce an intermediate hydrocarbon product, for example, the intermediate hydrocarbon product produced during the method.

[0096] Accordingly, in the separation section, for example, diesel fuel and marine fuel are withdrawn therefrom in a distillation column, and either these hydrocarbon products or a part thereof is supplied to HDI and / or HCR. Accordingly, such hydrocarbon products, for example, marine fuel hydrotreated in an HCR reactor, are advantageously added after combining with a waste tire pyrolysis oil feedstock and, suitably, a hydrotreated vegetable oil and / or fatty substance feedstock. As already described, a high synergistic effect has been found by hydrotreating each of these streams separately.

[0097] In one embodiment, the method includes a pre-solvent extraction step of a biocrude oil feedstock such as a toluene extraction step before, to produce the waste tire pyrolysis oil feedstock.

[0098] In a second aspect, it relates to a plant for implementing a method according to any of the above embodiments according to the first aspect of the present invention. The plant comprises - a conduit for providing a biocrude oil feedstock containing 0.1 to 5% by mass of oxygen (O), where the biocrude oil feedstock is a waste tire pyrolysis oil feedstock; - a conduit for providing a vegetable oil and / or fatty substance feedstock; - a mixing point, such as a mixing unit or a junction, for producing a hydrocarbon feedstock by combining a biocrude oil containing 0.1 to 5% by mass of O and a vegetable oil and / or fatty substance feedstock; - optionally, upstream of the mixing point, a stabilization reactor arranged to receive a waste tire pyrolysis oil feedstock and provide a stabilized waste tire pyrolysis oil feedstock, and includes.

[0099] It is understood that any of the embodiments of the first aspect of the present invention can be used in connection with the related benefits in connection with the second aspect of the present invention.

Examples

[0100] Example: Increase the cetane index of diesel while improving the low-temperature flow properties and reducing the heavy end fraction. Bio-crude oil was produced from the pyrolysis of waste tires (i.e., waste tire pyrolysis oil feedstock). The oxygen (O) content ranges from 0.5 to 2% by mass. This feedstock is combined with hydrogenated vegetable oil (HVO) hydrogenated at different weight ratios, such as 1:1 (50% by mass hydrogenated waste tire pyrolysis oil (H-WTP oil) and 50% by mass HVO).

[0101] Despite the low O content, waste tire pyrolysis oil has a high aromatic content, too high a density for the diesel fraction, and too low a cetane index to meet the EN590 diesel standard. HVO has a very high cetane index and low density but poor low-temperature fluidity. H-WTP and HVO were found to be miscible. Furthermore, the mixture of these two feedstocks interacts synergistically to provide a diesel fuel that meets the EN590 standard by providing a high cetane index and a low amount of heavy end fraction in the produced diesel. Additionally, when combined within a specific range of mass ratios, a dramatic improvement in low-temperature flow properties is achieved. The results are shown in the following table.

[0102] The cetane index is 36 (CCI according to standard D4737) and the cloud point (CP) is 6 °C (according to standard D 5773) of the stabilized and hydrotreated waste tire pyrolysis oil (H-WTP oil) was mixed with HVO (CCI is 104 and CP is 22 °C) using the following mass ratios: 75:25, 50:50, and 26:74. The results in the table show that when HVO is mixed with the hydrogenated (hydrotreated) waste tire pyrolysis oil (H-WTP oil), the CCI of the waste tire pyrolysis oil increases, that is, when the hydrogenated tire pyrolysis oil is co-fed with vegetable oil, diesel with the desired CCI is produced. Furthermore, it was also shown that when HVO is mixed with H-WTP oil, the CP of the H-WTP oil also surprisingly decreases, although HVO has a much higher CP. Without being bound by any theory, this is related to an increase in the solubility of the heavy end fraction of the H-WTP oil, which is more soluble in the lighter fraction when mixed with the C15-C18 alkanes present in HVO and thus reduces the CP. Therefore, the mixing of HVO and H-WTP oil improves not only the cetane index but also the cloud point; especially when the mass ratio of H-WTP oil to HVO is 60:40 mass% or 75:25 mass% or 80:20 mass% or 90:10 mass%.

[0103]

Table 2

Claims

1. A method for producing a hydrocarbon feedstock, comprising the following steps: - providing a biocrude feedstock containing 0.1 to 5% by mass of oxygen (O); - providing a vegetable oil and / or fatty substance feedstock; - producing the hydrocarbon feedstock by combining the biocrude feedstock containing 0.1 to 5% by mass of O with the vegetable oil and / or fatty substance feedstock; The method, wherein the biocrude feedstock containing 0.1 to 5% by mass of O is a waste tire pyrolysis oil feedstock.

2. - prior to the combining step, feeding the waste tire pyrolysis oil feedstock to a stabilization step in a stabilization reactor to produce a stabilized waste tire pyrolysis oil feedstock: The method according to claim 1, further comprising.

3. The stabilization step is carried out in a fixed bed reactor in continuous operation mode, in the presence of any of Ni-Mo, Co-Mo, Ni-Cu, Mo, Pt, Pd, Ru, or Ni-based catalysts, at a temperature of 20-240 °C, a pressure of 50-150 barg, optionally 0.1-2 h －１ of liquid hourly space velocity (LHSV), and a hydrogen-to-liquid oil ratio defined as the volume ratio of hydrogen to the flow rate of the liquid oil stream of 250-3000 NL / L, for example 500-2500 NL / L, comprising feeding the bio-crude oil feed together with hydrogen, thereby forming the stabilized waste tire pyrolysis oil feed, the method according to claim 2.

4. The method according to any one of claims 1 to 3, further comprising a pyrolysis step in the pyrolysis unit, which comprises feeding a solid feed stream containing at least 50% by mass of waste tire particles to the pyrolysis unit to produce the waste tire pyrolysis oil feedstock.

5. The method according to claim 4, wherein the solid feed stream contains at least 60% by mass, or at least 70% by mass, or at least 80% by mass, or at least 90% by mass of waste tire particles, and the waste tire pyrolysis oil feedstock contains 0.5 to 2% by mass of O.

6. The method according to any one of claims 1 to 5, wherein the vegetable oil and / or fatty substance feedstock is a hydroprocessed vegetable oil and / or fatty substance feedstock, such as a hydrogenated vegetable oil and / or fatty substance feedstock.

7. The method according to any one of claims 1 to 5, further comprising feeding the vegetable oil and / or fatty substance feedstock to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor to produce a hydroprocessed vegetable oil and / or fatty substance feedstock before combining with the waste tire pyrolysis oil feedstock.

8. Before combining with the vegetable oil and / or fatty substance, or before combining with the hydrogenated vegetable oil and / or fatty substance feed, the waste tire pyrolysis oil feed or the stabilized waste tire pyrolysis oil feed is supplied to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor to produce a hydrogenated waste tire pyrolysis oil feed or a hydrogenated stabilized waste tire pyrolysis oil feed. The method according to any one of claims 1 to 7, further comprising this.

9. The HDO / DO step of the waste pyrolysis oil feed or the stabilized waste tire pyrolysis oil feed is carried out in the same HDO / DO reactor as that for carrying out the HDO / DO step of the vegetable oil and / or fatty substance feed. The method according to any one of claims 7 to 8.

10. Optionally, in a subsequent HDO / DO reactor, further comprising supplying the hydrocarbon feed to a subsequent HDO / DO step to produce a hydrogenated hydrocarbon feed. The method according to any one of claims 1 to 9.

11. - Supplying the hydrocarbon feed or the hydrogenated hydrocarbon feed to subsequent hydroprocessing steps in a downstream hydroprocessing section, such as a hydroisomerization (HDI) step in an HDI reactor, and / or a hydrocracking (HCR) step in an HCR reactor, and / or a hydrodearomatization (HDA) step in an HDA reactor, to produce a further hydrogenated hydrocarbon feed The method according to any one of claims 1 to 10, further comprising this.

12. - Further comprising supplying the further hydrogenated hydrocarbon feed to a separation step in a separation section to produce a hydrocarbon product, The method according to claim 11, wherein the hydrocarbon product is any one of naphtha, diesel, jet fuel, marine (ship) fuel as a heavy fraction, or a combination thereof.

13. The mass ratio (A:B) of the waste tire pyrolysis oil feed (A) to the vegetable oil and / or fatty substance feed (B) is in the range of 50:50% by mass to 90:10% by mass, for example 60:40, 70:30, 75:25, 80:20 or 85:15% by mass, and optionally, any of said HDO / DO steps is carried out in continuous mode using a fixed bed catalyst where the catalyst is NiMoS and / or MoS, under conditions of 250 - 400 °C and a pressure of 50 - 150 bar, optionally, the method according to any one of claims 1 to 12.

14. The method according to any one of claims 1 to 13, wherein the vegetable oil and / or fatty substance feed is any one of soybean oil, rapeseed oil, corn oil, castor oil, cooked oil, animal fat, and combinations thereof.

15. The method according to any one of claims 6 to 14, wherein the hydrogenated vegetable oil and / or fatty substance is selected from hydrogenated vegetable oil (HVO) or hydrogenated cooked oil.

16. The method according to any one of claims 1 to 15, wherein the step of combining the waste tire pyrolysis oil feed with the vegetable oil and / or fatty substance feed is combined with a further feed; suitably the further feed is: A fossil feed, for example, diesel, kerosene, naphtha, vacuum gas oil (VGO), and / or An intermediate hydrocarbon product, for example, recycled oil, that is, a recycled oil by reusing a part of the intermediate hydrocarbon product produced in the method, for example, of the hydrogenated hydrocarbon feed or of the further hydrogenated hydrocarbon feed, the method.

17. The method according to any one of claims 12 to 16, further comprising feeding the diesel and the marine (ship) fuel as heavy fraction or combinations thereof to a hydroisomerization (HDI) step in an HDI reactor and / or a hydrocracking (HCR) step in an HCR reactor to provide the intermediate hydrocarbon product, for example, the intermediate hydrocarbon product produced within the method.

18. A plant for carrying out the method according to any one of claims 1 to 17, - A conduit for providing a biocrude feedstock containing 0.1 to 5% by mass of oxygen (O), wherein the biocrude feedstock is a waste tire pyrolysis oil feedstock; - A conduit for providing a vegetable oil and / or fatty substance feedstock; - A mixing point for producing a hydrocarbon feedstock by combining the biocrude containing 0.1 to 5% by mass of O with the vegetable oil and / or fatty substance feedstock; - Optionally, upstream of the mixing point, a stabilization reactor arranged to receive the waste tire pyrolysis oil feedstock and provide a stabilized waste tire pyrolysis oil feedstock, The plant comprising.

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