Hydroprocessing of waste tire pyrolysis oil with vegetable and / or fat materials

Abstract

The present application provides a process and apparatus for producing a hydrocarbon feed, the process comprising: providing a bio-crude oil feed comprising from 0.1 to 5 wt% of oxygen (O); providing a vegetable oil and / or fat material feed; combining a bio-crude oil feed comprising from 0.1 to 5 wt% O with a vegetable oil and / or fat material feed to produce the hydrocarbon feed; wherein the bio-crude oil feed comprising from 0.1 to 5 wt% of O is a waste tire pyrolysis oil feed.

Description

[0001] The present invention relates to a method and apparatus for hydroprocessing a biocrude feed produced by thermal decomposition of a solid feed stream comprising waste tires, the thermal decomposition being pyrolysis, and a vegetable and / or fatty material feed. The solid feed stream comprises waste tires, the thermal decomposition being pyrolysis, and the biocrude feed being waste tire pyrolysis oil.

[0002] Co-processing of hydrocarbon fuel feeds by combining fossil fuel feeds (e.g., petroleum feeds) with vegetable oil feeds in hydroprocessing is well known. However, biocrude produced by thermal decomposition of solid renewable feedstocks (e.g., lignocellulosic biomass) (e.g., by pyrolysis and hydrothermal liquefaction (HTL)) is generally not miscible with vegetable oils and / or fatty materials including fatty acids, and thus co-processing of these feeds in hydroprocessing steps (e.g., hydrodeoxygenation (HDO)) has hitherto been a formidable challenge.

[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 disclosed a study in which catalytic fast pyrolysis (CFP) oil was mixed with vegetable oil (here soybean oil) in a stirred batch reactor.

[0004] However, the applicant has found that vegetable oils are incompatible with most untreated catalytic cracking oils, making it difficult to operate them in industrial hydroprocessing reactors. When operated under industrially relevant conditions, hydroprocessing reactors processing co-feeds will become plugged after a few days.

[0005] It was found that although vegetable oils are immiscible in biocrude oils from catalytic and non-catalytic pyrolysis and hydrothermal liquefaction (HTL), they are miscible in waste tire pyrolysis oil, which has a lower oxygen (O) content and can therefore be considered partially deoxygenated.

[0006] Thus, in a general embodiment according to the first aspect of the present invention there is provided a method of producing a hydrocarbon feed comprising the steps of:

[0007] - providing a bio-crude feed comprising 0.1-5 wt% oxygen (O);

[0008] - providing a feed of vegetable oil and / or fatty material;

[0009] - combining a biocrude feed comprising 0.1-5 wt% O with a vegetable oil and / or fatty material feed to produce said hydrocarbon feed;

[0010] The bio-crude oil feed containing 0.1-5 wt % of O is waste tire pyrolysis oil feed.

[0011] For example, separate waste tire pyrolysis oil feeds may be combined into a single waste tire pyrolysis oil feed containing 0.1-5 wt % O.

[0012] For example, a waste tire pyrolysis oil feed may be combined with a vegetable oil feed or a fatty material feed (such as an animal fat feed).

[0013] For example, a waste tire pyrolysis oil feed may be first combined with a vegetable oil feed and then combined with a fatty material feed (such as an animal fat feed).

[0014] Optionally, additional feed is provided.

[0015] It should be understood that the term "waste tire pyrolysis oil feed" refers to liquid oil produced by pyrolysis of waste tires.

[0016] A biocrude feed comprising 0.1-5 wt% oxygen (O) can be considered a partially deoxygenated biocrude feed.

[0017] Thus, it is now possible to combine waste pyrolysis oil with a vegetable oil and / or fatty material feed without the risk of plugging downstream hydroprocessing reactors (e.g., hydrotreating in a hydrodeoxygenation and / or deoxygenation (HDO / DO) reactor) or any associated units (e.g., pumps and heat exchangers). In addition, the vegetable oil is used to cool the effluent from the HDO / DO reactor (i.e., partially deoxygenated biocrude feed), or as cooling between catalytic beds in the first HDO reactor. In addition, the formation of a heavy fraction in the downstream separation section is reduced, thereby increasing the yield of hydrocarbon fuels such as diesel. Although an oxygen (O) content of less than 2 wt% in the biocrude feed may help to make it miscible with vegetable oil and / or fatty material, such low oxygen values ​​in the biocrude feed are often accompanied by low aromatic content. In contrast, it has been found that waste pyrolysis oil having an oxygen content as low as 0.1-5 wt% (e.g., 0.5-2 wt%) is not only miscible with vegetable oil and / or fatty material feed, but also maintains a high level of aromatic compounds. As will be explained further below, the presence of a significant amount of aromatic compounds is desirable because it reduces the formation of heavy ends in the downstream production and / or separation of hydrocarbon products such as diesel.

[0018] In one embodiment, before the combining step, the method further comprises:

[0019] - Prior to the combining step, the waste tire pyrolysis oil feed is supplied to a stabilization step in a stabilization reactor to produce a stabilized waste tire pyrolysis oil feed.

[0020] The stabilization reactor is also referred to herein as a selective hydrogenation unit.

[0021] Since waste tire pyrolysis oil has a high concentration of aromatics, the formation of heavy fractions in the downstream stage of producing hydrocarbon fuels can be reduced; this is suitably achieved by hydroprocessing (e.g. hydrotreating (HDO / DO)) the stabilized tire pyrolysis oil and then combining it with the vegetable oil and / or fatty material.

[0022] In one embodiment, the stabilization step is carried out in a fixed bed reactor in a continuous operation mode, comprising supplying hydrogen to the bio-crude feed in the presence of any one 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, and optionally a liquid hourly space velocity (LHSV) of 0.1-2 h -1 , and the ratio of hydrogen to liquid oil is 250-3000NL / L, such as 500-2500NL / L, thereby forming the stabilized waste tire pyrolysis oil feed, wherein the ratio of hydrogen to liquid oil is defined as the volume ratio of hydrogen to liquid oil flow rate.

[0023] 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 titanium dioxide), or a Pt / TiO2 based catalyst.

[0024] The terms "Ni-Mo based catalyst", "Co-Mo based catalyst" and the like mean that Ni-Mo is an active element of the catalyst.

[0025] Suitably, Ni—Mo, Co—Mo or Mo is in the form of a sulfide, such as NiMoS. Also suitably, Ni is in the form of a sulfide or a reduced form.

[0026] The term "stabilization" refers to converting the carbonyl group present in liquid oil compounds (such as aldehydes, ketones and acids) into alcohols. Other molecules (such as sugars and furans) can also be converted in the stabilization step. In addition, dienes (such as conjugated dienes) are hydroprocessed. For example, the stabilization step can be carried out by NiMo-based catalysts, as disclosed by Shumeico et al. (Shumeico et al. "Efficient one-stage bio-oil upgrading over sulfidecatalysts", ACS Sustainable Chem. Eng. 2020, 8, 15149-15167). Suitably, stabilization is carried out according to the method disclosed in the applicant's co-pending European patent application 21152117.4 (corresponding to international application PCT / EP2022 / 050877).

[0027] In one embodiment, the vegetable oil and / or fatty material feed is a non-hydroprocessed vegetable oil and / or fatty material feed. Thus, the feed has not been subjected to a prior hydroprocessing step, such as hydrodeoxygenation (HDO).

[0028] For the purposes of this application, the term "first aspect of the invention" relates to a method. The term "second aspect of the invention" refers to a process device, ie an apparatus.

[0029] The terms "present invention" and "this application" are used interchangeably.

[0030] The term "comprising" includes "consisting only of", ie "consisting of.

[0031] The term "suitably" is used interchangeably with the term "optionally", ie an optional embodiment.

[0032] The term "bio-crude feed comprising 0.1-5 wt% oxygen (O)" may be used interchangeably with the term "partially deoxygenated bio-crude feed".

[0033] The term "bio-crude feed" refers to the waste tire pyrolysis oil product of the thermal decomposition step in the thermal decomposition unit, wherein the thermal decomposition unit is a pyrolysis unit. The term "unit" is understood herein as a "reactor".

[0034] Bio-crude feed, here specifically refers to waste tire pyrolysis oil, which can also be understood as "advanced bio-crude".

[0035] The term "vegetable oil feed and / or fatty material" includes vegetable oils such as soybean oil, and fatty materials such as animal fats. Fatty materials include fatty acids.

[0036] The term "section", such as "hydroprocessing section", refers to a physical section comprising a unit or combination of units for performing one or more steps and / or sub-steps (eg, producing a hydroprocessed hydrocarbon feed or a further hydroprocessed hydrocarbon feed).

[0037] The term "hydroprocessing" includes hydrotreating and thus includes hydrodeoxygenation or deoxygenation (HDO / DO). The term "hydroprocessing" also includes hydroisomerization (HDI) or hydrocracking (HCR) or hydrodearomatization (HDA). It is understood that the hydroprocessing step (e.g., HDO / DO step) is carried out in a hydroprocessing reactor (e.g., HDO / DO reactor) or in a catalytic bed of a hydroprocessing reactor (e.g., a catalytic bed of a HDO / DO reactor). The hydroprocessing reactor may include one or more catalytic beds.

[0038] Additional definitions are set forth below in connection with one or more embodiments of the present invention.

[0039] Suitably, in the combining step, the weight ratio (A:B) of the bio-crude feed, i.e. the waste tire pyrolysis oil feed (A) to the vegetable oil and / or fatty material feed (B) is in the following range: 9:1 (i.e. the wt% ratio is 90:10), to 1:9 (i.e. the wt% ratio is 10:90), for example 3:1 (i.e. the wt% ratio is 75:25), 2:1 (i.e. the wt% ratio is 66.6:33.3), 1:1 (i.e. the wt% ratio is 50:50), 1:2 (i.e. the wt% ratio is 33.3:66.6), 1:3 (i.e. the wt% ratio is 25:75), 1:4 (i.e. the wt% ratio is 20:80), 1:5 (i.e. the wt% ratio is 17:83), 1:6 for example 1:5.7 (i.e. the wt% ratio is 15:85).

[0040] It should be understood that the above weight ratios also apply when hydroprocessed feeds are combined, such as when a hydrotreated scrap tire pyrolysis oil feed is combined with a hydrotreated vegetable oil feed.

[0041] In one embodiment, the method further comprises a pyrolysis step in a pyrolysis unit, comprising feeding the pyrolysis unit with a solid feed stream comprising at least 50 wt% waste tire particles for producing the waste tire pyrolysis oil feed.

[0042] In one embodiment, the solid feed stream comprises at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt% of waste tire particles, and the waste tire pyrolysis oil feed comprises 0.5-2 wt% O.

[0043] The higher the content of waste tire particles in the solid feed stream, the lower the oxygen content that can be obtained in the waste pyrolysis oil feed. For example, the solid feed stream entering the pyrolysis unit contains at least 90 wt% of waste tire particles, and the waste tire pyrolysis oil feed produced contains 1 wt% or less O, thereby also achieving milder conditions in the stabilization step, such as by using a temperature in a lower range, or achieving milder conditions in the post-hydroprocessing step.

[0044] In one embodiment, the pyrolysis step is a flash pyrolysis step.

[0045] The pyrolysis step may include the use of a pyrolysis unit, such as a fluidized bed, a conveyed bed, or a circulating fluidized bed, as is well known in the art. For example, the pyrolysis step may include the use of a pyrolysis unit (also referred to herein as a pyrolysis reactor), a cyclone separator (for removing particulate solids, such as char), and a cooling unit, thereby producing the first waste gas stream (i.e., pyrolysis waste gas) and the first liquid oil stream, i.e., condensed pyrolysis oil. The first waste gas stream includes light hydrocarbons, such as C1-C4 hydrocarbons, CO, and CO2. The first liquid oil stream, also known as pyrolysis oil or bio-oil, is a liquid substance rich in a molecular mixture, typically consisting of more than two hundred different compounds, including aldehydes, ketones, and / or other compounds, such as furfural with a carbonyl group, which is formed by the depolymerization of the products of the pyrolysis treatment.

[0046] For the purposes of the present invention, the pyrolysis step is preferably fast pyrolysis, also known in the art as flash pyrolysis. Fast pyrolysis refers to the thermal decomposition of solid renewable raw materials under anaerobic conditions at a temperature of 350-650° C. (e.g., about 500° C.) and a reaction time of 10 seconds or less (e.g., less than 10 seconds, e.g., 5 seconds or less, e.g., about 2 seconds); i.e., a steam residence time of 10 seconds or less (e.g., 2 seconds or less, e.g., about 2 seconds). Traditionally, fast pyrolysis can also be carried out, for example, by autothermal operation, for example in a fluidized bed reactor. The latter is also known as autothermal pyrolysis, which is characterized in that air (optionally with an inert gas or a recycled gas) is used as a fluidizing gas, or a mixture of air and an inert gas or a recycled gas is used. Therefore, partial oxidation of the pyrolysis compounds produced in the pyrolysis reactor (autothermal reactor) provides energy for pyrolysis while improving heat transfer. For detailed information on autothermal pyrolysis, see, for example, the following: Robert Brown, “Heterodoxy in Fast Pyrolysis of Biomass”:

[0047] https: / / dx.doi.org / 10.1021 / acs.energyfuels.0c03512

[0048] Therefore, in one embodiment of the present application, the use of autothermal pyrolysis, ie, autothermal operation, is provided as a specific embodiment for performing rapid pyrolysis, ie, the pyrolysis step is performed by autothermal pyrolysis.

[0049] There are several types of fast pyrolysis in which catalysts are used. Sometimes an acidic catalyst (e.g., a zeolite catalyst) is used in the pyrolysis unit (pyrolysis reactor) to upgrade the pyrolysis steam; this technology is called catalytic fast pyrolysis (CFP), which can be operated in either an in-situ mode (the catalyst is located in the pyrolysis unit) or an ex-situ mode (the catalyst is placed in a separate reactor; that is, the pyrolysis gas is sent to a deoxygenation (DO) reactor, catalytically deoxygenated, and then the pyrolysis oil is condensed, as described above). More specifically, in in-situ catalytic fast pyrolysis, the catalyst is located in the pyrolysis unit, and deoxygenation (by, for example, decarbonylation, decarboxylation by an acidic catalyst such as a zeolite catalyst) occurs in the pyrolysis reactor immediately after the pyrolysis steam is formed. Catalysts suitable for CFP include alumina and all types of zeolite catalysts commonly used for cracking in hydrocracking (HCR) and oil refining processes, such as HZSM-5. A more extensive list of HCR catalytic materials is provided below in this application.

[0050] Similarly, in in-situ HDO (also known as reactive catalytic fast pyrolysis, RCFP), the hydroprocessing (HDO) catalyst is located in the pyrolysis unit and the pyrolysis vapors are hydrodeoxygenated in the pyrolysis reactor immediately after formation. Suitable catalysts for hydrodeoxygenation are metal-based catalysts including Ni, Mo, Co, Pt, Pd, Re, Ru, Fe in reduced form, such as CoMo or NiMo catalysts, also suitably in sulfide form: CoMoS, NiS, NiMoS, NiWS, RuS. The catalyst support may be the same as that in conventional HDO in refining processes, typically a refractory support such as alumina, silica or titania, or a combination thereof. In the following of this application, HDO conditions are also described.

[0051] In ex situ deoxygenation (DO), the steam is deoxygenated in a separate DO reactor located after the pyrolysis unit. Thus, in ex situ catalytic fast pyrolysis, the steam is deoxygenated using an acidic catalyst, such as a zeolite catalyst.

[0052] In ex situ hydrodeoxygenation (HDO), the pyrolysis vapors are hydrodeoxygenated using a hydrotreating catalyst in a separate HDO reactor located after the pyrolysis reactor.

[0053] The use of catalysts in the pyrolysis reactor has the advantage of lowering the activation energy of the reaction, thereby significantly reducing the temperature required to carry out pyrolysis. In addition, it can also increase the selectivity to the desired pyrolysis oil compounds.

[0054] It is understood that when hydrogen is added to catalytic fast pyrolysis, this is referred to as reactive catalytic fast pyrolysis (RCFP). In addition, if catalytic fast pyrolysis is carried out under high hydrogen pressure (~>5 barg), it is usually referred to as catalytic hydropyrolysis (CHP). Hydropyrolysis (HP) refers to the addition of hydrogen to the pyrolysis at atmospheric pressure.

[0055] The pyrolysis step is also suitably a simple fast pyrolysis, which for the purposes of this application means that the fast pyrolysis is carried out in the absence of a catalyst and hydrogen in the pyrolysis unit, i.e. the fast pyrolysis is not any of the following: catalytic fast pyrolysis (CFP), hydropyrolysis (HP), reactive catalytic fast pyrolysis (RCFP) or catalytic fast hydropyrolysis (CHP). The HDO reactor may not be included downstream of the pyrolysis unit. This makes the process simpler and cheaper.

[0056] The following table summarizes the different options for fast pyrolysis in addition to autothermal pyrolysis:

[0057]

[0058] Thus, in one embodiment, the pyrolysis step is fast pyrolysis, wherein the steam residence time is 10 seconds or less, e.g., less than 10 seconds, such as 5 seconds or less, e.g., about 2 seconds or 1 second, or in the range of 1-5 seconds, and is selected from: simple fast pyrolysis; in situ catalytic fast pyrolysis (in situ CFP); ex situ catalytic fast pyrolysis (ex situ CFP); reactive catalytic fast pyrolysis (RCFP); hydropyrolysis (HP); catalytic fast hydropyrolysis (CHP).

[0059] In another embodiment, the pyrolysis step is an intermediate pyrolysis, wherein the steam residence time is in the range of 10 seconds to 5 minutes, for example 11 seconds to 3 minutes. As for fast pyrolysis, the temperature is also in the range of 350-650° C., for example about 500° C. Typically, this pyrolysis is carried out in a pyrolysis reactor for treating different types of waste, wherein the steam is burned after the pyrolysis reactor. Typical reactors are: Herreshoff furnace, rotary drum, amaron, CHOREN paddle pyrolysis kiln, auger reactor and vacuum pyrolysis reactor.

[0060] In another embodiment, the pyrolysis step is a slow pyrolysis in which the solid residence time is in the range of 5 minutes to 2 hours, for example 10 minutes to 1 hour. The temperature is suitably about 300°C. This pyrolysis produces a high char yield, and the char can be used as fertilizer or char coal; pyrolysis still produces some gas and bio-crude oil, and if the carbon is used as fertilizer, the final bio-oil can have more than 100% GHG, so it is carbon negative. Typical reactors are spiral reactors (but the residence time is different from that of intermediate pyrolysis), fixed bed reactors, kilns, lambiotte SIFIC / CISR retorts, Lurgi process, wagon reactors, and carbo twin resorts.

[0061] In one embodiment, the pyrolysis step further comprises a preliminary step of passing the solid renewable raw material through a solid renewable raw material preparation section, which step comprises, for example, drying to remove water and / or comminution to reduce particle size. Any water / moisture present in the solid renewable raw material, after evaporation in, for example, the pyrolysis section, will condense in the pyrolysis oil stream and thus be retained in the process, which may be undesirable. In addition, the heat used to evaporate the water absorbs the heat required for pyrolysis. By removing water and providing a smaller particle size in the solid renewable raw material, the thermal efficiency of the pyrolysis step can be improved.

[0062] The preparatory step may also include an acid wash to remove metals. This is particularly important for pyrolysis processes where the catalyst is located in the pyrolysis reactor. Removing metals from solid renewable feedstocks can extend the life of the catalyst.

[0063] In particular, it has been found that the hydrocarbon fuel diesel produced from a waste tire pyrolysis oil feed containing 0.1-5 wt%, such as 0.5-2 wt%, of O is rich in aromatics, so that the density and cetane index of the diesel fraction are too high to meet the EN590 diesel specification. Therefore, an important problem associated with this advanced bio-crude oil, i.e. waste tire pyrolysis oil, is that it contains so much aromatics that it is not necessarily sufficient to perform a hydrodearomatization (HDA) step alone in a HDA reactor, since the cetane number of the cycloalkanes is also not optimal, and thus requires ring opening by hydrocracking. However, by co-processing it 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 a cetane index (CCI according to standard ASTM D4737), hereinafter also referred to as CCI, above 40, such as 45-60, while increasing the diesel yield.

[0064] For example, hydrotreated vegetable oil (HVO) or hydrotreated cooked oil (hydrotreated waste cooking oil) has a very high cetane index (CCI) and low density, but poor low temperature flow properties. Low temperature flow properties are suitably measured by cloud point (CP according to ASTM D57773), hereinafter also referred to as CP. Combining a waste tire pyrolysis oil feed obtained by pyrolysis of waste tires with HVO or hydrotreated cooked oil, optionally followed by hydroisomerization (HDI), can produce a particularly good diesel fuel that meets EN590 specifications; including meeting the required low temperature flow properties, such as cloud point (CP).

[0065] A significant synergistic effect is thereby achieved at least with regard to the reduction of CP and / or the reduction of the formation of heavy fractions.

[0066] 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 surprisingly be reduced to values ​​significantly lower than that of H-WTP or HVO, such as -4° C.

[0067] Thus, in one embodiment, the vegetable oil and / or fatty material feed is hydroprocessed, such as a hydrotreated vegetable oil and / or fatty material feed (e.g. a hydrotreated vegetable oil feed and / or a hydrotreated fatty material feed). Suitably, the feed is of external origin.

[0068] In one embodiment, the vegetable oil and / or fatty material feed is supplied to a hydrodeoxygenation or deoxygenation (HDO / DO) step in a HDO / DO reactor prior to being combined with the waste tire pyrolysis oil feed to produce a hydroprocessed (e.g., hydrotreated) vegetable oil and / or fatty material feed. Thus, for example, the hydrotreated vegetable oil (e.g., HVO or hydrotreated cooked oil) is sourced internally and integrated into the process.

[0069] In one embodiment, the method further comprises supplying the waste tire pyrolysis oil feed or the stabilized waste tire pyrolysis oil feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in a HDO / DO reactor prior to combining with the vegetable oil and / or fat material or the hydrotreated vegetable oil and / or fat material feed to produce a hydroprocessed waste tire pyrolysis oil feed or a hydroprocessed stabilized waste tire pyrolysis oil feed.

[0070] Since the waste tire pyrolysis oil is rich in aromatics despite the low oxygen content, the formation of heavy fractions can be reduced by hydroprocessing the waste tire pyrolysis oil feed or the stabilized waste tire pyrolysis oil feed with vegetable oil and / or fat material, such as hydrotreating.

[0071] In one embodiment, the waste tire pyrolysis oil feed may contain a large amount of aromatics. Thus, the waste tire pyrolysis oil feed may contain 35-65 wt% aromatics (total), such as 45-55 wt% aromatics (total), measured according to ASTM D6591.

[0072] The hydroprocessed stabilized scrap tire pyrolysis oil feed may contain 25-55 wt% aromatics (total), such as 35-50 wt% aromatics (total), as measured according to ASTM D6591.

[0073] In a particular embodiment, said HDO / DO step of the waste pyrolysis oil feed or stabilized waste tire pyrolysis oil feed is carried out in the same HDO / DO reactor as the HDO / DO step of the vegetable oil and / or fatty material feed is carried out.

[0074] Therefore, through the integration of methods and equipment, simplification is achieved while reducing the footprint, thereby reducing capital and operating expenses. For example, in the same HDO / DO reactor, vegetable oil is hydrotreated in the first catalytic bed and then combined with waste tire pyrolysis oil feed or stabilized waste tire pyrolysis oil feed and then enters the second catalytic bed downstream of the HDO / DO reactor.

[0075] It should be understood that while deoxygenation (DO) is technically performed without the presence of hydrogen (eg, by addition), it is still considered a hydroprocessing step for purposes of this application.

[0076] A hydrocarbon feedstock, which combines A) waste tire pyrolysis oil feedstock and B) vegetable oil and / or fatty material, can be produced from the following feedstocks:

[0077] A) waste tire pyrolysis oil feed, or stabilized waste tire pyrolysis oil feed, or hydroprocessed waste tire pyrolysis oil feed, or hydroprocessed stabilized waste tire pyrolysis oil feed;

[0078] and

[0079] B) Vegetable oil and / or fatty material, or hydroprocessed vegetable oil and / or fatty material.

[0080] Additional feeds may also be combined, as described below.

[0081] Thus, the waste tire pyrolysis oil may or may not be subjected to hydroprocessing (eg, hydrotreating); and the vegetable oil and / or fatty material may or may not be subjected to hydroprocessing (eg, hydrotreating) before being incorporated into the hydrocarbon feed.

[0082] In one embodiment, the process further comprises supplying the hydrocarbon feed to a subsequent HDO / DO step, optionally in a subsequent HDO / DO reactor, to produce a hydroprocessed hydrocarbon feed.

[0083] Therefore, several layouts have been proposed; for example:

[0084] - Providing at least two HDO / DO reactors, for example, in which vegetable oil is hydrotreated to produce hydrotreated vegetable oil, which is then mixed with waste tire pyrolysis oil feed or stabilized waste tire pyrolysis oil feed, and the mixture, i.e., the hydrocarbon feed, is sent to a subsequent (second) HDO / DO reactor.

[0085] - Only one HDO / DO reactor is provided, and vegetable oil or hydrotreated vegetable oil is co-processed in the first catalytic bed, and then mixed with waste tire pyrolysis oil feed or stabilized waste tire pyrolysis oil feed, and the mixture is fed into the lower (downstream) catalytic bed in the HDO / DO reactor.

[0086] The present application enables co-processing of fatty materials such as vegetable oils and / or fatty acids with waste tire pyrolysis oil, which was not possible before. In addition, for example, vegetable oil can be used to cool the products from the HDO / DO reactor or as cooling between beds in the HDO reactor.

[0087] In one embodiment, the method further comprises:

[0088] - supplying the hydrocarbon feed or the hydroprocessed hydrocarbon feed to a subsequent hydroprocessing step in a downstream hydroprocessing section, such as a hydroisomerization (HDI) step in a HDI reactor, and / or a hydrocracking (HCR) step in a HCR reactor, and / or a hydrodearomatization (HDA) step in a HDA reactor, to produce a further hydroprocessed hydrocarbon feed.

[0089] Subsequent hydroprocessing steps thus include treating the combined feed in one or more additional catalytic hydroprocessing units (e.g., a third catalytic hydroprocessing unit or a cracking stage) with the addition of hydrogen. For example, it will be appreciated that when a hydrocarbon product boiling in the jet fuel range is desired, such as before sending the thus hydroprocessed stream to HDI, a hydrocracking (HCR) unit is suitably used.

[0090] It should be understood that this embodiment encompasses processes wherein the hydrocarbon feed does not include a scrap tire pyrolysis feed that has been subjected to a HDO / DO step and / or a vegetable oil and / or fatty material feed that has been subjected to a HDO / DO step.

[0091] Typically, pyrolysis oil contains a large amount of oxygenates and unsaturated hydrocarbons. When this feed is hydrotreated, oxygen is removed primarily in the form of H2O, resulting in a fuel composed primarily of naphthenes and aromatics. This is called the hydrodeoxygenation (HDO) pathway. Oxygen can also be removed via the decarboxylation pathway, which produces CO2 instead of H2O:

[0092] HDO pathway:

[0093] Decarboxylation pathway:

[0094] Furthermore, while decarbonylation is generally not dominant in the HDO process of triglycerides from typical renewable feedstocks, it is dominant in the HDO process of pyrolysis oils:

[0095] Decarbonylation pathway: RCH2COH+H2<->RCH3+CO

[0096] Materials catalytically active in HDO (as used herein interchangeably with the term "hydroprocessing") typically include an active metal (a sulfided base metal such as nickel, cobalt, tungsten and / or molybdenum, but may also include elemental noble metals such as platinum and / or palladium) and a refractory support such as alumina, silica, or titania, or combinations thereof.

[0097] HDO conditions involve temperatures in the range of 250-400°C, pressures in the range of 30-150 bar and liquid hourly space velocities (LHSV) in the range of 0.1-2, optionally combined with intermediate cooling by quenching with cold hydrogen, feed or product.

[0098] The materials having catalytic activity in the hydroisomerization of HDI generally include an active metal (elemental noble metals such as platinum and / or palladium, or sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum), an acidic support (generally a molecular sieve having high shape selectivity and having a topology such as MOR, FER, MRE, MWW, AEL, TON and MTT) and a refractory support (e.g. alumina, silica or titania, or a combination thereof).

[0099] The HDI conditions involve a temperature in the range of 250-400°C, a pressure in the range of 20-100 bar, and a liquid hourly space velocity (LHSV) in the range of 0.5-8.

[0100] The materials catalytically active in hydrocracking (HCR) are of similar nature to those catalytically active in isomerization and generally comprise active metals (elemental noble metals such as platinum and / or palladium or sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum), an acidic support (generally a molecular sieve with high cracking activity and having a topology such as MFI, BEA and FAU) and a refractory support (such as alumina, silica or titania, or a combination thereof). The difference with the materials catalytically active in isomerization generally lies in the nature of the acidic support, which may have a different structure (even amorphous silica-alumina) or have a different acidity, for example due to the silica / alumina ratio.

[0101] HCR conditions include temperatures in the range of 250-400°C, pressures in the range of 30-150 bar and liquid hourly space velocities (LHSV) in the range of 0.5-8, optionally combined with intermediate cooling by quenching with cold hydrogen gas, feed or product.

[0102] Materials that are catalytically active in HDA typically include an active metal (usually an elemental noble metal such as platinum and / or palladium, but may also include sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum) and a refractory support (e.g., amorphous silica-alumina, alumina, silica or titania, or combinations thereof).

[0103] HDA conditions involve a temperature in the range of 200-350°C, a pressure in the range of 20-100 bar or 20-200 bar, and a liquid hourly space velocity (LHSV) in the range of 0.5-8.

[0104] In one embodiment, the method comprises:

[0105] - Supplying the further hydroprocessed hydrocarbon feed to a separation step in a separation section to produce a hydrocarbon product which is any one of: naphtha, diesel, jet fuel, marine (ship) fuel as a heavy fraction, or a combination thereof.

[0106] Therefore, the marine (bunker) fuel is conveniently taken as the heavy fraction.

[0107] In one embodiment, the weight ratio (A:B) of the waste tire pyrolysis oil feed (A) to the vegetable oil and / or fatty material feed (B) is in the range of 50:50 wt% to 90:10 wt%, such as 60:40, 70:30, 75:25, 80:20 or 85:15 wt%; and optionally, any HDO / DO step is carried out in a continuous mode under the following conditions: 250-400°C, such as 350-380°C, a pressure of 50-150 bar, such as 100 bar, and a fixed bed catalyst is used in which the catalyst is NiMoS and / or MoS.

[0108] At the above weight ratio (A:B), for example, by combining hydroprocessed (e.g., hydrotreated) waste tire pyrolysis oil with hydrotreated vegetable oil (e.g., HVO), the resulting diesel exhibits desirable results in terms of cetane index and compliance with specifications (EN590 specifications), including improved cold flow properties in terms of cloud point. High synergy is achieved at least by making the cloud point of the resulting diesel lower than A or B. In addition, providing a MoS catalyst (e.g., loading it on the top of the HDO / DO reactor) can further reduce the formation of heavy fractions.

[0109] It should 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.

[0110] Suitably, the stabilization reactor and any hydroprocessing reactors such as the HDO / DO reactor or the HDI or HCR reactor or the HDA reactor are adiabatic fixed bed reactors.

[0111] As described above, the specific combination of co-processing at these weight ratios and providing NiMoS and / or MoS catalysts in the subsequent HDO / DO step can further reduce the heavy fraction (C18+ formation). Thus, the yield of diesel in the C15-C18 range is increased.

[0112] In one embodiment, the hydrocarbon product required downstream is diesel, i.e., a hydrocarbon product with a boiling point in the range of transportation fuels, which is appropriately represented by C15-C18 hydrocarbons. Hydrocarbons with a carbon number higher than 18 (C18+) can be taken out as a heavy fraction portion (also referred to herein as a heavy fraction) downstream of the separation section, but it is desirable to reduce the heavy fraction portion, thereby increasing the yield of the C15-C18 fraction, thereby increasing the yield of diesel. It has been found that the present invention can reduce the yield of the heavy fraction portion while still maintaining the appropriate miscibility of the feed. Without being bound by any theory, it is believed that, despite the low O content as described above, the aromatics in the waste tire pyrolysis oil feed still act as hydrogen donors, thereby reducing the formation of heavy fractions. When processing heavy fractions, the traditional method is to hydrocracking the heavy part of the product, thereby removing the heavy fractions. However, hydrocracking can lead to yield losses, and therefore, minimizing the formation of heavy fractions can increase the total yield of the process, particularly diesel yield. In addition, as described above, the low temperature flow properties in terms of cloud point are significantly improved.

[0113] In one embodiment, the vegetable oil and / or fat material feed is any of the following:

[0114] Soybean oils, such as soybean oil, rapeseed oil, corn oil, castor oil, cooked oil, animal fats, such as beef, pork; milk and chicken fat; and combinations thereof.

[0115] For example, the fatty material feed comprises fatty acids; the fatty material feed is suitably any one of: triglycerides, diglycerides, monoglycerides and free fatty acids.

[0116] As mentioned above, in one embodiment, the hydroprocessed vegetable oil and / or fatty material is selected from hydrotreated vegetable oils (HVO) or hydrotreated cooked oils.

[0117] This special co-feed can produce diesel that meets EN590 specifications, including improved cold flow properties, and produces a diesel with a high cetane index, such as in the range of 40-60, and a low heavy fraction content. In addition, the cloud point can be significantly reduced by providing a much lower cloud point than waste tire pyrolysis oil alone or, for example, vegetable oil alone, as described above.

[0118] When the bio-crude oil (i.e. waste tire pyrolysis oil) containing 0.1-5 wt% O is combined with a vegetable oil and / or fatty material feed to produce the hydrocarbon feed, an additional feed may be provided. Therefore, in one embodiment, the step of combining the waste tire pyrolysis oil feed with the vegetable oil and / or fatty material feed is also combined with an additional feed; the additional feed is suitably:

[0119] Fossil feedstocks, i.e. feedstocks derived from fossil fuel sources, such as diesel, kerosene, naphtha and vacuum gas oil (VGO), and / or

[0120] Intermediate hydrocarbon products such as recycle oil, ie, intermediate hydrocarbon products produced by recycling the process, such as a portion of the hydroprocessed hydrocarbon feed produced downstream, ie, the hydroprocessed hydrocarbon feed or the further hydroprocessed hydrocarbon feed.

[0121] Thus, suitably, said intermediate hydrocarbon product produced in the process is a hydroprocessed hydrocarbon feed or part of a further hydroprocessed hydrocarbon feed.

[0122] In one embodiment, the process further comprises supplying said diesel and said marine fuel as a heavy fraction or a combination thereof to a hydroisomerization step in a hydroisomerization (HDI) reactor, and / or a hydrocracking step in a hydrocracking (HCR) reactor, for providing said intermediate hydrocarbon products, such as those produced in the process.

[0123] Thus, any of these hydrocarbon products or a portion thereof is supplied to the HDI and / or HCR in a separation section, such as a distillation column from which diesel and bunker fuel are extracted. Thus, such hydrocarbon products (such as bunker fuel hydroprocessed in the HCR reactor) are advantageously added after merging the stabilized waste tire pyrolysis oil feed with a suitable hydrotreated vegetable oil and / or fatty material feed. As described above, a high degree of synergy has been found by hydrotreating each of these streams separately.

[0124] In one embodiment, the method comprises a preliminary solvent extraction step of the biocrude feed, such as a preliminary toluene extraction step, to produce the spent pyrolysis oil feed.

[0125] In a second aspect, the present invention also envisages an apparatus for carrying out the method according to any of the above-mentioned embodiments of the first aspect of the present invention.

[0126] The equipment includes:

[0127] - a conduit providing a bio-crude feed comprising 0.1-5 wt% of oxygen (O), wherein the bio-crude feed is a waste tire pyrolysis oil feed;

[0128] - a conduit which provides a feed of vegetable oil and / or fatty material;

[0129] - a mixing point for combining a biocrude feed comprising 0.1-5 wt% O with a vegetable oil and / or fatty material feed to produce a hydrocarbon feed;

[0130] - Optionally, upstream of the mixing point, a stabilization reactor is arranged to receive the waste tire pyrolysis oil feed and provide stabilized waste tire pyrolysis oil feed.

[0131] It should be understood that any embodiment according to the first aspect of the present invention and its associated advantages may be used in combination with the second aspect of the present invention.

[0132] Example: Increase the cetane index of diesel fuel, improve cold flow properties, and reduce the heavy fraction.

[0133] Biocrude oil (hence, waste tire pyrolysis oil feed) was produced from waste tire pyrolysis. The oxygen (O) content was in the range of 0.5-2 wt% O. The feed was combined with hydrotreated vegetable oil (HVO) in different weight ratios, such as 1:1 (50 wt% hydrotreated waste tire pyrolysis oil (H-WTP oil) and 50 wt% HVO).

[0134] Despite the low O content, waste tire pyrolysis oil is rich in aromatics, the density of the diesel fraction is too high, and the cetane index is too low to meet the EN590 diesel specification. HVO has a very high cetane index and low density, but poor low-temperature flow properties. It was found that H-WTP and HVO are miscible. In addition, the mixture of these two feeds works synergistically to provide a diesel fuel that meets the EN590 specification by providing a high cetane index diesel and a small amount of heavy fractions. In addition, when combined within a specific weight ratio range, the low-temperature flow properties are significantly improved. The following table shows the results.

[0135] Stabilized and hydrotreated waste tire pyrolysis oil (H-WTP oil) having a cetane index of 36 (CCI according to standard D4737) and a cloud point (CP) of 6°C (according to standard D5773) was mixed with HVO (CCI 104 and CP 22°C) in the following weight ratios: 75:25, 50:50 and 26:74. The results in the table show that mixing HVO with hydroprocessed (hydrotreated) waste tire pyrolysis oil (H-WTP oil) can increase the CCI of waste tire pyrolysis oil, that is, co-feeding hydrotreated tire pyrolysis oil with vegetable oil can produce diesel with a desired CCI. In addition, the results also show that mixing HVO with H-WTP oil also surprisingly reduces the CP of H-WTP oil, even though HVO has a much higher CP. Without being bound by any theory, this may be related to the increased solubility of the heavy fraction portion of the H-WTP oil, which, when mixed with the C15-C18 alkanes present in HVO, is more soluble in the light fraction, thereby reducing the CP. Therefore, blending HVO with H-WTP oil can improve not only the cetane index but also the cloud point; especially when the weight ratio of H-WTP oil to HVO is 60:40wt% or 75:25 or 80:20 or 90:10wt%.

[0136] H-WTP oil concentration (wt%) 100 75 50 26 0 CCI (ASTM D4737) 36 44 58 78 104 CP (ASTM D5773) 6℃ -4℃ 8℃ 15℃ 22℃

Claims

1. A method for producing a hydrocarbon feed comprising the following steps: - providing a bio-crude feed comprising 0.1-5 wt% oxygen (O); - providing a feed of vegetable oil and / or fatty material; - combining a biocrude feed comprising 0.1-5 wt% O with a vegetable oil and / or fatty material feed to produce said hydrocarbon feed; The bio-crude oil feed containing 0.1-5 wt % of O is waste tire pyrolysis oil feed.

2. The method according to claim 1, further comprising: - Prior to the combining step, the waste tire pyrolysis oil feed is supplied to a stabilization step in a stabilization reactor to produce a stabilized waste tire pyrolysis oil feed.

3. The process according to claim 2, wherein the stabilization step is carried out in a fixed bed reactor in a continuous operation mode, comprising supplying hydrogen to the bio-crude feed in the presence of any one 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, and optionally a liquid hourly space velocity (LHSV) of 0.1-2 h -1 , and the ratio of hydrogen to liquid oil is 250-3000NL / L, such as 500-2500NL / L, thereby forming the stabilized waste tire pyrolysis oil feed, wherein the ratio of hydrogen to liquid oil is defined as the volume ratio of hydrogen to liquid oil flow rate.

4. The method according to any one of claims 1 to 3, further comprising: - a pyrolysis step in a pyrolysis unit, comprising feeding the pyrolysis unit: a solid feed stream comprising at least 50 wt% of waste tire particles, to produce said waste tire pyrolysis oil feed.

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

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

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

8. The method according to any one of claims 1 to 7, further comprising a hydrodeoxygenation or deoxygenation (HDO / DO) step of supplying the scrap tire pyrolysis oil feed or the stabilized scrap tire pyrolysis oil feed to a HDO / DO reactor before combining with the vegetable oil and / or fatty material or the hydroprocessed vegetable oil and / or fatty material feed to produce a hydroprocessed scrap tire pyrolysis oil feed or a hydroprocessed stabilized scrap tire pyrolysis oil feed.

9. The process according to any one of claims 7-8, wherein the HDO / DO step of the waste pyrolysis oil feed or stabilized waste tire pyrolysis oil feed is carried out in the same HDO / DO reactor as the vegetable oil and / or fatty material feed is subjected to the HDO / DO step.

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

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

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

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

14. The method according to any one of claims 1 to 13, wherein the vegetable oil and / or fat material feed is any one of the following: 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 hydroprocessed vegetable oil and / or fatty material is selected from hydrotreated vegetable oil (HVO) or hydrotreated cooked oil.

16. A method according to any one of claims 1 to 15, wherein the step of combining the waste tyre pyrolysis oil feed with the vegetable oil and / or fatty material feed is also combined with an additional feed; the additional feed is suitably: Fossil feedstocks such as diesel, kerosene, naphtha and vacuum gas oil (VGO), and / or Intermediate hydrocarbon products, such as recycle oil, are produced by recycling intermediate hydrocarbon products produced in the process, such as a portion of the hydroprocessed hydrocarbon feed or a further hydroprocessed hydrocarbon feed.

17. The process according to any one of claims 12 to 16, wherein the process further comprises supplying the diesel and marine (marine) fuel as a heavy fraction or a combination thereof to a hydroisomerization (HDI) step in a HDI reactor and / or a hydrocracking (HCR) step in a HCR reactor to provide the intermediate hydrocarbon products, such as the intermediate hydrocarbon products produced in the process.

18. Apparatus for carrying out the method according to any one of claims 1 to 17, comprising: - a conduit providing a bio-crude feed comprising 0.1-5 wt% of oxygen (O), wherein the bio-crude feed is a waste tire pyrolysis oil feed; - a conduit which provides a feed of vegetable oil and / or fatty material; - a mixing point for combining a biocrude feed comprising 0.1-5 wt% O with a vegetable oil and / or fatty material feed to produce a hydrocarbon feed; - Optionally, upstream of the mixing point, a stabilization reactor is arranged to receive the waste tire pyrolysis oil feed and provide stabilized waste tire pyrolysis oil feed.

Images