Liquefied material processing method

Abstract

1. A process for hydrotreating a liquid oil stream in a fixed bed reactor in continuous operation, comprising: the liquid stream is a thermochemically cracked oil stream and comprises polymerizable reactive compounds; the fixed bed reactor comprising at least a first reactor bed comprising a first hydrotreating catalyst and a second reactor bed comprising a second hydrotreating catalyst; 1. A method comprising: Next steps: (i) passing at least 50% by volume of a liquid oil stream through a first reactor bed and then through a second reactor bed during a first operating period; (ii) during a second operating period, based on a determination of the deposition of material formed from the polymerizable reactive compound on the first reactor bed, passing a reduced proportion of the liquid oil stream through the first reactor bed and passing an increased proportion of the liquid oil stream that has not passed through the first reactor bed through the second reactor bed; A method is provided, comprising:

Description

[Technical Field]

[0001] The present invention relates to the field of hydroprocessing of liquid oils such as pyrolysis oils, and more particularly to the stabilization of liquid oils by hydrotreating prior to upgrading by further hydroprocessing. More particularly, the present invention relates to the stabilization of pyrolysis oils containing polymerizable reactive compounds. [Background technology]

[0002] The field of renewable feedstocks is receiving significant attention not only in Europe but also in the United States and China. The use of renewable feedstocks allows for a sustainable approach to the production of hydrocarbon products boiling in the transportation fuel range, particularly diesel, jet fuel and naphtha, as well as petrochemical production, such as steam crackers and feedstocks for plastics production.

[0003] Hydroprocessing of renewable feedstocks is a challenging task due to the diversity and complexity of these feedstocks. Currently, three generations of renewable feedstocks are generally recognized. The first generation are renewable feedstocks that are already liquid and include virgin oils such as rapeseed oil and soybean oil. The second generation are waste greases such as used cooking oil, animal fats, and crude tall oil (CTO). The third generation is, for example, much larger in volume than the second generation, i.e., more readily available. This third generation includes solid renewable feedstocks, including i) solid renewable feedstocks such as plastic waste, municipal solid waste, agricultural and forestry waste, and lignocellulosic biomass, e.g., grass; and ii) low indirect land use change (ILUC) crops, such as castor bean, which offer the advantage of not competing for space with food crops and can be grown in challenging climates.

[0004] Growing interest in reducing petroleum hydrocarbon feedstocks for the petrochemical sector (plastics production) and fuel production is expected to drive demand for hydroprocessing of highly renewable feedstocks, such as pyrolysis oil derived from solid renewable feedstocks. In addition, hydroprocessing is particularly beneficial for the approximately one-third of plastic waste that is not sorted by polymer type.

[0005] Pyrolysis oils and similar products from waste plastics are highly unsaturated and contain olefins, diolefins, conjugated diolefins, aromatics, vinyl aromatics, and saturated hydrocarbons. These oils also contain heteroatoms such as nitrogen, oxygen, sulfur, and halogens. The exact nature of the oil derived from plastics depends largely on the polymer composition of the feedstock to the liquefaction process. To meet the requirements as a petrochemical feedstock (for steam clickers), the olefinic hydrocarbons must be saturated, and the number of heteroatoms must be significantly reduced. In addition, pyrolysis oils and similar products from biomass can have very high oxygen contents; this high carbon content must be reduced before they can be used efficiently as liquid fuels, i.e., hydrocarbon fuels boiling in the transportation fuel range. Heteroatoms (e.g., nitrogen, oxygen, sulfur, and halogens) are typically removed by hydroprocessing in catalytic hydrotreating (HDT) reactors using high pressures (30-200 bar) and high temperatures (320-400°C). However, liquid oils such as pyrolysis oils or hydrothermal liquefaction oils (hereinafter also referred to as HTL oils) are highly unstable and tend to polymerize when heated. This leads to rapid catalyst deactivation and plugging of the catalyst beds of HDT reactors due to coking or gum formation. In particular, pyrolysis oil streams often contain polymerizable reactive compounds, such as conjugated diolefins, styrene homologs, and oxygenates, which can lead to deposit formation, such as gum formation or coking in the catalyst beds during various hydroprocessing steps. This results in a high pressure drop through the reactor bed, which in turn requires cleaning or replacement of the bed layer(s). Even with mild stabilization, coking of the catalyst beds can occur, leading to rapid deactivation of the hydroprocessing catalyst. Furthermore, when the process temperature is increased in the second step, a similar risk of deposit formation exists in this step, since less reactive compounds may become activated.

[0006] In view of catalyst bed coking and, in particular, the resulting high pressure drop, an additional reactor, either parallel or in series with the first reactor, is usually required. FIG. 1 shows a processing unit with two reactors arranged in parallel, and FIG. 2 shows a processing unit with two reactors arranged in series. In the configurations of FIGS. 1 and 2, due to the high pressure drop that develops across the reactor beds during hydrotreating, the first reactor must be shut down or bypassed after a certain period of time. In this case, the second reactor, added in parallel or in series, continues the normal hydrotreating operation. However, adding a second reactor in this manner within a processing unit increases the overall capital expenditures (CAPEX) and operating expenses (OPEX) of the process unit.

[0007] Furthermore, when the parallel reactor configuration of Figure 1 is used, the catalyst volume requirement is typically doubled, further increasing the overall CAPEX and OPEX of the process unit. Additionally, when the series reactor configuration of Figure 2 is used, this is typically in the form of a lead-lag configuration. In this case, when the pressure drop across the lead reactor bed becomes too high, the lead reactor is shut down for catalyst replacement or cleaning. This arrangement requires auxiliary systems, including heaters, compressors, separators, and pumps, which further increase the CAPEX and OPEX of the process unit. [Prior art documents] [Non-patent literature]

[0008] [Non-Patent Document 1] “Heterodoxy in Fast Pyrolysis of Biomass” by Robert Brown: https: / / dx.doi.org / 10.1021 / acs.energyfuels.0c03512 [Non-patent document 2] Golakota et al., “A review of hydrothermal liquefaction of biomass”, Renewable and Sustainable Energy Reviews, vol. 81, Part 1, Jan. 2018, p. 1378-1392 Summary of the Invention [Problem to be solved by the invention]

[0009] It would therefore be desirable to provide a method for stabilizing liquid oil streams prone to polymerization without significantly increasing CAPEX and OPEX. [Means for solving the problem]

[0010] In one aspect, a process for hydrotreating a liquid oil stream in a continuous operation in a fixed bed reactor comprises: the liquid oil stream is a thermochemically cracked oil stream and comprises polymerizable reactive compounds; the fixed bed reactor comprising at least a first reactor bed comprising a first hydrotreating catalyst and a second reactor bed comprising a second hydrotreating catalyst; 1. A method comprising: Next steps: (i) during a first operating period, passing at least 50 volume percent of the liquid oil stream as a first reactor bed liquid oil sidestream through the first reactor bed and then through the second reactor bed; (ii) during a second operating period, based on a determination of the deposition of material formed from the polymerizable reactive compound on the first reactor bed, passing a reduced proportion of the liquid oil stream as a first reactor bed liquid oil sidestream and passing an increased proportion of the liquid oil stream that has not passed through the first reactor bed as a second reactor bed liquid oil sidestream to the second reactor bed; Including, During the second period of operation, the volume of the first reactor bed liquid sidestream is at least 10 volume percent and less than 90 volume percent of the first reactor bed liquid oil sidestream during the first period of operation; The method is provided. [Detailed Description of the Invention] As described herein, in one aspect, a process for hydrotreating a liquid oil stream in a continuous operation in a fixed bed reactor comprises: the liquid oil stream is a thermochemically cracked oil stream and comprises polymerizable reactive compounds; the fixed bed reactor comprising at least a first reactor bed comprising a first hydrotreating catalyst and a second reactor bed comprising a second hydrotreating catalyst; 1. A method comprising: Next steps: (i) during a first operating period, passing at least 50 volume percent of a liquid oil stream as a first reactor bed liquid oil sidestream through said first reactor bed and then through a second reactor bed; (ii) during a second operating period, based on a determination of the deposition of material formed from the polymerizable reactive compound on the first reactor bed, passing a reduced proportion of the liquid oil stream as a first reactor bed liquid oil sidestream and passing an increased proportion of the liquid oil stream that has not passed through the first reactor bed as a second reactor bed liquid oil sidestream to the second reactor bed; Including, During the second period of operation, the volume of the first reactor bed liquid sidestream is at least 10 volume percent and less than 90 volume percent of the first reactor bed liquid oil sidestream during the first period of operation; The method is provided.

[0011] According to the present invention, thermochemically cracked oils, such as pyrolysis oils or hydrothermal liquefaction oils, are stabilized by converting at least the most reactive compounds in the liquid oil stream, such as furfural, furans, aldehydes, ketones, and acids, to alcohols, for example, by effectively converting carbonyls to alcohols and saturating conjugated diolefins and styrene homologs. The present invention provides a method for this stabilization while avoiding problems associated with coking of the catalyst bed as a result of the reaction of polymerizable reactive compounds, such as diolefins, in the liquid oil at the temperatures used. In particular, the present method provides a configuration that avoids intermediate reactor shutdowns by providing a reactor that can be configured to bypass the first reactor bed. This, in turn, provides a method for hydrotreating liquid oil streams without significantly increasing CAPEX and / or OPEX. Additionally, configuring a second downstream reactor operating at a relatively high temperature to similarly bypass the reactor bed may be beneficial in some circumstances.

[0012] The method of the present invention provides one or more of the following advantages.

[0013] The volume of the hydrotreating catalyst can be reduced, which in turn results in a corresponding reduction in OPEX. For the entire catalyst cycle life, only one reactor is required for the hydrotreating process. This results in an overall CAPEX reduction. This CAPEX reduction can be on the order of approximately 40%. This is compared to a typical process unit containing at least two reactors. Because only one reactor is required, rather than two or more reactors with significant auxiliary equipment, less plot space is required for the processing unit. The process of the present invention has a lower carbon footprint due to the reduced catalyst volume and steel required for the reactor and auxiliary equipment.

[0014] liquid oil stream As used herein, the terms "liquid stream" and "liquid oil" refer to feedstocks containing compounds that, at elevated temperatures (>80°C), but below temperatures that result in substantially complete hydrotreating, may react to form larger molecules, potentially resulting in complete or partial blockage of reactors, tubing, heaters, heat exchangers, and catalysts. Examples of such mixtures may be feedstocks rich in conjugated diolefins or styrene and its homologues from the thermochemical decomposition of plastic waste, municipal solid waste, refuse-derived fuel, and solid recovered fuel; feedstocks rich in carbonyls and sugars from the thermochemical decomposition of lignocellulosic biomass; nitrogen-rich feedstocks from the thermochemical decomposition of nitrogen-rich biomass, such as manure and sludge; and similar compositions from other sources. Reactive compounds may react within the same functional group (e.g., diolefin with diolefin) or between different functional groups (e.g., aldehyde with phenol).

[0015] As described herein, the methods of the present invention relate to the hydrothermal treatment of liquid oil streams, such as thermochemically cracked oil streams, including renewable crude oil streams or bio-crude oil streams. In one aspect, the liquid oil stream comprises at least 20 wt% oxygen (O), such as at least 30 wt% O, or at least 45 wt% O. In one aspect, the liquid oil stream comprises 1 to 50 wt% O, such as 5 to 50 wt% O, such as 10 to 50 wt% O, such as 15 to 50 wt% O, such as 20 to 50 wt% O, such as 25 to 50 wt% O, such as 30 to 50 wt% O, such as 35 to 50 wt% O, such as 40 to 50 wt% O, or such as 45 to 50 wt% O. The oxygen is suitably determined by standard elemental analysis. This oxygen content is representative of particularly reactive liquid oil feeds, such as pyrolysis or hydrothermal liquefaction (THL) oils, because the oxygen content can serve as an indicator of how reactive the liquid oil is. Thus, highly reactive liquid oil streams can contain as much as or even more than 45 wt.% oxygen.

[0016] In one aspect, the liquid oil stream comprises at least 500 wt. ppm O, such as 0.1 wt.% O, for example at least 0.5 wt.% O, such as at least 1 wt.%, for example at least 1.5 wt.% O, such as at least 2 wt.% O, for example at least 2.5 wt.% O, such as at least 3 wt.% O, for example at least 3.5 wt.% O, such as at least 4.5 wt.% O, for example at least 5 wt.% O, such as at least 10 wt.% O, for example at least 15 wt.% O, which is representative of a feedstock derived from the pyrolysis of plastic waste rich material. In one aspect, the liquid oil stream comprises from 0.1 to 15 wt% O, such as from 0.5 to 15 wt% O, for example from 1 to 15 wt% O, such as from 2 to 15 wt% O, for example from 3 to 15 wt% O, such as from 4 to 15 wt% O, for example from 5 to 15 wt% O, such as from 6 to 15 wt% O, for example from 7 to 15 wt% O, such as from 8 to 15 wt% O, for example from 9 to 15 wt% O, such as from 10 to 15 wt% O, for example from 11 to 15 wt% O, such as from 12 to 15 wt% O, for example from 13 to 15 wt% O, for example from 14 to 15 wt% O.

[0017] In one aspect, the thermochemically cracked oil stream is a pyrolysis oil stream or a hydrothermal liquefaction (HTL) stream. In one aspect, the thermochemically cracked oil stream is a pyrolysis oil stream. In one aspect, the thermochemically cracked oil stream is a hydrothermal liquefaction (HTL) stream.

[0018] In one aspect, the thermochemical decomposition stream is a pyrolysis oil stream containing at least 0.5 mol / kg of one or more of aldehyde compounds, ketones, alcohols, and furfural as determined by ASTM E3146-20.

[0019] In one aspect, the method of the present invention further comprises the step of pre-pyrolyzing a solid renewable feedstock to produce said thermochemically cracked oil stream.

[0020] As used herein, the term "pyrolysis" is used broadly to refer to any decomposition process in which a material is partially decomposed at elevated temperatures (typically from 250°C to 800°C or even 1000°C) in the presence of less than stoichiometric amounts of oxygen (including the absence of oxygen). The products are typically a mixed stream of liquids and gases, as well as a quantity of solid char. The term is intended to include the processes known as pyrolysis and hydrothermal liquefaction, both in the presence or absence of a catalyst.

[0021] Thus, in one particular embodiment, the pyrolysis is pyrolysis, such as fast pyrolysis as defined below, thereby producing the pyrolysis oil stream.

[0022] It will be understood that thermal decomposition occurs in the thermal decomposition section, pyrolysis occurs in the pyrolysis section, and hydrothermal liquefaction occurs in the hydrothermal liquefaction section.

[0023] As used herein, the term "section" refers to a physical section containing a unit or a combination of units for performing one or more steps and / or substeps. For purposes of the present invention, the pyrolysis section produces two main streams: a pyrolysis off-gas stream and a pyrolysis oil stream. The pyrolysis section can be in the form of a fluidized bed, a transported bed, or a circulating fluid bed, as known in the art. For example, the pyrolysis section can include a pyrolyzer unit (pyrolysis reactor), cyclone(s) for removing particulate solids, such as char, and a cooling unit for producing the pyrolysis off-gas stream and the pyrolysis oil stream, i.e., the condensed pyrolysis oil. The pyrolysis off-gas stream contains light hydrocarbons, such as C1-C4 hydrocarbons, CO, and CO2. The pyrolysis oil stream can also be referred to as a liquid material enriched in a blend of molecules, including saturated and unsaturated hydrocarbons, cyclic and aliphatic hydrocarbons, and hydrocarbons containing heteroatoms, such as nitrogen, oxygen, halogens, and sulfur. Heteroatom-containing hydrocarbons include nitriles, amines, amides, thiols, sulfides, thiophenes, aldehydes, ketones, and / or other compounds, such as furfural, that contain carbonyl groups, resulting from the depolymerization of the feedstock treated in pyrolysis.

[0024] For the purposes of the present invention, pyrolysis is preferably fast pyrolysis or slow pyrolysis. Fast pyrolysis refers to the thermal decomposition of solid renewable feedstocks in the absence of oxygen at temperatures ranging from 350 to 650°C, e.g., 500°C, for a reaction time of 10 seconds or less, e.g., 5 seconds or less, e.g., 2 seconds. For example, fast pyrolysis can be carried out by autothermal operation, e.g., in a fluidized-bed reactor. The latter, also called autothermal pyrolysis, is characterized by the use of air, optionally with an inert or recycle gas as the fluidizing gas, or a mixture of air and an inert or recycle gas. In this case, partial oxidation of the pyrolysis compounds produced in the pyrolysis reactor (autothermal reactor) provides the energy for pyrolysis while simultaneously improving heat transfer. For details of autothermal pyrolysis, see, for example, "Heterodoxy in Fast Pyrolysis of Biomass" by Robert Brown: https: / / dx.doi.org / 10.1021 / acs.energyfuels.0c03512 (Non-Patent Document 1).

[0025] "Intermediate" or "slow" pyrolysis is also suitable for feedstocks derived from waste plastics, and these can be significantly more suitable than fast pyrolysis. One reason is that high-N-content feedstocks tend to contain more alkaline metals, thus increasing the risk of agglomeration and defluidization. In addition, slow pyrolysis is currently the most popular form of pyrolysis used for plastic waste, and it provides good oil yields.

[0026] Thus, in another embodiment, the pyrolysis step is intermediate pyrolysis, in which the vapor residence time ranges from 10 seconds to 5 minutes, e.g., from 11 seconds to 3 minutes. For fast pyrolysis, the temperature again ranges from 350 to 650°C, e.g., about 500°C. Often, this pyrolysis is carried out in pyrolysis reactors for various types of waste, with subsequent combustion of vapors after the pyrolysis reactor. Typical reactors are: Herreshoff furnaces, rotary drums, Amaron, CHOREN paddle pyrolysis kilns, auger reactors, and vacuum pyrolysis reactors.

[0027] In another embodiment, the pyrolysis step is slow pyrolysis, with a solids residence time ranging from 5 minutes to 2 hours, e.g., 10 minutes to 1 hour. The temperature is suitably about 300°C. This pyrolysis provides a high char yield, and the char can be used as fertilizer or as charcoal; it still produces some gas and renewable crude products, and if the carbon is used as fertilizer, the final bio-oil can have more than 100% GHG and is therefore carbon negative. Typical reactors are auger reactors (but with different residence times than in intermediate pyrolysis), fixed-bed reactors, kilns, Lambiot SIFIC / CISR retorts, Lurgi process, wagon reactors, and Carbotzwin retorts.

[0028] Therefore, for purposes of the present invention, it will be understood that autothermal pyrolysis, i.e., the use of autothermal operation, is one particular embodiment for carrying out fast pyrolysis.

[0029] There are several types of fast pyrolysis in which a catalyst is used. To upgrade the pyrolysis vapor, an acid catalyst, such as a zeolite or silica-alumina catalyst, is sometimes used in the pyrolysis reactor; this technique is referred to as catalytic fast pyrolysis and can be operated in both in situ mode (where the catalyst is placed in the pyrolysis reactor) and ex situ mode (where the catalyst is placed in a separate reactor). The use of a catalyst has the advantage of lowering the activation energy for the reaction, thereby significantly reducing the temperature required to carry out the pyrolysis. Additionally, enhanced selectivity to the desired pyrolysis oil compounds can be achieved. In some cases, hydrogen is added to the catalytic pyrolysis, which is referred to as reactive catalytic fast pyrolysis. When catalytic pyrolysis is carried out at high hydrogen pressures (approximately >5 barg), it is often referred to as catalytic hydropyrolysis, and the pyrolysis product typically contains relatively small amounts of oxygen, e.g., 1% to 5% by weight. In one aspect, the pyrolysis step is a fast pyrolysis carried out in the absence of a catalyst and hydrogen, i.e., the fast pyrolysis step is not a catalytic fast pyrolysis, a hydrogenation pyrolysis, or a catalytic hydrogenation pyrolysis, which allows for a significantly simpler and less expensive process.

[0030] In one aspect, the pyrolysis off-gas stream comprises CO, CO2 and light hydrocarbons, such as C1-C4 hydrocarbons, and optionally H2S, HCl, HCN, and NH3.

[0031] In one respect, pyrolysis is hydrothermal liquefaction. Hydrothermal liquefaction refers to the thermochemical conversion of biomass to liquid fuel by processing in a high-temperature, pressurized water environment for a time sufficient to decompose solid biopolymer structures into primarily liquid components. Typical hydrothermal processing conditions are temperatures ranging from 250 to 375°C and operating pressures ranging from 40 to 220 bar. This technology offers advantages over pyrolysis, such as fast pyrolysis, in terms of operation at relatively low temperatures, relatively high energy efficiency, and relatively low tar yields. For details on the hydrothermal liquefaction of biomass, see, for example, Golakota et al., "A review of hydrothermal liquefaction of biomass," Renewable and Sustainable Energy Reviews, vol. 81, Part 1, January 2018, pp. 1378-1392 (Non-Patent Document 2).

[0032] In one aspect, pyrolysis further includes passing the solid renewable feedstock through a solid renewable feedstock preparation section, which may include, for example, drying to remove water and / or atomization to reduce particle size. For example, water / moisture in the solid renewable feedstock that vaporizes in the pyrolysis section may condense in the pyrolysis oil stream and thus become entrained in the process. This may be undesirable. Furthermore, the heat used to vaporize the water removes heat otherwise required for pyrolysis. By removing water and providing smaller particles in the solid renewable feedstock, the thermal efficiency of the pyrolysis section is increased.

[0033] In one aspect, the solid renewable feedstock is lignocellulosic biomass, including wood products, forestry waste, and agricultural waste. In another aspect, the solid renewable feedstock is municipal waste, particularly the organic portion thereof. For purposes of this invention, the term "municipal waste" is interchangeable with the term "municipal solid waste" and refers to feedstocks containing materials from items discarded by the public, such as mixed municipal waste, which is assigned waste code 200301 in the European Waste Catalogue.

[0034] In one aspect, the lignocellulosic biomass is forestry waste and / or agricultural waste, including biomass derived from plants such as turfgrass, e.g., natural turf (grass derived from natural landscapes), wheat, e.g., wheat straw, oats, rye, reedgrass, bamboo, sugarcane or sugarcane derivatives, e.g., bagasse, corn, and other grains.

[0035] In one aspect, the solid renewable feedstock is waste plastic.

[0036] Any combination of the above is also envisioned.

[0037] As used herein, the term "lignocellulosic biomass" means biomass that contains cellulose, hemicellulose, and optionally lignin, the lignin or a substantial portion of which may have been removed, for example, by a prior bleaching step.

[0038] As described herein, the liquid stream comprises a polymerizable reactive compound. In one aspect, the polymerizable reactive compound is at least a conjugated diolefin. In one aspect, the polymerizable reactive compound is at least a carbonyl. In one aspect, the polymerizable reactive compound is at least a sugar. In one aspect, the polymerizable reactive compound is at least a styrene homolog. In one aspect, the polymerizable reactive compound is at least a vinyl aromatic.

[0039] In one aspect, the liquid flow is from 1 gl / 100g to 25 gl / 100g, for example from 2 gl / 100g to 25 gl / 100g, for example from 3 gl / 100g to 25 gl / 100g, for example from 4 gl / 100g to 25 gl / 100g, for example from 5 gl / 100g to 25 gl / 100g, for example from 6 gl / 100g to 25 gl / 100g, For example, it has a diene value of from 7gl / 100g to 25gl / 100g, for example from 8gl / 100g to 25gl / 100g, for example from 9gl / 100g to 25gl / 100g, for example from 10gl / 100g to 25gl / 100g, for example from 15gl / 100g to 25gl / 100g, for example from 20gl / 100g to 25gl / 100g. In one aspect, the liquid stream has a diene number of from 1 gl / 100g to 20 gl / 100g, such as from 1 gl / 100g to 15 gl / 100g, for example from 1 gl / 100g to 10 gl / 100g, for example from 1 gl / 100g to 9 gl / 100g, such as from 1 gl / 100g to 8 gl / 100g, for example from 1 gl / 100g to 7 gl / 100g, for example from 1 gl / 100g to 6 gl / 100g, such as from 1 gl / 100g to 5 gl / 100g, for example from 1 gl / 100g to 4 gl / 100g, for example from 1 gl / 100g to 3 gl / 100g, for example from 1 gl / 100g to 2 gl / 100g. In one aspect, the liquid stream has a diene number of at least 1 gl / 100g, such as at least 2 gl / 100g, for example at least 3 gl / 100g, such as at least 4 gl / 100g, for example at least 5 gl / 100g, such as at least 6 gl / 100g, for example at least 7 gl / 100g, such as at least 8 gl / 100g, for example at least 9 gl / 100g, such as at least 10 gl / 100g, for example at least 15 gl / 100g, such as at least 20 gl / 100g, for example at least 25 gl / 100g. The diene number of the liquid stream can be derived using ASTM standard UOP-326.

[0040] Hydrotreating As described herein, the process of the present invention relates to hydrotreating a liquid oil stream in a continuous operation in a fixed bed reactor, wherein the fixed bed reactor comprises at least a first reactor bed comprising a first hydrogenation catalyst and a second reactor bed comprising a second hydrotreating catalyst.

[0041] The method for hydrotreating a liquid oil stream of the present invention is a continuous operation. As is well known in the art, the term "continuous operation" means that during a given production cycle, the input of liquid oil is constant, and the stabilized liquid oil stream discharged as resulting product is likewise constant. This is in contrast to batch operations, also well known in the art. In such operations, the entire amount of liquid oil and catalyst is introduced at the beginning of the process, and the resulting product is discharged after a period of time.

[0042] In one aspect, the liquid oil has a temperature below 400°C, such as below 390°C, for example below 380°C, for example below 370°C, for example below 360°C, such as below 350°C, for example below 340°C, for example below 330°C, such as below 320°C, for example below 310°C, such as below 300°C, for example below 290°C, for example below 280°C, such as below 270°C, for example below 260°C, for example below 250°C, such as below 240°C. It is hydrotreated in a fixed bed reactor at a temperature below 30°C, such as below 220°C, for example below 210°C, for example below 200°C, such as below 190°C, for example below 180°C, for example below 170°C, such as below 160°C, for example below 150°C, for example below 140°C, such as below 130°C, for example below 120°C, such as below 110°C, for example below 100°C, such as below 90°C, for example below 80°C, for example below 70°C.

[0043] In one aspect, the liquid oil has a saturation temperature of from 70 to 400°C, such as from 70 to 390°C, for example from 70 to 380°C, for example from 70 to 370°C, for example from 70 to 360°C, for example from 70 to 350°C, for example from 70 to 340°C, for example from 70 to 330°C, for example from 70 to 320°C, for example from 70 to 310°C, for example from 70 to 300°C, for example from 70 to 290°C, for example from 70 to 280°C, for example from 70 to 270°C, for example from 70 to 260°C, for example from 70 to 250°C, for example from 70 to 240°C. C., for example from 70 to 230.degree. C., for example from 70 to 220.degree. C., for example from 70 to 210.degree. C., for example from 70 to 200.degree. C., for example from 70 to 190.degree. C., for example from 70 to 180.degree. C., for example from 70 to 170.degree. C., for example from 70 to 160.degree. C., for example from 70 to 150.degree. C., for example from 70 to 140.degree. C., for example from 70 to 130.degree. C., for example from 70 to 120.degree. C., for example from 70 to 110.degree. C., for example from 70 to 100.degree. C., for example from 70 to 90.degree. C., for example from 70 to 80.degree.

[0044] In one aspect, the liquid oil is hydrotreated in a fixed bed reactor at a temperature of from 70 to 250° C., for example from 80 to 200° C. In one aspect, the liquid oil is hydrotreated in a fixed bed reactor at a temperature ranging from 250 to 400° C.

[0045] In one aspect, the temperature ranges from 250 to 400°C; the pressure is from 20 to 175 barg and the LHSV is from 0.5 to 8 / h and the H2 to oil ratio is from 5 to 2000 NI / L.

[0046] In one aspect, the first and second hydrotreating catalysts convert at least one conjugated diolefin to the corresponding monoolefin or paraffin. In one aspect, the first and second hydrotreating catalysts convert styrene to ethylbenzene. In one aspect, the first and second hydrotreating catalysts convert halogenated hydrocarbons to non-halogenated hydrocarbons. In one aspect, the first and second hydrotreating catalysts convert at least one of furfural, furans, aldehydes, ketones, and acids to alcohols and / or carbonyls to alcohols. The alcohols can be further converted to saturated organic compounds during stabilization and / or in a subsequent hydroprocessing step such as HDO.

[0047] In one aspect, the first and second hydrotreating catalysts are each independently selected from catalysts based on Mo, Ni, W, Pt, Pd, Cu, Fe, Zn, and Ru, and combinations thereof. In one aspect, the catalysts are in sulfided, partially sulfided (i.e., surface passivated with sulfur), or reduced form.

[0048] In one aspect, the catalyst is a supported catalyst, wherein the support is selected from alumina, silica, titania, magnesia, and combinations thereof, optionally combined with a molecular sieve having MFI, BEA, or FAU topology, which may be a physical mixture or an oxide system, such as silica-alumina, alumina-magnesia spinel, and other spinel group oxide systems.

[0049] In one aspect, the catalyst is Ni-based, Mo-based, CoMo-based, NiMo-based, W-based, NiW-based, or Ru-based, optionally in sulfided or reduced form.

[0050] In one aspect, the Ni-based catalyst comprises at least 90 wt. %, such as at least 95 wt. %, for example at least 99 wt. %, for example 100 wt. %, Ni, based on the Group 1 to 12 materials in the catalyst. In one aspect, the Mo-based catalyst comprises at least 90 wt. %, for example at least 95 wt. %, for example at least 99 wt. %, for example 100 wt. %, Mo, based on the Group 1 to 12 materials in the catalyst. In one aspect, the W-based catalyst comprises at least 90 wt. %, for example at least 95 wt. %, for example at least 99 wt. %, for example 100 wt. %, W, based on the Group 1 to 12 materials in the catalyst. In one aspect, the Ru-based catalyst comprises at least 90 wt. %, for example at least 95 wt. %, for example at least 99 wt. %, for example 100 wt. %, Ru, based on the Group 1 to 12 materials in the catalyst.

[0051] In one aspect, the Ni-based catalyst contains 2 to 30 wt% Ni, which is sulfided or reduced. In one aspect, the Mo-based catalyst contains 2 to 30 wt% Mo, preferably sulfided. In one aspect, the CoMo-based catalyst contains 1 to 10 wt% Co and 2 to 30 wt% Mo, preferably sulfided. In one aspect, the NiMo-based catalyst contains 1 to 10 wt% Ni and 2 to 30 wt% Mo, preferably sulfided. In one aspect, the W-based catalyst contains 2 to 30 wt% W, preferably sulfided. In one aspect, the NiW-based catalyst contains 1 to 10 wt% Ni and 2 to 30 wt% W, preferably sulfided. In one aspect, the Ru-based catalyst contains 0.1 to 10 wt% Ru, preferably reduced.

[0052] In one aspect, the first and / or second hydrotreating catalyst comprises Mo. In one aspect, the first and / or second hydrotreating catalyst comprises Ni. In one aspect, the first and / or second hydrotreating catalyst comprises W. In one aspect, the first and / or second hydrotreating catalyst comprises Pt. In one aspect, the first and / or second hydrotreating catalyst comprises Pd. In one aspect, the first and / or second hydrotreating catalyst comprises Cu. In one aspect, the first and / or second hydrotreating catalyst comprises Fe. In one aspect, the first and / or second hydrotreating catalyst comprises Zn. In one aspect, the first and / or second hydrotreating catalyst comprises Ru.

[0053] In one aspect, the catalyst is sulfided. In one aspect, the hydrotreating catalyst is a sulfided form of a Ni-Mo based catalyst, i.e., NiMoS. The catalyst may be pre-sulfided by exposure to a sulfur-containing stream, or it may be sulfided in situ, i.e., on-stream, by sulfur present in, for example, pyrolysis oil.

[0054] In one aspect, the Ni-Mo based catalyst is a supported catalyst having a Ni content of 3-5 wt%, a Mo content of 15-25 wt%, and optionally a P content of 1-3 wt%, based on the total weight of the catalyst. In one aspect, the Ni-Mo based catalyst is a supported catalyst, wherein the support is selected from alumina, silica, titania, and combinations thereof, optionally combined with a molecular sieve having MFI, BEA, or FAU topology.

[0055] According to the present invention, alcohols in pyrolysis oil or hydrothermal liquefaction oil are first dehydrated to the corresponding unsaturated organic compounds, such as alkenes, and then hydrogenated to the corresponding saturated organic compounds, such as alkanes. For example, 1-octanol present in pyrolysis oil or hydrothermal liquefaction oil is first dehydrated to octene and then hydrogenated to octane. On the other hand, ketones such as cyclopentanone (a type of cyclic ketone) are first hydrogenated to the corresponding alcohol, i.e., cyclopentanol, then dehydrated to cyclopentene, and then hydrogenated to cyclopentane. Dehydration is prevented by pyridine (C5H5N, i.e., a compound containing organic nitrogen) present in the pyrolysis oil. This indicates that pyridine is adsorbed on acid sites. However, hydrogenation is not prevented by pyridine. This indicates that the catalyst according to the conditions of the present invention can convert aldehydes and ketones or other compounds containing carbonyl groups, which usually contain organic sulfur and nitrogen, in pyrolysis oil into alcohols. In other words, the desired reaction of converting compounds containing carbonyl groups, such as aldehydes and ketones, to their corresponding alcohols by hydrogenation becomes possible. These alcohols can be dehydrated to the corresponding alkanes as part of the reaction occurring during stabilization or in subsequent hydrodeoxygenation. In addition, the saturation of conjugated diolefins and styrene homologues in the liquid oil and the reduction of the heteroatom content become possible.

[0056] As described herein, the fixed bed reactor includes at least a first reactor bed and a second reactor bed. In one aspect, the fixed bed reactor includes a mixer between the first reactor bed and the second reactor bed. In one aspect, the mixer is a quench mixer. The quench system installed between each bed ensures proper mixing of the second reactor bed feed and the second reactor bed effluent to avoid flow non-uniformities in the second reactor bed.

[0057] In one aspect, the volumetric ratio of the first reactor bed to the second reactor bed is from 20:80 to 80:20. In another aspect, the volumetric ratio of the first reactor bed to the second reactor bed is from 20:80 to 75:25. In another aspect, the volumetric ratio of the first reactor bed to the second reactor bed is from 20:80 to 70:30. In another aspect, the volumetric ratio of the first reactor bed to the second reactor bed is from 20:80 to 65:35. In another aspect, the volumetric ratio of the first reactor bed to the second reactor bed is from 20:80 to 60:40. In another aspect, the volumetric ratio of the first reactor bed to the second reactor bed is from 20:80 to 55:45. In another aspect, the volumetric ratio of the first reactor bed to the second reactor bed is from 20:80 to 50:50.

[0058] First operation period As described herein, the process of the present invention includes a first operational period during which at least 50 volume percent of the liquid oil stream is passed as a first reactor bed liquid oil sidestream through the first reactor bed and then through the second reactor bed.

[0059] During the first run, at least 50% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 55% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 60% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 65% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 70% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 75% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 80% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 85% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 90% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 95% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, at least 99% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed. In one aspect, 100% by volume of the liquid oil stream passes through the first reactor bed and then the second reactor bed.

[0060] In one aspect, during the first period of operation, from 50 to 100 vol%, such as from 55 to 100 vol%, for example from 60 to 100 vol%, for example from 65 to 100 vol%, for example from 70 to 100 vol%, for example from 75 to 100 vol%, for example from 80 to 100 vol%, for example from 85 to 100 vol%, for example from 90 to 100 vol%, for example from 95 to 100 vol%, for example from 99 to 100 vol% of the liquid oil stream is passed through the first reactor bed and then the second reactor bed.

[0061] Second operation period As described herein, the process of the present invention includes a second operating period in which, based on a determination of the accumulation of material formed from the polymerizable reactive compound in the first reactor bed, a reduced proportion of the liquid oil stream is passed through the first reactor bed, and an increased proportion of the liquid oil stream that has not passed through the first reactor bed is passed through the second reactor bed. This stream is also referred to as the second reactor bed liquid oil sidestream. In the present invention, during this period, the first reactor bed liquid oil sidestream is maintained to avoid backflow in the first reactor bed.

[0062] As described herein, during the hydroprocessing of liquid oil streams containing polymerizable reactive compounds, the reaction of these reactive compounds, such as diolefins, can result in coking (gum formation) in the catalyst bed. This can lead to a pressure drop in the reactor bed, which can have a detrimental effect on the hydroprocessing process and result in increased process unit CAPEX and OPEX. To address this issue, the process of the present invention can at least partially divert the liquid oil stream so that it passes through a second reactor bed when material is estimated to have built up in the first reactor bed.

[0063] In one aspect, the rate of liquid oil flow through the first reactor bed during the second operating period is reduced by at least 10% compared to the first operating period. In one aspect, the rate of liquid oil flow through the first reactor bed during the second operating period is reduced by at least 20% compared to the first operating period. In one aspect, the rate of liquid oil flow through the first reactor bed during the second operating period is reduced by at least 30% compared to the first operating period. In one aspect, the rate of liquid oil flow through the first reactor bed during the second operating period is reduced by at least 40% compared to the first operating period. In one aspect, the rate of liquid oil flow through the first reactor bed during the second operating period is reduced by at least 50% compared to the first operating period. In one aspect, the rate of liquid oil flow through the first reactor bed during the second operating period is reduced by at least 60% compared to the first operating period. In one aspect, the rate of liquid oil flow through the first reactor bed during the second operating period is reduced by at least 70% compared to the first operating period. In one aspect, during the second period of operation, the rate of liquid oil flow through the first reactor bed is reduced by at least 80% compared to the first period of operation. In one aspect, during the second period of operation, the rate of liquid oil flow through the first reactor bed is reduced by at least 90% compared to the first period of operation.

[0064] In one aspect, during the second operating period, the proportion of liquid oil flow passing through the first reaction bed is reduced compared to the first operating period by 10 to 90%, such as 20 to 90%, for example 30 to 90%, for example 40 to 90%, for example 50 to 90%, for example 60 to 90%, for example 70 to 90%, for example 80 to 90%.

[0065] In one aspect, during the second operating period, the proportion of the liquid oil flow passing through the first reactor bed is decreased over time, and the proportion of the liquid oil flow passing through the second reactor bed that did not pass through the first reactor bed is increased over time.

[0066] In one aspect, the deposition of material formed from the polymerizable reactive compound onto the first reactor bed is determined by at least one of pressure drop, outlet gas temperature, reactant concentration, product concentration, catalyst bed temperature, time on of the first run period, and combinations thereof. In one aspect, the deposition of material formed from the polymerizable reactive compound onto the first reactor bed is determined by pressure drop. In one aspect, the deposition of material formed from the polymerizable reactive compound onto the first reactor bed is determined using a pressure differential indicator controller (PDIC).

[0067] In one aspect, the determination of the deposition of material formed from the polymerizable reactive compound begins with a process control signal that initiates the second run period.

[0068] In one aspect, shown in Figure 3, the flow to the first and second reactor beds can be regulated using a three-way valve installed on the main feed line. In one aspect, shown in Figure 4, the flow to the first and second reactor beds can be regulated using a control valve on the feed line to the second reactor bed. In the embodiments of Figures 3 and 4, the opening of the control valve is controlled by a signal from a PDIC that measures the pressure drop across the first reactor bed.

[0069] Other reactor beds and operation periods In one aspect, the fixed bed reactor further comprises a third reactor bed comprising a third hydrotreating catalyst, wherein the method includes a third operating period in which, based on a determination of the accumulation of material formed from the polymerizable reactive compound on the second reactor bed, a reduced proportion of the liquid oil stream is passed through the first reactor bed and the second reactor bed, and an increased proportion of the liquid oil stream that has not passed through the first reactor bed or the second reactor bed is passed through the third reactor bed.

[0070] In one aspect, the fixed bed reactor includes a mixer, such as a quench mixer, between the second and third reactor beds. The quench system installed between each bed ensures adequate mixing of the third reactor bed feed with the effluent from the second reactor bed to avoid flow non-uniformities in the third reactor bed.

[0071] In one aspect, the rate of liquid oil flow through the first and second reactor beds during the third operating period is reduced by at least 10% compared to the first and second operating periods. In one aspect, the rate of liquid oil flow through the first and second reactor beds during the third operating period is reduced by at least 20% compared to the first and second operating periods. In one aspect, the rate of liquid oil flow through the first and second reactor beds during the third operating period is reduced by at least 30% compared to the first and second operating periods. In one aspect, the rate of liquid oil flow through the first and second reactor beds during the third operating period is reduced by at least 40% compared to the first and second operating periods. In one aspect, the rate of liquid oil flow through the first and second reactor beds during the third operating period is reduced by at least 50% compared to the first and second operating periods. In one aspect, the rate of liquid oil flow through the first and second reactor beds during the third operating period is reduced by at least 60% compared to the first and second operating periods. In one aspect, during the third period of operation, the rate of liquid oil flow through the first and second reactor beds is reduced by at least 70% compared to the first and second periods of operation. In one aspect, during the third period of operation, the rate of liquid oil flow through the first and second reactor beds is reduced by at least 80% compared to the first and second periods of operation. In one aspect, during the third period of operation, the rate of liquid oil flow through the first and second reactor beds is reduced by at least 90% compared to the first and second periods of operation.

[0072] In one aspect, during the third operating period, the proportion of liquid oil flow passing through the first and second reaction beds is reduced compared to the first and second operating periods by 10 to 90%, such as 20 to 90%, for example 30 to 90%, for example 40 to 90%, for example 50 to 90%, for example 60 to 90%, for example 70 to 90%, for example 80 to 90%.

[0073] In one aspect, during the third operating period, the proportion of the liquid oil stream passing through the first and / or second reactor bed is decreased over time, and the proportion of the liquid oil stream passing through the third reactor bed that has not passed through the first and / or second reactor bed is increased over time.

[0074] In one aspect, the deposition of material formed from the polymerizable reactive compound onto the second reactor bed is determined by at least one of pressure drop, outlet gas temperature, reactant concentration, product concentration, catalyst bed temperature, and combinations thereof. In one aspect, the deposition of material formed from the polymerizable reactive compound onto the second reactor bed is determined by pressure drop. In one aspect, the deposition of material formed from the polymerizable reactive compound onto the second reactor bed is determined using a pressure differential indicator controller (PDIC).

[0075] The method of the present invention may include one or more further steps, which may be before, after or intermediate to the steps described herein.

[0076] In one aspect, the method includes passing the stabilized pyrolysis oil stream through a hydrotreating (HDT) step, typically operated in a separate reactor at a higher temperature, to remove organic heteroatoms such as nitrogen, sulfur, oxygen, chlorine, bromine, and fluorine present in the stabilized pyrolysis oil stream and produce a hydrotreated stream that can be further processed to produce hydrocarbon products boiling in the transportation fuel range, such as diesel, jet fuel, and naphtha. Such further processing can include either hydrodewaxing or isomerization, as is well known in the field of fossil fuel refining. Other types of hydrotreating, such as hydrodearomatization (HDA), are also contemplated. Materials that are catalytically active in hydrodearomatization typically include an active metal (typically an elemental noble metal such as platinum and / or palladium, but optionally also a sulfide base metal such as nickel, cobalt, tungsten and / or molybdenum), and a refractory support (e.g., amorphous silica-alumina, alumina, silica, magnesia or titania, or a combination thereof).

[0077] In one aspect, the hydrotreating (HDT) reactor is configured to operate for a first period of operation and a second period of operation corresponding to the first and second periods of operation of the fixed bed reactor on the same or separate basis.

[0078] Aspects of the present invention will now be described, by way of example only, with reference to the accompanying drawings, which illustrate exemplary aspects of the invention only and therefore should not be considered as limiting its scope, since the invention may be capable of other alternative aspects. [Brief explanation of the drawings]

[0079] [Figure 1] FIG. 1 shows a process unit containing two reactors in a parallel arrangement. [Figure 2] FIG. 2 shows a process unit containing two reactors in a series arrangement. [Figure 3]FIG. 3 shows a process unit according to the present invention in which the flow to each reactor bed is regulated using one three-way valve installed on the main feed line. [Figure 4] FIG. 4 shows a process unit according to the present invention in which the flow to each reactor bed is regulated using one control valve on the feed line to the second reactor bed.

[0080] The invention will now be illustrated by the following non-limiting examples. [Example]

[0081] [Table 1]

[0082] In the above example, Scenario A (not the present invention) is when two reactors are in a parallel configuration and the catalyst volume requirement is typically doubled. The first reactor is in operation, while the second reactor is loaded with hydrotreating catalyst and is completely bypassed, but not in operation. If the pressure drop across the first reactor bed increases or the activity of the catalyst in the first reactor is insufficient to operate the process, the process unit would typically need to be shut down for a short period of time to remove the first reactor from operation and start the second reactor. CAPEX and OPEX are referred to as "baseline" in this scenario for comparison purposes. The greater or longer the amount of hydrotreating catalyst, the number of reactors, and the duration required to shut down the process unit, switch the reactors, and start the process unit with the second reactor, the greater the CAPEX and OPEX in Scenario A.

[0083] In Scenario B (not of the present invention), when the reactor arrangement is in series (also known as lead-lag operation), the first and second reactors are operated in series, and each reactor is used at half the total catalyst volume requirement. In this scenario, if the pressure drop across the lead reactor bed increases, the lead reactor is shut down for catalyst replacement or cleaning. This arrangement requires auxiliary systems, including heaters, compressors, separators, and pumps, which further increase the CAPEX and OPEX of the process unit. The process unit can continue to operate with the second reactor until the first reactor is ready for a catalyst replacement. The first reactor, loaded with fresh catalyst, operates as a lag reactor, while the second reactor remains in operation as a lead reactor until the pressure drop across the second reactor increases.

[0084] In the proposed scheme of Scenario C according to the present invention, a reactor is used with two or more beds, each capable of receiving fresh feed. In this example, the first bed can be bypassed and the second bed can receive the bypass feed, thus eliminating the need to shut down the unit or the need for auxiliaries, additional catalysts or reactors, etc. In this example of the present invention, the CAPEX and OPEX savings are the highest for Scenarios A, B, and C, respectively.

[0085] Various modifications and variations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in chemistry and related fields are intended to be within the scope of the following claims.

Claims

1. 1. A process for hydrotreating a liquid oil stream in a fixed bed reactor in continuous operation, comprising: the liquid oil stream is a thermochemically cracked oil stream and contains polymerizable reactive compounds; the fixed bed reactor comprising at least a first reactor bed comprising a first hydrotreating catalyst and a second reactor bed comprising a second hydrotreating catalyst; 1. A method comprising: Next steps: (i) during a first period of operation, passing at least 50 volume percent of said liquid oil stream as a first reactor bed liquid oil side stream through said first reactor bed and then through said second reactor bed; (ii) during a second run period, based on a determination of the accumulation of material formed from the polymerizable reactive compound on the first reactor bed, passing a reduced proportion of the liquid oil stream as a first reactor bed liquid oil sidestream, and passing an increased proportion of the liquid oil stream that has not passed through the first reactor bed as a second reactor bed liquid oil sidestream to the second reactor bed; Including, during said second period of operation, the volume of said first reactor bed liquid sidestream is at least 10 volume percent and less than 90 volume percent of said first reactor bed liquid oil sidestream during said first period of operation; The method.

2. 10. The method of claim 1, wherein the polymerizable reactive compound is selected from the group consisting of conjugated diolefins, sugars, carbonyls, styrene homologs, and vinyl aromatics.

3. 3. The process of claim 1 or 2, wherein, during the first operating period, the first reactor bed liquid oil side stream comprises at least 70% by volume, such as at least 90% by volume, for example at least 99% by volume, of the liquid oil stream.

4. 4. The method of claim 1, wherein the proportion of said liquid oil stream contained in said first reactor bed liquid oil side stream during said second period of operation is reduced by at least 10%, such as at least 20%, such as at least 40%, such as at least 80%, compared to said first period of operation.

5. 5. The method according to claim 1, wherein (i) during the first period of operation, from 50 to 100 volume percent of the liquid oil stream is contained in the first reactor bed liquid oil sidestream, and from 0 to 50 volume percent of the liquid oil stream that has not passed through the first reactor bed is passed through the second reactor bed; and (ii) during the second period of operation, from 25 to 75 volume percent of the liquid oil stream is passed to the first reactor bed and then to the second reactor bed, and from 25 to 75 volume percent of the liquid oil stream is passed as a second reactor bed liquid oil side stream; The method.

6. 6. The method of claim 1, wherein during the second operating period, the first reactor bed liquid oil sidestream is decreased over time and the second reactor bed liquid sidestream is increased over time.

7. 7. The method of any one of claims 1 to 6, wherein the deposition of material formed from the polymerizable reactive compound onto the first reactor bed is determined by at least one of pressure drop, outlet temperature, reactant concentration, product concentration, catalyst bed temperature, and combinations thereof.

8. 8. The process of claim 1, wherein the fixed bed reactor comprises a mixer between the first reactor bed and the second reactor bed, the mixer being, for example, a quench mixer.

9. 9. The method of any one of claims 1 to 8, wherein the volume ratio of the first reactor bed to the second reactor bed is from 20:80 to 80:20, such as the volume ratio of the first reactor bed to the second reactor bed is from 20:80 to 50:50, such as the volume ratio of the first reactor bed to the second reactor bed is from 20:80 to 40:

60.

10. 10. The method of claim 1, wherein the fixed bed reactor further comprises a third reactor bed comprising a third hydrotreating catalyst; Next steps: (iii) during a third run period, based on a determination of the accumulation of material formed from the polymerizable reactive compound on the second reactor bed, passing a reduced proportion of the liquid oil stream as the first reactor bed liquid oil sidestream and the second reactor bed liquid oil sidestream, and passing an increased proportion of the liquid oil stream that has not passed through the first reactor bed or the second reactor bed as a third reactor bed liquid oil sidestream to the third reactor bed; The method further comprises:

11. 11. The process of claim 10, wherein the fixed bed reactor comprises a mixer, e.g., a quench mixer, between the second reactor bed and the third reactor bed.

12. 12. The method of any one of claims 1 to 11, wherein the first hydrotreating catalyst and the second hydrotreating catalyst are independently selected from the group consisting of Mo-, Ni-, W-, Pt-, Pd-, Cu-, Fe-, Zn-, and Ru-based catalysts and combinations thereof.

13. 13. The method of claim 12, wherein the first hydrotreating catalyst and / or the second hydrotreating catalyst is a supported Ni-Mo based catalyst having a Ni content of from 3 to 5 wt. %, a Mo content of from 15 to 25 wt. %, and optionally a P content of from 1 to 3 wt. %, based on the total weight of the catalyst, the support being selected from, for example, alumina, silica, titania, magnesia, and combinations thereof; optionally combined with a molecular sieve having the topology MFI, BEA, or FAU; and optionally the Ni-Mo based catalyst is in a sulfided form, i.e., NiMoS.

14. The method of any one of claims 1 to 13, wherein the thermochemically cracked oil stream is provided by thermal cracking of a solid renewable feedstock.

15. 15. The method of claim 14, wherein the pyrolysis comprises: pyrolysis, such as slow pyrolysis, fast pyrolysis and catalytic fast pyrolysis, to produce a pyrolysis oil stream; or - hydrothermal liquefaction to produce a hydrothermal liquefied oil stream; The method of claim 14, wherein

16. 16. The method of claim 14 or 15, wherein the solid renewable feedstock comprises: - Lignocellulosic biomass, including wood products, forestry waste, sludge and agricultural waste; and / or - a fraction rich in waste plastics; and / or - municipal waste, in particular (a) the organic fraction thereof, where municipal waste is defined as a feedstock comprising materials from articles discarded by the public, such as mixed municipal waste, which is given waste code 200301 in the European Waste Catalogue; and / or (b) a fraction comprising at least 50% by weight of plastic waste: The method according to claim 1,

17. A process plant configured to carry out the method according to any one of claims 1 to 16.

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