Hydrocarbon upgrading process with recycle

Abstract

A process for upgrading a bio-oil stream is disclosed. The process includes reacting the bio-oil stream with hydrogen in the presence of a catalyst and a stabilizing oil in a reactor to produce an upgraded bio-oil stream. A recycle oil stream is withdrawn from the upgraded bio-oil stream. The recycle oil stream is recycled to the reactor to provide the stabilizing oil. The contents of the reactor can be measured using various techniques and characterized based on the concentration of one or more functional groups, such as oxygenates. In addition, a fuel oil stream can be withdrawn from the upgraded bio-oil stream.

Description

Priority Statement

[0001] This application claims the benefit of U.S. Patent Application Serial No. 18 / 542,180, filed December 15, 2023, and U.S. Patent Application Serial No. 18 / 905,970, filed October 3, 2024, the entire disclosure of which is incorporated herein by reference. Technical Field

[0002] This field relates to a method for modifying bio-oil streams. Specifically, this field relates to a method for modifying bio-oil streams for use as fuel oil or for modification in an FCC unit, hydrotreating unit, or reforming unit. Background Technology

[0003] Hydrocarbon conversion methods typically require reactor systems and associated conduits and piping suitable for hydrocracking, reforming, fluidized catalytic cracking, and other similar methods.

[0004] Bio-oil is obtained through thermochemical liquefaction (particularly pyrolysis, such as flash pyrolysis, fast pyrolysis, slow pyrolysis, or catalytic pyrolysis). Pyrolysis is a thermal decomposition process that thermally cracks a feedstock into gaseous, liquid, and solid products in the absence of oxygen. Catalysts can be added to improve the conversion rate in so-called catalytic pyrolysis. Various technologies have been deployed for large-scale biomass pyrolysis. These technologies include bubbling fluidized beds, circulating fluidized beds, ablation pyrolysis, vacuum pyrolysis, and rotating conical pyrolysis reactors. Catalytic pyrolysis typically produces bio-oil with a lower oxygen content compared to bio-oil obtained through thermal decomposition. The selectivity among gas, liquid, and solid products is closely related to the reaction temperature and vapor residence time. Lower temperatures (e.g., around 400°C) and longer residence times (e.g., minutes to hours) obtained through slow pyrolysis favor the production of solid products (also known as charcoal or wood charcoal), which typically have 35 wt% gas, 30 wt% liquid, and 35 wt% charcoal. Very high temperatures above 800°C used in gasification processes favor gas production (typically greater than 85 wt%). For so-called pyrolysis, an intermediate reaction temperature (typically 450°C to 550°C) and a short steam residence time (typically 10 to 20 s) favor liquid yields: typically 30 wt% gas, 50 wt% liquid, and 20 wt% char. For so-called flash pyrolysis or fast pyrolysis, an intermediate reaction temperature (typically 450°C to 550°C) and a very short steam residence time (typically 1 to 2 s) are even more favorable for liquid yields: typically 10 wt% to 20 wt% gas, 60 wt% to 75 wt% liquid, and 10 wt% to 20 wt% char. The highest liquid yields, up to 75 wt%, can be obtained through flash pyrolysis.

[0005] Bio-oils can be processed to provide low-cost, renewable liquid fuels; in fact, they can be used as fuel for boilers, as well as for stationary gas turbines and diesel engines. Furthermore, rapid pyrolysis has been demonstrated on a fairly large scale (approximately several hundred tons per day). However, this technology has not yet achieved any significant commercial applications. The reason is likely primarily related to the generally poor physical and chemical properties of bio-oils, especially those produced by rapid pyrolysis. For example, some of the undesirable properties of pyrolysis bio-oils may include: (1) corrosivity due to their high water and acid content; (2) relatively low specific heat due to their high oxygen content (typically around 40% by mass); (3) chemical instability due to the large number of reactive functional groups (such as carboxyl and phenolic groups) that can lead to polymerization during storage and subsequent phase separation; (4) relatively high viscosity and sensitivity to phase separation under high shear conditions, such as in nozzles; (5) incompatibility with conventional hydrocarbon fuels due to their insolubility in these fuels; and (6) nozzle and pipe blockage caused by the occasional carbon particles that will always be present to some extent in unfiltered bio-oils. All these factors combined make the disposal, transportation, storage, and use of bio-oils difficult and expensive.

[0006] Therefore, the economic viability of bio-oil production for fuel or energy applications depends on finding appropriate methods to convert it into higher-quality liquid fuels at a sufficiently low cost.

[0007] Over the past two decades, methods for the direct hydrotreating of bio-oils to convert them into stable oxygenated compounds or hydrocarbons have been extensively studied. A major obstacle to the catalytic hydrotreating of bio-oils is their tendency to polymerize when heated above 100°C, ultimately leading to the formation of foreign solids or coke at temperatures above 140°C, resulting in reactor blockage and catalyst deactivation.

[0008] Therefore, there is a need for an improved method for the hydrotreating of bio-oils that minimizes solid formation and catalyst deactivation and provides modified deoxygenated oil products that can be used to produce useful fuels. Summary of the Invention

[0009] This disclosure provides a method for upgrading a bio-oil stream. The method includes reacting the bio-oil stream with hydrogen in a reactor in the presence of a catalyst and a stabilizing oil to produce a upgraded bio-oil stream. A recycle stream is removed from the upgraded bio-oil stream. The recycle stream is recycled back to the reactor to provide the stabilizing oil. The contents of the reactor can be analyzed to measure the concentration of selected components and compared to predetermined ranges. If the measured values ​​are within the predetermined ranges, the upgraded bio-oil stream can be removed from the reactor and used directly as fuel or fed into an FCC unit, hydrotreating unit, reforming unit, or other downstream processing unit to produce one or more intermediate blends and fuels. The recycle stream can be recycled back to the reactor to compensate for the petroleum feed stream. Additionally, a fuel oil stream can be removed from the upgraded bio-oil stream. The catalyst can be separated from the upgraded bio-oil stream and recycled back to the reactor along with the recycle stream. The upgraded bio-oil stream can be used directly to produce intermediate blends or fuels. Attached Figure Description

[0010] Figure 1 A schematic diagram illustrating a method for upgrading a bio-oilseed stream according to an exemplary embodiment of the present disclosure is shown.

[0011] Figure 2 The ATR-IR spectra of different oils according to this disclosure are shown.

[0012] Figure 3 The integral areas of various 1H NMR spectral regions of different oils according to this disclosure are shown.

[0013] Figure 4 The integrated areas of various 13C NMR spectral regions of different oils according to this disclosure are shown.

[0014] Figure 5 The carboxylic acid values ​​of different oils according to this disclosure are shown.

[0015] Figure 6 The oxygen concentrations of different oils according to this disclosure are shown.

[0016] definition

[0017] As used herein, the terms “reactor,” “method apparatus,” “method unit,” or “reactor assembly” shall include any method apparatus and method unit used in a hydrocarbon conversion process, as well as all method apparatus and method units, including any upstream and / or downstream apparatus from a particular unit and / or auxiliary equipment, such as furnace tubes, associated piping, heat exchangers, heater tubes, etc.

[0018] As used herein, the terms “major” or “dominant” or “primary” mean greater than 50%, suitably greater than 75%, and preferably greater than 90%.

[0019] As used in this article, the term "carbon number" refers to the number of carbon atoms in each hydrocarbon molecule, and typically in an alkane molecule.

[0020] As used in this article, "petroleum feedstock" or "petroleum raw materials" can refer to crude oil, crude oil refinery distillates, crude oil refinery residues, cracking products or hydrocarbons from crude oil refineries, liquefied coal, and bitumen, which are typically extracted from underground or the seabed.

[0021] As used herein, the term “true boiling point” (TBP) refers to a test method conforming to ASTM D-2892 for determining the boiling point of a substance. ASTM D-2892 is used to produce standardized masses of liquefied gases, distillate fractions, and residues for which analytical data are available, and to determine the yield of the aforementioned fractions by both mass and volume, based on which a graph of distillation temperature versus mass% is obtained using fifteen theoretical plates in a column with a reflux ratio of 5:1.

[0022] As used herein, the terms “T10” or “T90” refer to the boiling temperature of a sample at 10% or 90% mass (as the case may be) as determined by ASTM D-86 or TBP.

[0023] As used herein, the term “vacuum gas oil” (VGO) includes hydrocarbons having an initial boiling point above 343°C (650°F), a T10 boiling point temperature of 370°C (698°F) according to ASTM D1160, and a T90 boiling point temperature of 500°C (932°F) according to ASTM D1160.

[0024] As used herein, the term “stabilized oil” means a modified oil having a desired concentration of functional groups or properties that enable it to be used directly as fuel or for the production of intermediate blends or fuel streams that can be transported or processed in a refinery process unit.

[0025] As used herein, the terms “molar %H” and “molar %C” refer to the percentage of the number of moles of hydrogen or carbon atoms in the oil relative to the total number of moles of hydrogen or carbon atoms in the oil, respectively. For example, if a bio-oil composition contains 5 moles of hydrogen atoms and 10 moles of carbon atoms, and is said to contain 10 moles %H of aldehydes and 20 moles %C of carboxylic acids and esters, this means that 0.5 moles of hydrogen atoms in the bio-oil correspond to H atoms in a molecule with an aldehyde functional group, and 2 moles of carbon atoms in the bio-oil correspond to C atoms in a molecule with a carboxylic acid or ester functional group.

[0026] As used herein, the terms “bio-derived” or “bio-based” materials mean, but are not limited to, materials derived from or made from plants, animals, microorganisms, algae, or biopolymers.

[0027] As used herein, the term “recirculation ratio” or “recirculation rate” refers to the ratio of the recirculation flow rate to the fresh feed flow rate. Detailed Implementation

[0028] When attempting to convert bio-oil into fuel, bio-oil polymerization during deoxygenation or hydrorefining reactions presents a major challenge. This disclosure provides a method for modifying biomass-based feedstocks, such as bio-oil, to produce modified bio-oil in the presence of a catalyst and a stabilizing oil. The modified bio-oil can be used directly as fuel oil, such as marine fuel. Alternatively, the modified bio-oil can be used as feedstock for FCC units, hydrotreating units, or reforming units to produce intermediate blends or fuels. The modification method may include various analyses of the reactor contents to generate spectral data to identify molecular functional groups that lead to bio-oil polymerization. Identifying and tracking the evolution of functional groups as catalyst or process conditions change helps to target groups that lead to rapid polymerization and carbonization, providing the potential to selectively eliminate these groups, thereby improving the performance of the modification method. As described in detail later, the method includes converting oxygen-containing compound groups present in the feedstock, for example, to control carbonization potential.

[0029] Bio-oil, derived from lignocellulosic biomass, is likely a complex mixture of compounds, including oxygenated compounds obtained from the breakdown of biopolymers in the biomass. Bio-oil can be derived from plants such as grasses and trees, sawdust, husks, cereals, grass, corn, corn husks, weeds, aquatic plants, hay, and other lignocellulosic material sources such as municipal waste, food processing waste, forestry waste and cuttings, energy crops, or agricultural and industrial waste (such as bagasse, oil palm waste, sawdust, or straw). Bio-oil can also be derived from pulp and paper byproducts (recycled or not). Bio-oil is typically obtained from these biomass feedstocks through thermochemical liquefaction (particularly pyrolysis, such as flash pyrolysis, rapid pyrolysis, slow pyrolysis, or catalytic pyrolysis). Hydrothermal liquefaction can also be used to generate bio-oil feedstocks. Several different methods for producing bio-oil can be used to produce bio-oil crude oil feedstocks.

[0030] Bio-oil is a highly oxidized polar hydrocarbon product that, on an anhydrous basis, typically contains at least 10% by mass oxygen, typically 10% to 60% by mass oxygen, and more typically 30% to 50% by mass oxygen. Generally, bio-oil contains oxygenated compounds, which may include alcohols, aldehydes, ketones, acetates, ethers, esters, organic acids, and aromatic oxygenated compounds. Oxygen is also present as at least 10% by mass of free water, typically 15% to 35% by mass. These properties make bio-oil immiscible with fuel-grade hydrocarbons, and even with aromatics that typically contain little or no oxygen.

[0031] In one aspect of this disclosure, the biomass-based feed stream may include a bio-oil stream obtained through the pyrolysis of biomass feedstock.

[0032] The biomass-based feed streams of this disclosure may also contain other oxygenated compounds derived from biomass, such as oils derived from vegetable or animal fats. Oils derived from vegetable or animal fats contain fatty substances and therefore correspond to natural or refined substances of animal or plant origin, primarily containing triglycerides. This essentially involves oils from renewable resources, such as fats and oils from plant and animal resources (such as lard, tallow, poultry fat, bone fat, fish oil, and dairy-derived fats), and compounds and mixtures derived therefrom, such as fatty acids or fatty acid alkyl esters. Products generated from the recycling of animal fats and vegetable oils from the food processing industry may also be used alone or blended with other ingredient categories described above. Feeds may include vegetable oils from oilseeds, such as rapeseed, erucic acid rape, soybean, jatropha, sunflower, palm, coconut meat, palm nuts, peanuts, olives, corn, cocoa butter, nuts, flaxseed oil, or oils from any other plant. These vegetable oils are predominantly composed of fatty acids (typically above 97% by mass) in the form of triglycerides having long alkyl chains in the range of 8 to 24 carbon atoms, such as butyric acid, hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, codoleic acid, eicosapentaenoic acid (EPA), behenic acid, erucic acid, docosahexaenoic acid (DHA), and tetracosanoic acid. Fatty acid salts, fatty acid alkyl esters, and free fatty acid derivatives (such as fatty alcohols) produced by hydrolysis, fractionation, or transesterification of, for example, triglycerides or mixtures of these oils and their derivatives also fall within the definition of "oils of plant or animal origin" feedstocks in this disclosure. All products or mixtures of products from the thermochemical conversion of algae, or products from the hydrothermal conversion of lignocellulosic biomass or algae (with or without a catalyst) or pyrolysis of lignin, are also usable feedstocks.

[0033] Furthermore, feedstocks containing bio-oil can be co-processed with petroleum and / or coal-derived hydrocarbon feedstocks. Petroleum-derived hydrocarbon feedstocks can be straight-run vacuum distillates, vacuum distillates from conversion processes such as those from coking, fixed-bed hydroconversion, or hydrorefining of heavy fractions from fluidized bed or slurry hydrocracking, or these vacuum distillates from solvent-deasphalted oils. Feedstocks can also be formed by mixing these various fractions, particularly deasphalted oils and vacuum distillates, in any proportion. They may also contain products from fluidized catalytic cracking units, such as light cycle oils (LCO) from various sources, heavy cycle oils (HCO) from various sources, and any distillate fractions from fluidized catalytic cracking typically having a distillation range of 150°C to 370°C. They may also contain aromatic extracts and alkanes obtained from the manufacture of lubricating oils. Coal-derived hydrocarbon feedstocks can be products of coal liquefaction. Aromatic fractions from coal pyrolysis or coal gasification can also be used as biomass-based feedstocks.

[0034] Figure 1 An exemplary embodiment of a method for modifying a bio-oil stream is shown. The bio-oil stream enters line 122 from a source (e.g., bio-oil storage tank 120). The bio-oil stream in line 122 can be passed to mixer 140. Alternatively, the bio-oil stream in line 122 can be pumped via pump 123, and the pumped bio-oil stream in line 124 can be passed to mixer 140. In one aspect, a control valve 125 is provided to maintain the desired flow rate of the bio-oil stream to mixer 140.

[0035] According to this disclosure, a non-biologically derived feed stream can also be passed to a mixer and mixed with a bio-oil stream. In one embodiment of this disclosure, the oil stream is a non-biologically derived feed stream. The oil stream enters line 132 from a source (e.g., oil storage tank 130). The oil stream in line 132 can be passed to mixer 140. Alternatively, the oil stream in line 132 can be pumped via pump 133, and the pumped oil stream in line 134 can be passed to mixer 140. In one aspect, control valve 135 is provided to maintain the desired flow rate of the oil stream to mixer 140. In one embodiment, a sulfur source including a sulfurizing agent in line 131 can be added to the oil stream in line 132 or the bio-oil stream in line 122 and passed to mixer 140. Control valves 125 and 135 can be used to control or regulate the ratio of the bio-oil stream to the oil stream fed to mixer 140. On the one hand, the oil flow in pipeline 132 can be characterized as a stable oil flow with a desired concentration of functional groups (such as oxygen-containing compounds).

[0036] In mixer 140, the bio-oil stream from line 124 and the petroleum stream from line 134 are mixed and maintained sufficiently mixed at the start of the process, possibly with an excess of petroleum stream. In one embodiment, the bio-oil stream from line 124 and the petroleum stream from line 134 are mixed in mixer 140 at a bio-oil stream to petroleum stream mass ratio of less than 1 at startup to provide a mixed stream. After mixing, the mixed stream from line 142 is removed from mixer 140. In one aspect, mixed stream 142 comprises a bio-oil stream and a petroleum stream at a mass ratio of 0:100 to 80:20 at startup. In an exemplary embodiment, the petroleum stream from line 134 is vacuum gas oil (VGO). The mixed stream from line 142 may be reacted with hydrogen in a reactor in the presence of a catalyst to produce a modified bio-oil stream.

[0037] In one embodiment, the mixed feed stream in line 142 is passed to liquid-phase hydrorefining (LPH) reactor 150. As described in detail later, the recycle feed stream in line 163 may also be passed to reactor 150. The hydrogen feed stream in line 144 may also be passed to reactor 150. In one embodiment, the hydrogen feed stream in line 144 may be co-mixed or mixed with the mixed feed stream in line 142 and passed to reactor 150. The catalyst feed stream in line 145 may also be passed to reactor 150. In one embodiment, the catalyst feed stream may be co-mixed or mixed with the mixed feed stream in line 142 to provide a combined feed stream in line 146, which is passed to reactor 150. In another embodiment, the catalyst feed stream 145 may be added to the recycle feed stream in line 163 to provide a combined recycle feed stream, which is passed to reactor 150. In reactor 150, petroleum feed stream, bio-oil feed stream, recycle feed stream, and hydrogen feed stream can be reacted on a catalyst in a continuous liquid phase to provide a modified bio-oil feed stream in line 154. At least 50% by weight of the modified bio-oil feed stream is bio-derived. Preferably, at least 100% by weight of the modified bio-oil feed stream is bio-derived.

[0038] The modified biofuel stream in pipeline 154 can be fed into an FCC unit, a hydrotreating unit, or a reforming unit to produce an intermediate blend or a fuel stream, as described in detail later. Alternatively, a fuel stream can be withdrawn from the modified biofuel stream in pipeline 154. In one aspect, a portion of the modified biofuel stream in pipeline 154 can be withdrawn and fed into an FCC unit, a hydrotreating unit, or a reforming unit to produce an intermediate blend or a fuel stream. Another portion of the modified biofuel stream in pipeline 154 can be considered as a fuel stream.

[0039] In an exemplary embodiment, the modified biofuel stream in pipeline 154 can be separated into a light modified biofuel stream in pipeline 159 and a heavy modified biofuel stream in pipeline 179.

[0040] Liquid-phase hydrorefining (LPH) is used to upgrade heavy hydrocarbon feedstocks to produce distillate products. Hydrorefining catalysts typically consist of solid particulate compounds of catalytically active metals, metal sulfides, or metals in elemental form, either alone or supported on refractory materials such as inorganic metal oxides (e.g., alumina, silica, titanium dioxide, zirconium oxide, and mixtures thereof). Other suitable refractory materials include carbon, coal, and clay. Zeolite and non-zeolite molecular sieves can also be used as solid supports. One advantage of using solid particles alone or in a supported manner is that these particles can act as “coke absorbents” or adsorbents for asphaltenes, which tend to contaminate process equipment during precipitation.

[0041] Catalytically active metals used in LPH include those from Groups IVB, VB, VIB, VIIB, or VIII of the periodic table. These metals are incorporated into heavy hydrocarbon feedstocks in amounts effective for the desired hydrorefining reaction to provide, for example, lower-boiling hydrocarbons that can be fractionated from LPH effluents as naphtha and / or distillate products in the absence of substantially any solid particles. Representative metals include iron, nickel, molybdenum, vanadium, tungsten, cobalt, ruthenium, and mixtures thereof. Catalytically active metals can exist as solid particles in elemental form or as organic or inorganic compounds (such as sulfides, e.g., iron sulfide) or other ionic compounds. Metal or metal compound nanoaggregates can also be used to form solid particles.

[0042] In some embodiments, the metal compound can be formed in situ into solid particles from a catalyst precursor (such as a metal sulfite, e.g., ferrous sulfite monohydrate) that decomposes or reacts in the LPH reaction zone environment or during a pretreatment step to form the desired, well-dispersed catalytically active solid particles (e.g., as iron sulfide). The catalyst precursor also includes an oil-soluble organometallic compound containing the catalytically active metal of interest, which thermally decomposes to form catalytically active solid particles (e.g., iron sulfide). Such compounds are typically highly dispersed in heavy hydrocarbon feedstocks and are usually converted into solid particles contained in the slurry effluent under pretreatment or LPH reaction conditions. The catalyst precursor also includes oil-soluble organometallic compounds, inorganic molybdenum compounds, or chelated metal compounds containing a catalytically active metal. Molybdenum chelates (including molybdenum octanoate, molybdenum dithiocarbamate, and molybdenum naphthenate) and molybdenum compounds (such as ammonium heptamolybdate and phosphomolybdic acid) undergo thermal decomposition to form solid particles by reacting with sulfidation components or other sulfidation additives in the feed (such as dimethyl disulfide, di-tert-butyl(poly)sulfide, dibenzyl disulfide, (di)allyl(di)sulfide, ammonium sulfite, dimethyl sulfite, dithiothreitol, elemental sulfur, or thiourea). This results in the formation of, for example, catalytically active molybdenum disulfide. For instance, U.S. Patent No. 5,474,977 describes an exemplary in-situ solid particle preparation involving the pretreatment of heavy hydrocarbon feedstocks and precursors of the ultimately desired metal compound.

[0043] On the other hand, a catalyst precursor having a sulfidation component or sulfidation additive can be provided in pipeline 131, and the catalyst precursor can be added to the petroleum feed stream in pipeline 132. On the other hand, a catalyst or catalyst precursor can be added to the feed stream in pipeline 122 or the petroleum feed stream in pipeline 132.

[0044] Alternatively, such metal sulfides or other active metal compounds can be formed in situ by typical methods used for the production of metal sulfides or in a separate process step. One such method involves hydrothermal synthesis, in which a molybdenum compound and a sulfide component are added to water along with an additional reducing agent, such as citric acid, oxalic acid, or hydrochloric acid or gaseous hydrogen. In some cases, the sulfide component may also act as a reducing agent, such as thiourea, ammonium sulfite, dimethyl sulfite, or dithiothreitol. The hydrothermal synthesis solution can be loaded into an autoclave reactor and sealed. If gaseous hydrogen is the reducing agent, the autoclave reactor can be pressurized from 1378 kPag (200 psig) to 10342 kPag (1500 psig) using hydrogen, or hydrogen can be flowed through the autoclave reactor and bubbled. The autoclave reactor is then heated to a synthesis temperature of 200°C to 300°C under the aforementioned hydrogen or inert gas pressure and held at this synthesis temperature for 0.5 to 16 hours. The autoclave reactor is allowed to cool to room temperature before depressurization and unloading. Solid catalysts can be collected, for example, by centrifugation, filtration, or drying. An example of hydrothermal metal sulfide synthesis is described in J. Espano, “Phase Control in the Synthesis of Iron Sulfides” (145, J. Am. Chem. Soc., 18948–18955, 2023).

[0045] Another method for the non-in-situ formation of metal sulfides can be a sulfidation process in a fixed-bed reactor. This method involves loading a powdered or spherical molybdenum compound into a fixed-bed reactor and allowing a sulfiding gas (such as hydrogen sulfide) or a sulfiding liquid (such as oil doped with a sulfiding agent) to flow over a catalyst bed. The fixed-bed reactor is heated, for example, to a sulfidation temperature of 200°C to 350°C under the flow of sulfiding gas and / or hydrogen. Before or after heating to the sulfidation temperature, the reactor is pressurized to a pressure of 1378 kPag (200 psig) to 13790 kPag (2000 psig). The reactor can be heated slowly, for example, at a rate of 1°C / min, and maintained at any temperature setpoint during the process of reaching the final sulfidation temperature. The reactor can be maintained at the temperature setpoint for several hours to several days. Once sulfidation is complete, the reactor is cooled to room temperature, and the catalyst is unloaded from the reactor in its metal sulfide form. The particle size of the sulfidation catalyst can be further reduced by grinding, milling or other methods, so that the sulfidation catalyst becomes a fine powder and is highly dispersible.

[0046] Another method for the non-in-situ formation of metal sulfides can be a sulfidation process relying on chemical vapor deposition (CVD) techniques. Such methods involve molybdenum compounds (such as molybdenum trioxide, molybdenum dioxide, molybdenum foil, or dipotassium tetrathiomolybdate) and sulfur compounds (such as elemental sulfur, alkali metal sulfates, alkaline earth metal sulfates, or other metal sulfates or similar metal sulfites). Substrates (such as SiO2 / Si wafers, graphene / graphite), or powdered or spherical substrates commonly used as catalyst supports (such as SiO2, Al2O3, or TiO2) are also used. Using a typical tube furnace synthesis reactor, the reactants and supports are placed in the reactor tube in a specific order: first the sulfur source (upstream), then the downstream molybdenum source, and then the substrate further downstream. All the compounds mentioned above are placed in the hot zone of the tube furnace, typically in ceramic or other heat- and chemically resistant holders, which can be controlled as separate zones or as a single zone. If necessary, the substrate can be placed outside the hot zone. This positioning ensures that the gas flow through the tube contacts the sulfur source first, then the molybdenum source, and then the substrate. The gas flow may include inert gas, hydrogen, steam, and / or oxygen / air. In typical operation, the gas flow is initiated, and the tubular furnace reactor zone is heated to a temperature suitable for evaporating one or more of the compounds mentioned above at ambient pressure, typically equal to or less than 1000°C. The compounds evaporate and flow downstream, where they react with each other and deposit onto a substrate. Synthesis can proceed until all reactants are completely consumed, or the substrate can be moved in and out of the apparatus, limiting the deposition time to a few minutes. After synthesis is complete, the generated metal sulfides are collected by removing the substrate holder. The metal sulfide catalyst can be used as is, or, in the case of depositing a flat substrate (such as a silicon wafer), the catalyst powder can optionally be scraped off for use in the absence of a silicon wafer. An example of the synthesis of metal sulfides by chemical vapor deposition is described in W. Fu, “Toward Edge Engineering of Two-Dimensional Layered Transition-Metal Dichalcogenides by Chemical Vapor Deposition” (17 (17), ACS Nano, 16348-16368, 2023).

[0047] Other suitable precursors include metal oxides that can be converted into catalytically active (or more catalytically active) compounds, such as metal sulfides. In specific embodiments, minerals containing metal oxides can be used as precursors for solid particles of catalytically active metals (e.g., iron sulfide) contained on an inorganic refractory metal oxide support (e.g., alumina). Bauxite represents a particular precursor in which the conversion of iron oxide crystals contained in the mineral provides iron sulfide catalysts as solid particles, wherein the converted iron sulfide is supported on alumina primarily present in the bauxite precursor.

[0048] The active metals used as the hydrogenation component in the hydrotreating catalysts disclosed herein are Group VIII base metals, namely iron, cobalt, and nickel. In addition to these metals, other promoters, including Group VIB metals such as molybdenum and tungsten, may be used in combination. The amount of the hydrogenating metal in the catalyst can vary over a wide range. Any amount between 0.05% by weight and 80% by weight can be used. In one aspect, molybdenum can be provided as a milled hydrorefining catalyst with a particle size typically less than 60 mesh, preferably less than 100 mesh, more preferably less than 200 mesh, and even more preferably less than 400 mesh. The hydrorefining catalyst can be sulfided in situ or ex-situ using any of the methods mentioned throughout the text. In one aspect, molybdenum can be provided as an organomolybdenum (such as molybdenum octoate or molybdenum dithiocarbamate), which, because it is oil-soluble or hydrocarbon-soluble, can be added directly to the hydrocarbon feed, either separately from or together with the carbon particles. Molybdenum can react with sulfur or additives provided in the hydrocarbon feed to produce molybdenum sulfide in the reactor as the active form of the molybdenum catalyst.

[0049] Nickel can be provided as a catalyst by adding molybdenum.

[0050] On the other hand, the catalyst is a nickel sulfide and molybdenum sulfide catalyst, wherein nickel is incorporated into the molecular structure of molybdenum sulfide to enhance catalytic activity, but a separate nickel sulfide phase with its own independent catalytic activity can also be formed. In the synthesis involving aqueous solutions as described throughout, nickel can be added by simply introducing the nickel compound into the aqueous solution before heating to the final synthesis temperature. In the synthesis involving solid and gas or solid and liquid methods, the nickel compound can be physically mixed with the molybdenum compound. To form nickel sulfide and molybdenum sulfide in situ in the LPH, oil-soluble nickel compounds can be added directly to the feed or from a separate line to the LPH. Usable nickel compounds include nickel octanoate, nickel nitrate hexahydrate, nickel sulfate, nickel sulfite, nickel acetate tetrahydrate, nickel citrate hydrate, nickel hydroxide, or basic nickel carbonate. The molar ratio of molybdenum to nickel can range from 1:1 to 5:1, preferably 2:1 to 4:1, or preferably 2.5:1 to 3.5:1.

[0051] Sulfur can be provided by a solid or liquid sulfiding agent, which is added via line 131 to the petroleum feed stream in line 132, or to the recirculated feed stream leading to the reactor, or premixed into the feed. A gaseous sulfiding agent (such as hydrogen sulfide) can be added to the hydrogen line 144. Some preferred sulfiding agents are hydrogen sulfide, dimethyl disulfide, di-tert-butyl(poly)sulfide, dibenzyl disulfide, (di)allyl(di)sulfide, ammonium sulfite, dimethyl sulfite, dithiothreitol, elemental sulfur, or thiourea.

[0052] Aqueous molybdenum can be derived from the reaction of MoO3 with acidic or alkaline aqueous solutions (such as phosphoric acid or ammonium hydroxide). Molybdenum, in water-soluble or oil-soluble liquid form and in volume chosen to achieve the target concentration, can be dropped onto carbon particles that can be used as a carrier.

[0053] Without the aid of other catalysts, the concentration of molybdenum in the liquid feed to the LPH reactor can be greater than 0 w ppm and not exceed 2 wt% in the liquid feed, suitably not exceed 0.5 wt%, and typically not exceed 2000 w ppm in the liquid feed. In some cases, the concentration of molybdenum in the liquid feed can be not less than 1000 w ppm, and preferably not less than 500 w ppm in the feed.

[0054] In a preferred embodiment where the catalyst contains both nickel and molybdenum, the concentration of molybdenum in the liquid feed to the LPH reactor is the same as specified above. The concentration of nickel in the liquid feed to the LPH reactor may be greater than 0 w ppm and not exceed 2% by weight in the liquid feed, suitably not exceed 0.5% by weight, and typically not exceed 2000 w ppm. In some cases, the concentration of nickel in the liquid feed may be not less than 1000 w ppm, and preferably not less than 500 w ppm of the feed. Feed means all feed streams leading to the reactor.

[0055] In a preferred embodiment, the feed stream containing the catalyst can be recycled back to the reactor. Therefore, the concentration of molybdenum in the reactor can be controlled at a steady-state level greater than the concentration of molybdenum in the liquid feed. The concentration of molybdenum in the reactor liquid is typically between 0.1 wt% and 10 wt%, preferably between 0.5 wt% and 7 wt%, more preferably between 2 wt% and 7 wt%, and even more preferably between 0.2 wt% and 3 wt%.

[0056] Conditions in the LPH reactor 150 typically include: temperatures of 315°C (600°F) to 538°C (1000°F), or 321°C (610°F) to 482°C (900°F), or 340°C (644°F) to 470°C (878°F); pressures of 3.5 MPa (500 psig) to 30 MPa (4351 psig), suitably 5.5 MPa (800 psig) to 19.3 MPa (2800 psig), preferably 6.8 MPa (1000 psig) to 13.8 MPa (2000 psig), or more preferably not exceeding 10.3 MPa (1500 psig); and reactor liquid residence times of 0.1 hours to 8 hours, preferably 2 hours to 6 hours, or 1 hour to 5 hours, or greater than 3 hours.

[0057] In another exemplary embodiment of this disclosure, reactor 150 may be a continuous stirred tank reactor (CSTR). Operating conditions in CSTR 150 may be as given above, but may preferably include a temperature of 300°C (572°F) to 500°C (932°F), a pressure of 6.8 MPa (1000 psig) to 13.8 MPa (2000 psig), and a residence time of 30 minutes to 8 hours. The modified bio-oil stream flows from reactor 150 into line 154.

[0058] On one hand, reactor 150 can be selected from bubble column reactors, slurry reactors, and fluidized bed reactors to promote contact and mixing of gas with liquid or slurry materials. Other types of reactors can be used to promote contact and mixing.

[0059] On the other hand, reactor 150 can be a single-pass reactor for processing the feed stream to produce a modified bio-oil stream.

[0060] According to this disclosure, method 100 may include an analyzer 161 for analyzing the composition of various feed streams entering and leaving reactor 150. Analyzer 161 may be adapted to take corrective actions to adjust the composition of one or more feed streams.

[0061] For a single-pass reactor 150, analyzer 161 can measure the composition of the materials within the single-pass reactor 150. If the composition of the materials does not fall within a predetermined range, the reactor conditions and feed conditions (such as the ratio of the bio-oil stream in line 122 to the stable oil stream including the petroleum stream in line 134) can be adjusted.

[0062] When recirculated oil is used, the composition of the materials within reactor 150 can also be analyzed. If the composition of the materials does not fall within a predetermined range, the reactor conditions and feed conditions (such as the ratio of the bio-oil stream in line 122 to the stable oil stream including the petroleum stream in line 134 and / or the recirculated feed stream in line 163 fed into reactor 150) can be adjusted.

[0063] For example, analyzer 161 may use one or more of, for example, infrared (IR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy to measure the composition of the reaction mixture within reactor 150. According to the 1H NMR spectrum, the reaction mixture within reactor 150 should include an aldehyde with a concentration of 0 mol%H to 3 mol%H, or preferably 0 mol%H to 2 mol%H, or more preferably 0 mol%H to 1 mol%H. According to the 13C NMR spectrum, the reaction mixture within reactor 150 should comprise: at least one of ketones and aldehydes at a concentration of 0 mol%C to 6 mol%C, or preferably 0 mol%C to 4 mol%C, or more preferably 0 mol%C to 2 mol%C; at least one of carboxylic acids and esters at a concentration of 0 mol%C to 6 mol%C, or preferably 0 mol%C to 4 mol%C, or more preferably 0 mol%C to 3 mol%C; and at least one of ethers, alcohols, phenylmethoxy groups, and carbohydrates at a concentration of 0 mol%C to 6 mol%C, or preferably 0 mol%C to 4 mol%C, or more preferably 0 mol%C to 2 mol%C.

[0064] The composition of the materials (such as the reaction mixture) within reactor 150 can also be characterized by the ratio of the band areas of oxygen-containing compounds as measured by ATR-IR spectroscopy. In an exemplary embodiment, the composition of the reaction mixture within reactor 150 should have one or more of the following oxygen-containing compound ratios: a (CO) / C ratio of 0 to 0.7, or preferably 0 to 0.5, or more preferably 0 to 0.4; a (C=O) / C ratio of 0 to 0.5, or preferably 0 to 0.4, or more preferably 0 to 0.3; an OH / C ratio of 0 to 2.5, or preferably 0 to 1.5, or more preferably 0 to 1; and an O / C ratio of 0 to 1.7, or preferably 0 to 1, or more preferably 0 to 0.6.

[0065] The applicant has discovered that producing modified bio-oil feed streams with missing or reduced levels of specific functional groups eliminates the challenge of fresh bio-oil polymerization in reactors such as CSTRs or slurry reactors. The reaction leading to bio-oil polymerization is inhibited because the specific functional groups in the reactor's liquid contents are depleted. The applicant has analyzed liquid effluents from the reactor, including modified bio-oil, to identify the specific functional groups that cause bio-oil polymerization. In a well-mixed CSTR reactor, the reactor liquid effluent represents the liquid composition at all locations within the reactor. The applicant discloses various methods or tests for analyzing liquid effluents from the reactor, including spectroscopy, such as nuclear magnetic resonance (NMR) spectroscopy and attenuated total reflectance-infrared (ATR-IR) spectroscopy. Other tests may include acid value testing and carbon-hydrogen-nitrogen-oxygen (CHNO) elemental analysis, such as ASTM D5291 CHN and ASTM UOP649 Oxygen. Acid value testing may include TAN (Total Acid Number) and CAN (Carboxylic Acid Number). Using one or more of these tests, the applicant identifies “adverse agents” that cause bio-oil polymerization. Furthermore, by identifying these groups, applicants can distinguish acceptable reactor effluent streams that can be used as is or passed on for further processing from unacceptable reactor effluent streams that are not stable enough for downstream processing.

[0066] The recirculated oil stream taken from the reactor effluent can be recycled back to the reactor along with the recirculating catalyst to reduce the concentration of adverse substances in the reactor and allow these adverse substances to undergo further transformation to produce a modified bio-oil stream. The recirculated stream can be passed to the reactor and can replace the petroleum feed stream. The modified bio-oil stream does not polymerize or generate carbon from bio-oil polymerization during further processing in downstream processes such as hydrorefining, FCC, hydrotreatment, or reforming. Identifying and tracking the evolution of functional groups as catalyst or process conditions change allows targeting of chemical functional groups that lead to rapid polymerization and carbonization and provides the potential to eliminate these chemical functional groups, thereby improving the performance of the modification method.

[0067] Re-reference Figure 1The modified bio-oil stream in line 154 is passed to thermal separator 160. In thermal separator 160, heavy oil is separated from light oil. The bottom feed stream from the bottom of thermal separator 160 enters line 156. In an exemplary embodiment, the bottom feed stream in line 156 is a stable oil stream. The bottom feed stream containing catalyst is separated and allowed to enter line 156 from thermal separator 160. The bottom feed stream in line 156 includes a majority of the catalyst; for example, all catalyst discharged from reactor 150 may enter the bottom feed stream in line 156. In one aspect, the bottom feed stream in line 156 may be characterized as a heavy oil stream including catalyst. Light oil enters the top feed stream in line 155 from thermal separator 160. Water is also separated in thermal separator 160 and enters the top feed stream in line 155 along with the light oil. The thermal separator 160 can operate at temperatures ranging from 250°C to 400°C and pressures comparable to those of the reactor 150.

[0068] On the one hand, the stable oil flow in pipeline 156 is characterized by an acid value not exceeding 60 mg KOH / g, preferably not exceeding 50 mg KOH / g, and more preferably not exceeding 40 mg KOH / g.

[0069] The bottom feed stream in line 156 is recirculated to reactor 150. The stabilized oil stream in line 156 can be transferred to recirculation tank 177. The recirculated oil stream, including stabilized oil and catalyst, enters line 158 from the bottom of recirculation tank 177. The heavy oil stream in line 179 can be removed from one side of recirculation tank 177. Most of the catalyst may be present in the recirculated oil stream in line 158. Controlled flow line 163 may recirculate the controlled flow of the recirculated oil stream to reactor 150 via pump 157. Control valve 162 may be provided on line 163 to regulate the flow of the recirculated oil stream, including stabilized oil, from line 158 to reactor 150, as described in detail later. Solid or liquid vulcanizing agent may be added to the recirculated stream in line 163 before recirculation to reactor 150.

[0070] In one implementation, the stable thermal tower bottom flow in line 156 can be directly recycled to reactor 150.

[0071] On one hand, the bottom feed stream in line 156 may contain low concentrations of unstable functional groups, such as oxygen-containing compounds. The heavy oil feed stream in line 179 can be removed in a manner that avoids allowing most of the catalyst to enter the stream. On the other hand, the heavy oil feed stream in line 179 may be filtered, centrifuged, vacuum flashed, or scraped-film evaporated to remove catalyst-lean heavy product streams.

[0072] In one embodiment, the heavy oil feed stream in line 179 is passed to catalyst separation vessel 136 for separation of any catalyst present. In an exemplary embodiment, catalyst separation vessel 136 may be selected from a filter vessel, centrifuge, vacuum distillation column, wiped-film evaporator, centrifuge, or a combination thereof. In catalyst separation vessel 136, the catalyst is separated from the heavy oil. The heavy oil product stream flows from catalyst separation vessel 136 into line 137. A concentrated catalyst feed stream, including the catalyst in the heavy oil, flows from vessel 136 into line 138. The heavy oil product stream in line 137 may be considered as a fuel oil product stream. The recirculated oil stream in line 158 may be recycled to reactor 150 to upgrade the biofuel stream in the presence of a stable oil. In another exemplary embodiment, the recirculated oil stream in line 158 may be combined with the concentrated catalyst feed stream in line 138 to provide a combined recirculated oil stream in line 139, which is then recycled to reactor 150. The bio-oil stream in line 122 is reacted with hydrogen in reactor 150 in the presence of catalyst and stabilizing oil in line 158 to produce a modified bio-oil stream in line 154.

[0073] A scraped-film evaporator (WFE) uses hinged blades with minimal clearance to the inner surface to agitate the flowing catalyst-containing feed to separate the catalyst from the heavy oil. In a catalyst separation vessel 136 comprising a WFE, the heavy oil feed in line 179 enters tangentially above a heated inner tube and is distributed uniformly on the inner circumference of the tube, possibly under vacuum, by rotating blades. Catalyst particles descend spirally along the wall, while bow-shaped waves generated by the rotor blades create highly turbulent flow and optimal heat flux. The heavy oil evaporates rapidly, and the vapor can flow in parallel or counter-current with the catalyst particles. In a simple WFE design, the heavy oil can be condensed in a condenser located outside the evaporator but as close as possible to it.

[0074] Other evaporation techniques can be used to separate the catalyst from the heavy oil in the catalyst separation vessel 136.

[0075] On one hand, the fuel oil stream in pipeline 166 can be extracted from the heavy oil stream in pipeline 137. In one embodiment, the remaining heavy oil stream in pipeline 184 can be processed in an FCC unit, a hydrotreating unit, or a reforming unit 180 to provide a product stream in pipeline 182. The fuel oil stream in pipeline 166 may have a typical boiling point profile of marine fuels known in the art, for example, the fuel oil stream in pipeline 166 may have a T5 of 150°C to 200°C and a T90 of 425°C to 600°C. The fuel oil stream in pipeline 166 may be delivered to a marine fuel oil pool.

[0076] According to this disclosure, analyzer 161 can be connected to control valve 162 to open the valve and release controlled flow of the recirculated oil stream in line 163. Analyzer 161 is used to monitor the chemical composition of the recirculated oil stream in line 158. The contents of the recirculated oil stream can be monitored using online analysis or by taking a sample and analyzing it offline. The composition of the stable oil stream in line 158 is monitored to determine whether the concentration of unstable functional groups is within a predetermined range. If the concentration of unstable oxygen-containing functional groups exceeds the predetermined range, the process conditions of reactor 150 can be changed to ensure that the modified bio-oil stream from reactor 150 in line 154 produces oxygen-containing functional groups at concentrations within the predetermined range.

[0077] In one embodiment, analyzer 161 measures the concentration of oxygen-containing compounds. In a specific embodiment, analyzer 161 measures the concentration of one or more oxygen-containing compounds, oxygen concentration, or acid value of one or more process feed streams. In one aspect, analyzer 161 measures the concentration of one or more oxygen-containing compounds, oxygen concentration, or acid value of a recirculated feed stream in line 158. Analyzer 161 can measure the concentration of oxygen-containing compounds in the recirculated feed stream in line 158 using one or more of NMR spectroscopy or ATR-IR spectroscopy. The analyzer can measure oxygen concentration by elemental analysis of carbon, hydrogen, nitrogen, and oxygen (CHNO) as a substitute for oxygen-containing compound concentration. In analyzer 161, the concentration of oxygen-containing compounds, oxygen concentration, or acid value is measured, and the measured values ​​are compared to predetermined ranges for the concentration of oxygen-containing compounds, oxygen concentration, and acid value, respectively. The analyzer can be an online analyzer, such as an IR spectrometer, or samples can be taken and analyzed in offline analysis. If the measured concentration of the recirculated oil stream in line 158 does not fall within a predetermined range, one or more of the operating conditions, temperature, pressure, or flow rate of the bio-oil stream, petroleum stream, hydrogen stream, sulfurizing agent stream, and catalyst stream, and / or the recirculation rate or ratio of the recirculated oil stream, can be adjusted so that the measured concentration or acid value present in the recirculated oil stream in line 158 moves towards a predetermined range satisfying the oxygen concentration, oxygen concentration, or acid value. For example, if, after measurement, the oxygen concentration, oxygen concentration, or acid value of the recirculated oil stream does not fall within a predetermined range, a higher proportion of the recirculated oil stream can be recirculated to reactor 150. This can be achieved by closing valve 143 on line 179 to reduce the flow rate of the heavy oil stream in line 179. Reducing the outflow rate of the heavy oil stream in line 137 results in a higher recirculation rate for the combined recirculated oil stream in line 158 and line 139. The outflow rate of the heavy oil stream in line 179 is reduced by closing valve 143 until the measured concentration of oxygen, oxygen or acid in the recirculated oil stream in line 158 falls within a predetermined range of the concentration of oxygen, oxygen or acid.

[0078] The recirculated oil flow in line 158 can be analyzed using one or more of infrared (IR) spectroscopy and NMR spectroscopy via analyzer 161 to determine whether the recirculated oil flow in line 158 has acceptable quality.

[0079] According to an exemplary embodiment, based on 1H NMR spectroscopy, the recirculated oil stream in pipeline 158 should include at least one or more of the following: aldehydes with a concentration of 0 mol%H to 3 mol%H, or preferably 0 mol%H to 2 mol%H, or more preferably 0 mol%H to 1 mol%H. Based on 13C NMR spectroscopy, the recirculated oil stream in pipeline 158 should include: at least one of the following groups: ketones and aldehydes with a concentration of 0 mol%C to 6 mol%C, or preferably 0 mol%C to 4 mol%C, or more preferably 0 mol%C to 2 mol%C; at least one of the following groups: carboxylic acids and esters with a concentration of 0 mol%C to 6 mol%C, or preferably 0 mol%C to 4 mol%C, or more preferably 0 mol%C to 3 mol%C; and at least one of the following groups: ethers, alcohols, phenolic methoxy compounds, and carbohydrates with a concentration of 0 mol%C to 6 mol%C, or preferably 0 mol%C to 4 mol%C, or more preferably 0 mol%C to 2 mol%C.

[0080] The recirculated oil stream in pipeline 158 may include an elemental oxygen concentration of 0% to 20% by weight, preferably 3% to 16% by weight, and more preferably 2% to 13% by weight. The concentration is based on non-solids.

[0081] The recirculated oil flow in line 158 can also be characterized by the ratio of the band areas of oxygen-containing compounds as measured by ATR-IR spectroscopy. In an exemplary embodiment, the recirculated oil flow in line 158 should have one or more of the following oxygen-containing compound ratios: a (CO) / C ratio of 0 to 0.7, or preferably 0 to 0.5, or more preferably 0 to 0.4; a (C=O) / C ratio of 0 to 0.5, or preferably 0 to 0.4, or more preferably 0 to 0.3; an OH / C ratio of 0 to 2.5, or preferably 0 to 1.5, or more preferably 0 to 1; and an O / C ratio of 0 to 1.7, or preferably 0 to 1, or more preferably 0 to 0.6.

[0082] The hot overhead feed stream, including light oil, in line 155 can be cooled and fed into cold separator 165. In cold separator 165, gaseous components are separated from the light oil. The separated gaseous components then flow from cold separator 165 into line 164. The cold overhead feed stream in line 164 can be purified to obtain a hydrogen feed stream, which can be recycled to reactor 150. The bottom light oil feed stream, including modified bio-oil and aqueous components, flows from cold separator 165 into line 169. The bottom light oil feed stream in line 169 includes water that should be separated from the modified bio-oil stream. Cold separator 165 can operate at temperatures from 0°C to 75°C and pressures equal to those of reactor 150.

[0083] In one embodiment, the bottom light oil stream in line 169 is passed to a water separator 147 to separate water from the modified bio-oil. The water is separated and flows from the water separator 147 into a bottom water-containing line 148. The light, modified bio-oil stream flows from the water separator 147 (where water concentration is lower) into line 159. The water separator 147 can operate at temperatures from 0°C to 75°C and pressures from 0 MPa (gauge pressure) (0 psig) to 1 MPa (gauge pressure) (150 psig).

[0084] Analyzer 161 can be connected to the light modified biofuel stream in line 159 to measure and analyze the concentration of unstable functional groups. Analyzer 161 can measure the concentration of one or more oxygenated compounds, oxygen concentration, or acid value of the light modified biofuel stream in line 159, as previously described. If the measured concentration of functional groups present in the light modified biofuel stream in line 159 does not fall within a predetermined range, one or more of the operating conditions, temperature, pressure, or flow rate of the biofuel stream, petroleum stream, hydrogen stream, sulfurizing agent stream, catalyst stream, and / or the recirculation rate or ratio of the recirculated stream can be adjusted so that the measured concentration or acid value present in the light modified biofuel stream in line 159 moves toward a predetermined range satisfying the oxygenated compound concentration, oxygen concentration, or acid value. If the measured value does not fall within an acceptable range after measurement, the recirculation rate of the recirculated oil stream in line 158 to reactor 150 can be increased, and the outflow rate of the heavy oil stream in line 179 can be decreased, as previously described.

[0085] Light, modified bio-oil streams can enter line 168 from line 159 via an open control valve 167 that is connected to analyzer 161.

[0086] According to this disclosure, the light modified biofuel stream in pipeline 159 can be analyzed at desired time intervals and offline by analyzer 161 using one or more of infrared (IR) spectroscopy and NMR spectroscopy to determine whether the modified biofuel stream has acceptable quality. NMR spectroscopy determines the physical and chemical properties of atoms or molecules. Proton (¹H) NMR is one of the most widely used NMR methods. Different nuclei—¹H (proton), ¹³C (carbon ¹³), ¹⁵N (nitrogen ¹⁵), ¹⁹F (fluorine ¹⁹), etc.—can also be detected by NMR spectroscopy. ¹H and ¹³C are the most widely used. Phenolic compounds can also be measured using NMR spectroscopy. With the aid of analyzer 161, characterization of the light modified biofuel stream can be used to determine the concentration of specific molecular functional groups, including aldehydes, ketones, esters, ethers, phenols, sugars, and carboxylic acids. Typically, ¹H and ¹³C values ​​are measured from NMR spectra in mol% of the corresponding H or C atoms.

[0087] According to an exemplary embodiment, based on 1H NMR spectra, the acceptable concentration of aldehydes in the light modified bio-oil stream in pipeline 159 should include a concentration of 0 mol%H to 4 mol%H, or preferably 0 mol%H to 2 mol%H, or more preferably 0 mol%H to 1 mol%H. According to another exemplary embodiment, based on 13C NMR spectroscopy, the light modified bio-oil stream in pipeline 159 shall include at least one or more of the following: at least one of ketones and aldehydes at a concentration of 0 mol%C to 6 mol%C, or preferably 0 mol%C to 5 mol%C, or more preferably 0 mol%C to 3.5 mol%C; at least one of carboxylic acids and esters at a concentration of 0 mol%C to 6 mol%C, or preferably 0 mol%C to 5 mol%C, or more preferably 0 mol%C to 4 mol%C; and at least one of ethers, alcohols, phenyl methoxy groups, and carbohydrates at a concentration of 0 mol%C to 11 mol%C, or preferably 0 mol%C to 9 mol%C, or more preferably 0 mol%C to 7 mol%C, or even more preferably 0 mol%C to 5 mol%C.

[0088] According to this disclosure, the light modified biofuel stream in pipeline 159 can be characterized by the ratio of the band areas of oxygenated compounds measured by ATR-IR spectroscopy. In an exemplary embodiment, the light modified biofuel stream in pipeline 159 should have one or more of the following oxygenated compound ratios: a (CO) / C ratio of 0 to 0.7, or preferably 0 to 0.5, or more preferably 0 to 0.4; a (C=O) / C ratio of 0 to 0.6, or preferably 0 to 0.5, or more preferably 0 to 0.4; an OH / C ratio of 0 to 3, or preferably 0 to 2, or more preferably 0 to 1.5; and an O / C ratio of 0 to 1.7, or preferably 0 to 1.3, or more preferably 0 to 0.8.

[0089] In one aspect of this disclosure, the light modified biofuel stream in pipeline 168 can be separated into several streams, and at least one of these streams can be transferred to the FCC unit or hydrotreating unit or reforming unit 180 or treated as a product stream.

[0090] In one embodiment, the feed stream can be taken from a light, modified biofuel stream in pipeline 168 and fed into an FCC unit, hydrotreating unit, or reforming unit 180 to produce an intermediate blend or fuel.

[0091] In one exemplary embodiment, a light, modified biofuel stream enters line 168 through an open control valve 167 and is delivered to FCC unit 180 to provide an FCC product stream in line 182. In another exemplary embodiment, a light, modified biofuel stream enters line 168 through an open control valve 167 and is delivered to hydrotreating unit 180 to provide a hydrotreating unit product stream in line 182. In yet another exemplary embodiment, a light, modified biofuel stream enters line 168 through an open control valve 167 and is delivered to reforming unit 180 to produce a reforming product stream in line 182.

[0092] In a preferred embodiment, the light, modified biofuel stream in line 168 can be fractionated in fractionation tower 170 to separate the light, modified biofuel stream in line 168 into one or more hydrocarbon streams. The light, modified biofuel stream in line 168 can be passed to fractionation tower 170 to provide overhead stream in line 171. The overhead stream in line 171 can be passed to receiver 173 for further separation of the overhead stream. LPG and light gases are separated into stream 172 from receiver 173. The liquid stream from receiver 173 in line 174 is separated into reflux stream in line 175 and naphtha stream in line 176. The kerosene stream can enter line 181 from one side of fractionation tower 170. The reflux stream in line 175 is recycled back to fractionation tower 170. The diesel feed stream can enter line 178 from the bottom of fractionation column 170. The reboiled feed stream can be taken from the diesel feed stream in line 178, heated in reboiler 183, and the reboiled feed stream in line 185 can be transferred to fractionation column 170.

[0093] Fractionating column 170 can be operated under vacuum pressure. In one embodiment, fractionating column 170 can be operated at a top pressure of 34 kPa (gauge pressure) (5 psig) to 173 kPa (gauge pressure) (25 psig) and a bottom temperature of 500°C (932°F) to 750°C (1382°F) or 500°C (932°F) to 600°C (1112°F).

[0094] Part or all of the naphtha stream in pipeline 176 can be transferred to reforming unit 180 or another downstream processing unit.

[0095] In one implementation, a portion or all of the diesel feed stream in pipeline 178 may be transferred to FCC unit 180, hydrotreating unit 180, or reforming unit 180.

[0096] In another embodiment, a portion or all of the kerosene stream in pipeline 181 may be transferred to FCC unit 180, hydrotreating unit 180, or reforming unit 180.

[0097] In an exemplary embodiment, the heavy fuel oil stream in line 137 is passed to FCC unit 180, hydrotreating unit 180, or reforming unit 180 to provide a product stream in line 182. In another exemplary embodiment, a marine fuel oil stream may flow from the heavy fuel oil stream in line 137 into line 166, while the remaining heavy fuel oil stream in line 184 is processed in the FCC unit, hydrotreating unit, or reforming unit 180.

[0098] On one hand, the fuel oil stream in line 166 can be passed to stripping tower 190 to strip lighter materials. A stripping medium (such as steam) can be passed to stripping tower 190 in stripping medium line 191. Lighter materials can enter the top line 192 from stripping tower 190. The stripped fuel oil stream can enter line 194 from the bottom of stripping tower 190. Stripping tower 190 can operate at a bottom temperature of 75°C to 250°C. The fuel oil stream can be marine fuel oil.

[0099] Although analyzer 161 is shown in communication with the light modified biofuel stream in line 159 and the recirculated fuel stream in line 158, analyzer 161 may be present above or elsewhere in one or all of the naphtha stream in line 176, the kerosene stream in line 181, and the diesel stream in line 178, to measure the concentration of functional groups in accordance with this disclosure.

[0100] When the recirculated oil flow in line 158 meets specifications, the recirculation rate of this recirculated oil flow towards reactor 150 can be increased by opening valve 162 to a greater extent to reduce the flow rate of the non-bio-based feed from line 134 towards reactor 150. On the other hand, the recirculated oil flow in line 158 can be analyzed by analyzer 161, independent of the analysis of the light, modified bio-based oil flow in line 159 by analyzer 161.

[0101] The recirculated oil stream in line 158 can be fed back into reactor 150 to blend the modified product with the reactor contents. The recirculation rate of the recirculated oil stream is selected such that the reactor contents consist of a specific ratio of fresh feed to modified feed, determined by both the recirculation rate and the residence time of the feed in reactor 150. The recirculation rate of the recirculated oil stream in line 158 can be regulated and transmitted to reactor 150 using control valve 162. According to this disclosure, the recirculated oil stream is recirculated to the reactor at a certain recirculation rate to provide a mixture within reactor 150 at start-up with a mass ratio of 0:100 to 85:15, or 1:99 to 80:20, or 5:95 to 85:15, comprising the recirculated oil stream in line 158, the bio-oil stream in line 122, and the modified bio-oil stream within reactor 150. When recirculation to the reactor begins in line 163, the volumetric flow rate of the non-bio-oil feed can be reduced as much as the recirculation mass flow rate. As the recirculation rate of the recirculated oil stream to the reactor increases, the flow rate of the non-bio-oil stream in line 134 may be proportionally reduced to produce a biomass-based feed stream with a dominant biomass feed. Therefore, once the recirculated oil stream begins to blend with the contents of reactor 150, the amount of oil stream 134 in the mixed stream in line 142 is proportionally reduced by controlling the flow rate of oil stream 134 through valve 135. On the other hand, the recirculation rate of the recirculated oil stream in line 158 is sufficiently increased to allow the flow rate of the oil stream in line 134 to be reduced to zero, thereby producing a 100% biomass-based modified bio-oil stream in line 154. On one hand, the recirculated oil stream in line 158 can be transferred and mixed into line 142, and then transferred to reactor 150. In one embodiment, the recirculated oil stream in line 158 is generally a bio-derived stream.

[0102] As described above, one key aspect of this disclosure involves minimizing the presence of certain unstable oxidative functional groups in reactor 150. The analytical and control methods described above are non-exclusive methods for achieving levels of chemical functional groups in the reactor below predetermined thresholds. Any control method that maintains the concentration of predetermined chemical functional groups below predetermined thresholds can be used. For example, prior experience operating the method in laboratory-scale, pilot-scale, or commercial-scale reactors can be used to establish tables or models relating process conditions and flow rates to the concentrations of chemical functional groups in the reactor, the recycle stream, or the product stream. The operation of the method can then utilize these correlations to adjust process conditions to meet desired product specifications and maintain levels of oxygen-containing functional groups below thresholds to prevent polymerization.

[0103] Measurable concentrations of oxygenated compounds may include one or more of aldehydes, ketones, esters, ethers, phenols, sugars, and carboxylic acids. According to this disclosure, phenols include phenolic acids. Modified bio-oil streams having these properties within a predetermined range can significantly reduce bio-oil polymerization in feed equipment or LPH reactors and provide modified bio-oil that can be used as feedstock for various other processes or units (such as FCC units, hydrotreating units, or reforming units 180) to produce blends and fuels. Alternatively, a portion of the modified bio-oil stream can be used directly as fuel, for example, by fractionating the modified bio-oil stream to remove lighter fractions and heavier products. The heavier products can be used as marine fuel. In this case, using the products as marine fuel may require stripping, distillation, or other methods to lower the desired fuel flash point.

[0104] Attenuated total internal reflection (ATR) is an infrared (IR) spectroscopy technique also applicable according to this disclosure. ATR-IR is a sampling technique in which a sample is placed in close contact with a crystal having a high refractive index. IR light is introduced from the bottom and reflected from the crystal surface. The sample is placed as is on a diamond crystal for ATR IR spectrum collection (64 scans, 2 cm⁻¹ resolution). The IR spectra are collected on a Nicolet iS 50 FTIR spectrometer, truncated and baseline corrected in GRAMS AI software, and deconvoluted and plotted in OriginPro 2016.

[0105] Two methods can be used for spectral integration and deconvolution. Simple integration can be performed over different functional groups. The integrated area of ​​each functional group is measured. According to this disclosure, the integrated areas for each functional group are approximately: 3100 cm⁻¹ to 3695 cm⁻¹ for hydroxyl groups, 2800 cm⁻¹ to 2995 cm⁻¹ for hydrocarbon groups, and 1000 cm⁻¹ to 1315 cm⁻¹ for methoxy groups. For the C=O and C=C regions, deconvolution can be performed by first baseline correction of the regions and then fitting multiple peaks using OriginPro software. Since there is no internal standard, the spectra may not be normalized before deconvolution; therefore, only the area ratio is available for sample comparison. The aromatic C=C band area typically originates from deconvoluted bands in the 1500 cm⁻¹ to 1600 cm⁻¹ region, olefin C=C band areas in the 1600 cm⁻¹ to 1700 cm⁻¹ region, and C=O band areas in the 1700 cm⁻¹ to 1800 cm⁻¹ region. Depending on the complexity of the region, some spectra can be deconvoluted into 6 or up to 9 bands.

[0106] The total carbon "C" value can also be calculated. The total carbon "C" value equals the sum of the integral regions of CHx stretching and C=C stretching, such that C equals the integral band area of ​​(CHx + C=C). Similarly, the total oxygen "O" value equals the sum of the integral regions of C=O stretching and CO stretching, such that O equals the integral band area of ​​(C=O + CO). All other band areas identify the specific molecular vibrations they represent.

[0107] Based on the band area values ​​of these functional groups, the band area ratios of various functional groups are also calculated. The band area ratio is a dimensionless parameter that remains constant across all measuring instruments. In one embodiment, the band area ratios of various oxygen-containing compounds are calculated to approximate the concentrations of these functional groups. In exemplary embodiments of this disclosure, the (CO) / C band area ratio should be in the range of 0 to 0.4, the (C=O) / C band area ratio should be in the range of 0 to 0.4, the OH / C band area ratio should be in the range of 0 to 1.5, and / or the O / C band area ratio should be in the range of 0 to 0.8.

[0108] Acid value is an additional suitable method for measuring carboxylic acid content. Briefly, acid value is obtained via a typical potentiometric titration using a solution of tetrabutylammonium hydroxide and isopropanol as the titrant. The standard method for benzoic acid and N,N-dimethylformamide is run every 3 hours to ensure results. The sample is weighed and added to a beaker. An N,N-dimethylformamide solution (internal standard) is added to the beaker, and the mixture is stirred under nitrogen for 5 minutes, followed by titration. In one embodiment, the carboxylic acid value should be below 60 mg KOH / g.

[0109] In addition to infrared spectroscopy, nuclear magnetic resonance spectroscopy, and titration, the oxygen content in oil can also be measured by gas chromatography (such as ASTM UOP960, GCxGC) or other chromatographic methods. Combustion analysis (such as ASTM UOP649) can be used to measure the total oxygen content in oil. Other methods known in the art can also be used.

[0110] Example

[0111] Example 1

[0112] Bio-oil and petroleum-derived VGO are stored in separate storage tanks 120 and 130, respectively. The petroleum-derived VGO feed stream is pumped and kept thoroughly mixed in mixer 140. The feed stream in line 142 is preloaded into reactor 150. A soluble Mo-based catalyst or solid Mo-based catalyst and a soluble sulfur compound are also co-blended into the feed stream. The reactor is heated with a hydrogen stream at a rate of 2 °C / h to 2 °C / min until the reactor reaches a reaction temperature of 350 °C to 450 °C. Once at the reaction temperature, the co-blended feed is pumped at a specified flow rate to maintain a reactor residence time between 30 minutes and 4 hours. Samples of the modified bio-oil feed stream are removed from the reactor at desired time intervals and analyzed using infrared and / or nuclear magnetic resonance spectroscopy.

[0113] After single-pass operation stabilizes, the recirculated feed stream 162 is removed and a portion of the modified product is blended back into reactor 150. Once stable operation with recirculation is established, the feed system gradually reduces the amount of petroleum VGO supplied to the reactor and increases the amount of bio-oil supplied, ultimately resulting in a 100% bio-oil feed. Samples of the recirculated feed stream are removed at desired time intervals and analyzed using infrared and / or nuclear magnetic resonance spectroscopy. The integrated ATR-IR spectral band area ratios of the recirculated feed stream, bio-oil feed stream, and petroleum VGO feed stream are measured. Figure 2 The results are shown in the image. Figure 2 As shown, the concentrations of aldehydes, ketones, and organic acids, expressed as band area ratios, are significantly lower in the recycled feed stream compared to fresh bio-crude oil. According to this disclosure, the concentration values ​​of functional groups in the recycled feed stream are within the expected range.

[0114] The integrated areas of various 1H and 13C NMR spectral regions were measured for recirculated feed streams, bio-oil feed streams, and petroleum VGO feed streams. The procedure for measuring the 1H and 13C NMR spectral regions is as follows:

[0115] 1 H liquid process

[0116] NMR spectra of the samples were collected using a Bruker Avance spectrometer operating at 500.1317 Hz for 1H experiments. Samples were prepared by dissolving 2 to 3 drops of bio-oil in 0.6 mL of deuterated chloroform, with trace amounts of tetramethylsilane added as an internal reference. Quantification was achieved using a 10 ms 90° pulse and a 10-second delay between acquisition. A total of 128 scans were performed. Processing included baseline correction and broadening with a 1 Hz exponential line prior to Fourier transform. The spectrum was further integrated by regions corresponding to the following lumped functional groups: 0.5 ppm to 1.5 ppm alkanes; 1.5 ppm to 3 ppm heteroatomic or unsaturated α-aliphatic compounds; 3 ppm to 4.4 ppm alcohols, methylene-diphenyl; 4.4 ppm to 6 ppm alkenes, methoxy compounds, carbohydrates; 6 ppm to 7.18 ppm (hetero)aromatic compounds, furans; 7.18 ppm to 8.5 ppm (hetero)aromatic compounds; 8.5 ppm to 10.1 ppm aldehydes.

[0117] 13 C Liquid process

[0118] NMR spectra of the samples were collected using a Bruker Avance spectrometer operating at 125.7715 Hz for 13C experiments. Samples were prepared using a 50:50 (v / v) mixture of deuterated chloroform and bio-oil analytes. Additionally, trace amounts of tetramethylsilane were added as an internal reference, and chromium acetylacetonate was used as a relaxant. Quantification was achieved using a reverse-gated pulse sequence, and all 13C spectra were acquired with a 10-second delay between the 11.3 μs pulse and acquisition. A total of 2048 scans were performed. Processing included baseline correction and exponential line broadening using a 3 Hz line before Fourier transform. The spectrum was further integrated by regions corresponding to the following lumped functional groups: 0 ppm to 27 ppm short-chain aliphatic compounds; 27 ppm to 54 ppm long-chain and branched aliphatic compounds; 54 ppm to 94 ppm alcohols, ethers, phenyl methoxy groups, and carbohydrates; 94 ppm to 167 ppm aromatic compounds, alkenes, heteroaromatic compounds, and furans; 167 ppm to 186 ppm esters and carboxylic acids; and 186 ppm to 225 ppm ketones and aldehydes.

[0119] Figure 3 The results of 1H NMR are shown in the figure. Figure 3 As shown, the concentration of aldehydes in the recirculated feedstock, expressed as mol%H, is zero compared to fresh biocrude oil with 0.8 mol%H.

[0120] Figure 4 The results of 13C NMR are shown in the figure. Figure 4As shown, the concentrations of ketones, aldehydes, and carboxylic acids, expressed as mol%H or mol%C, are significantly lower in the recycled feedstock compared to fresh bio-crude oil. Furthermore, the concentrations of desired long-chain and short-chain aliphatic compounds in the recycled feedstock are significantly higher compared to fresh bio-crude oil. According to this disclosure, based on 1H and 13C NMR spectroscopy, the concentrations of functional groups in the recycled feedstock are within the desired range clearly visible from mol%H or mol%C.

[0121] The acid values ​​of the recycled and bio-oilseed streams were measured according to the following method: Dence, CW (1992), “Determination of Carboxyl Groups,” in: Lin, SY, Dence, CW (eds.) Methods in Lignin Chemistry, Springer Series in Wood Science, Springer Publishers, Berlin and Heidelberg, pp. 458–464, https: / / doi.org / 10.1007 / 978-3-642-74065-7. Details of the acid value test are as follows:

[0122] Material :

[0123] 0.05N tetrabutylammonium hydroxide solution (TnBAH): Prepared by diluting 50.0 mL of 1.0N TnBAH (Aldrich, SAP#1014519, 100 mL) solution to 1.00 L in isopropanol. Mix all components thoroughly before transferring the solution to a Dosimat flask. Cover the 1.0N TnBAH solution with nitrogen and store in a refrigerator.

[0124] Benzoic acid: p-hydroxybenzoic acid, store in a desiccator when not in use.

[0125] Hydrochloric acid additive solution: Add 2 mL of concentrated HCl to 100 mL of deionized water and mix thoroughly. Add 4 mL of this solution to approximately 140 mL of dimethylformamide (DMF) for sample titration.

[0126] Standardization of titrants :

[0127] Add 0.15 g to 0.20 g of dried benzoic acid to a titration beaker and record the weight to the nearest 0.1 mg. Add 120 mL of DMF and titrate with TnBAH solution. Perform two parallel normalizations. Calculate the equivalent concentration to three significant figures using the following formula:

[0128]

[0129] When using this process, standardization is repeated every 3 hours.

[0130] Sample titration :

[0131] Before analyzing the first sample, weigh 0.05 g to 0.08 g of p-hydroxybenzoic acid into a titration beaker. Add 140 mL of DMF and 4 mL of HCl additive solution. Titrate the resulting solution through the third inflection point. This is a blank used to calculate the HCl correction and can be used as QC for the phenol hydroxyl titration.

[0132] Weigh 0.3 g to 0.4 g of lignin and 0.05 g to 0.08 g of p-hydroxybenzoic acid into a titration beaker. Add 140 mL of DMF and 4 mL of HCl additive solution. Cover the beaker with nitrogen and stir for 5 minutes, then titrate. Titrate with 0.05 NtnBAH to the third inflection point.

[0133] calculate :

[0134] Calculate the theoretical titer of the internal standard used in blank or sample titrations:

[0135]

[0136] Furthermore, HCl interference was calculated based on the blank.

[0137] c (mL) = [(measurement volume at the second inflection point of blank measurement) – (measurement volume at the first inflection point)] – (a (mL calculated above)).

[0138] Then,

[0139]

[0140]

[0141] in,

[0142] x = mL at the first inflection point;

[0143] y = mL at the second inflection point;

[0144] z = mL at the third inflection point.

[0145] For convenience, the aforementioned method is typically used to measure acid value without the use of p-hydroxybenzoic acid as an internal standard. However, the use of an internal standard is generally recommended. For acid value, carboxylic acid values ​​are measured in both recycled and bio-oil streams. Figure 5 The results are shown in the image. Figure 5As shown, the carboxylic acid value in the recirculated feed stream is significantly lower compared to fresh biocrude oil. The acid value of the recirculated feed stream is within the expected range according to this disclosure.

[0146] Elemental analysis of oxygen concentration was also performed on the recycled feed stream, bio-oil feed stream, and petroleum VGO feed stream. Elemental analysis was performed using ASTM method D5291 and ASTM UOP649. Figure 6 The results are shown in the image. Figure 6 As shown, the oxygen concentration, expressed as a percentage by weight, in the recirculated feedstock is significantly lower compared to fresh bio-crude oil. The oxygen concentration in the recirculated feedstock is within the desired range according to this disclosure.

[0147] Example 2 — Successful Semi-Batch Autoclave Test :

[0148] 320 g of pyrolysis oil was loaded into a 500 mL autoclave reactor. The hydrorefining catalyst, subjected to in-situ sulfidation via H2S gas, was ground to <400 mesh (fine powder). 7.5 g of the ground hydrorefining catalyst was loaded into the autoclave reactor along with the pyrolysis oil. The autoclave reactor was sealed and pressurized to 2000 psig of H2, with the H2 flowing at 700 sccm throughout the experiment. Subsequently, the autoclave reactor was heated to 450 °C at 2 °C / min while stirring at 600 rpm to 1000 rpm and maintained at the specified temperature for 2 hours. After the 2-hour reaction time, the autoclave reactor was cooled to room temperature (20 °C to 25 °C). Once cooled, the autoclave reactor was opened and the liquid in the reactor was collected. Similarly, a portion of the hydrocarbons turned into gas at the indicated reaction temperature and was carried out of the reactor via the H2 stream, subsequently condensing into liquid in a condenser container downstream of the reactor at room temperature. After the experiment was completed, the liquid was drained from the condenser container. The oxygen concentration of the condensed liquid product (light oil) was 11% by weight, and the oxygen concentration of the remaining oil (heavy oil) in the reactor was 9% by weight. Analysis of the oil by 1H and 13C NMR spectroscopy revealed the following concentrations of oxygen-containing functional groups (adverse agents): 1) light oil contained 0.98 mol%C of ketones and aldehydes, 0.69 mol%C of esters and carboxylic acids, 0.0 mol%C of alcohols, ethers, phenyl methoxy groups, total carbohydrates, and 0.0 mol%H of aldehydes; 2) heavy oil contained 0.0 mol%C of ketones and aldehydes, 0.0 mol%C of esters and carboxylic acids, 0.0 mol%C of alcohols, ethers, phenyl methoxy groups, total carbohydrates, and 0.0 mol%H of aldehydes. Analysis of the oil by ATR-IR spectroscopy revealed the following band area ratios of oxygen-containing compounds: 1) light oil has 0.26 (CO) / C, 0.11 (C=O) / C, 0.61 OH / C and 0.37 O / C, 2) heavy oil has 0.08 (CO) / C, 0.03 (C=O) / C, 0.21 OH / C and 0.11 O / C.

[0149] Example 3 — Successful Semi-Batch High-Pressure Reactor Experiment Using Hydrothermally Synthesized Nimos2 Nanoparticle Catalyst test :

[0150] The nanoparticle NiMoS2 catalyst was hydrothermally synthesized as follows: Water, ammonium heptamolybdate tetrahydrate, nickel nitrate hexahydrate, oxalic acid, and thiourea were combined in an autoclave reactor. The autoclave was filled with N2 atmosphere and N2 pressure of 500 psig. The mixture was heated to 220 °C with stirring at 800 rpm and held at this temperature for 12 hours. The reactor was cooled and depressurized, and the NiMoS2 nanoparticle catalyst suspended in water was recovered. The catalyst was then dried at 80 °C for 1 day under N2 to form a powder. 192 g of pyrolysis oil was loaded into a separate 300 mL autoclave reactor. 2.0 g of NiMoS2 nanoparticle catalyst was loaded into the autoclave reactor along with the pyrolysis oil. The autoclave reactor was sealed and pressurized to 1850 psig of H2, with the H2 flow rate at 700 sccm throughout the experiment. Subsequently, the autoclave reactor was heated to 450 °C at 2 °C / min with stirring at 600 rpm to 1000 rpm and held at the specified temperature for 2 hours. After a 2-hour reaction time, the autoclave reactor was cooled to room temperature (20°C to 25°C). Once cooled, the autoclave reactor was opened and the liquid in the reactor was collected. Similarly, a portion of the hydrocarbons turned into gas at the indicated reaction temperature and was carried out of the reactor via the H2 stream, subsequently condensing into liquid in a condenser vessel downstream of the reactor at room temperature. After the experiment was completed, the liquid was drained from the condenser vessel. The oxygen concentration of the condensed liquid product (light oil) was 13% by weight, and the oxygen concentration of the remaining oil (heavy oil) in the reactor was 9.6% by weight. Analysis of the oil by 1H and 13C NMR spectroscopy revealed the following concentrations of oxygen-containing functional groups (adverse substances): 1) Light oil contained 2.53 mol%C of ketones and aldehydes, 1.59 mol%C of esters and carboxylic acids, 0.60 mol%C of alcohols, ethers, phenyl methoxy groups, total carbohydrates, and 0.01 mol%H of aldehydes; 2) Heavy oil contained 0.0 mol%C of ketones and aldehydes, 0.0 mol%C of esters and carboxylic acids, 0.0 mol%C of alcohols, ethers, phenyl methoxy groups, total carbohydrates, and 0.0 mol%H of aldehydes. Analysis of the oil by ATR-IR spectroscopy revealed the following band area ratios of oxygen-containing compounds: 1) light oil has 0.31 (CO) / C, 0.29 (C=O) / C, 0.73 OH / C and 0.61 O / C, 2) heavy oil has 0.18 (CO) / C, 0.02 (C=O) / C, 0.77 OH / C and 0.20 O / C.

[0151] Example 4 — Continuous Bio-oil Upgrading in Pilot Plant :

[0152] The operation is similar in several different test schemes. Figure 1A pilot-scale 2L stirred tank reactor configuration was shown for the continuous upgrading of bio-oil or a blend of bio-oil and petroleum. A total of seven tests were performed. Bio-oil, a sulfur compound (such as dimethyl disulfide), and a molybdenum compound (such as molybdenum octoate) were co-integrated in a feed tank and fed into the reactor. A hydrogen feed stream was added to the bio-oil feed stream upstream of the reactor. After the reaction, the product streams passed through a thermal separator, a cold separator, and an oil-water separator, ultimately providing a light oil product stream, a heavy oil product stream, and a water-containing waste stream. For operations with a petroleum feed stream, the petroleum feed was maintained in a separate feed tank and may also contain sulfur compounds (such as dimethyl disulfide) and / or molybdenum compounds (such as molybdenum octoate). The petroleum feed stream was fed separately from the bio-oil feed stream and added together upstream of the reactor at a location similar to where hydrogen was added to the feed stream. In all operations, the heavy oil product stream was recycled back into the reactor to provide a source of regenerated activated catalyst and deoxygenated oil. Table 1 below summarizes the operating conditions and other parameters of the modification method:

[0153] Table 1

[0154]

[0155] Table 2 below provides the results of seven tests on the improvement method:

[0156] Table 2

[0157]

[0158]

[0159]

[0160] The integrated areas of various 1H and 13C NMR spectral regions of modified bio-oilseed streams with and without recycled feed were measured to calculate the concentrations of oxygen-containing compounds. Table 2 above lists the oxygen-containing compounds and their calculated values. IR spectral band area ratios were measured on a dry basis. As confirmed in Table 2, the concentrations of oxygen-containing compounds, including aldehydes, ketones, and hydroxyl groups, were all within the predetermined expected range. Acid values ​​were measured using the method described in Example 1 above.

[0161] Specific implementation plan

[0162] While the following description is presented in conjunction with specific embodiments, it should be understood that the description is intended to be illustrative and not to limit the scope of the foregoing description and the appended claims.

[0163] A first embodiment of this disclosure is a method for upgrading a bio-oil stream, the method comprising: reacting the bio-oil stream with hydrogen in a reactor in the presence of a catalyst and a stabilizing oil to produce a upgraded bio-oil stream; removing a recycled oil stream from the upgraded bio-oil stream; and recycling the recycled oil stream back to the reactor to provide the stabilizing oil. Embodiments of this disclosure are one, any, or all of the embodiments described in this paragraph, up to the first embodiment, and the method further includes removing fuel oil from the upgraded bio-oil stream. Embodiments of this disclosure are one, any, or all of the embodiments described in this paragraph, up to the first embodiment, and the method further includes: passing the recycled oil stream to the reactor to provide in the reactor a mixture comprising the recycled oil stream and the bio-oil stream, wherein the mass ratio of the mixture to a portion of the upgraded bio-oil stream in the reactor is 0.100 to 8.515. Embodiments of this disclosure are one, any, or all of the embodiments described in this paragraph, from the previous embodiments to the first embodiment described in this paragraph, wherein the contents of the reactor comprise at least one or more of the following: aldehydes at a concentration of 0 mol%H to 3 mol%H, at least one of ketones and aldehydes at a concentration of 0 mol%C to 6 mol%C, at least one of carboxylic acids and esters at a concentration of 0 mol%C to 6 mol%C, and at least one of ethers, alcohols, phenylmethoxy groups, and carbohydrates at a concentration of 0 mol%C to 6 mol%C. Embodiments of this disclosure are one, any, or all of the embodiments described in this paragraph, from the previous embodiments to the first embodiment described in this paragraph, wherein the contents of the reactor have an oxygen-containing compound ratio of 0 to 0.7, a (CO) / C ratio of 0 to 0.5, an (C=O) / C ratio of 0 to 2.5, and an O / C ratio of 0 to 1.7. The embodiments of this disclosure are one, any, or all of the embodiments described in the preceding embodiments to the first embodiment described in this paragraph, wherein the contents of the reactor are characterized by an acid value not exceeding 60 mg KOH / g. The embodiments of this disclosure are one, any, or all of the embodiments described in the preceding embodiments to the first embodiment described in this paragraph, wherein the reactor operates at a temperature of 300°C to 500°C and a pressure of 6.8 MPa to 13.8 MPa. The embodiments of this disclosure are one, any, or all of the embodiments described in the preceding embodiments to the first embodiment described in this paragraph, wherein the method further includes: passing the modified bio-oil stream to a thermal separator; and separating the modified bio-oil stream in the thermal separator to provide a hot tower overhead stream and a hot tower bottom stream comprising at least a portion of the stabilized oil.The embodiments of this disclosure are one, any, or all of the embodiments described in the preceding embodiments to the first embodiment described in this paragraph. The method further includes: passing the hot tower top feed stream to a cold separator to separate gaseous components and provide a light oil stream from the bottom of the tower; and separating water from the light oil stream from the bottom of the tower to produce a light, modified bio-oil stream. The embodiments of this disclosure are one, any, or all of the embodiments described in the preceding embodiments to the first embodiment described in this paragraph. The method further includes: separating a catalyst-containing stream from the hot tower bottom feed stream to provide a heavy oil stream and the recycle oil stream including the catalyst. The embodiments of this disclosure are one, any, or all of the embodiments described in the preceding embodiments to the first embodiment described in this paragraph. The method further includes: separating a catalyst-containing stream from the heavy oil stream to provide a heavy oil product stream and a concentrated catalyst stream; combining the concentrated catalyst stream with the recycle oil stream to provide a combined recycle oil stream; and recycling the combined recycle oil stream to the reactor to provide the stabilized oil. Embodiments of this disclosure are one, any, or all of the embodiments described in this paragraph, from the previous embodiments to the first embodiment described in this paragraph, wherein the heavy oil stream is passed to a filter vessel, a vacuum distillation column, a scraped film evaporator, a centrifuge, or a combination thereof to separate the catalyst. Embodiments of this disclosure are one, any, or all of the embodiments described in this paragraph, from the previous embodiments to the first embodiment described in this paragraph, wherein the method further includes feeding the light oil stream to an FCC unit, a hydrotreating unit, or a reforming unit.

[0164] A second embodiment of this disclosure is a method for upgrading a bio-oil stream, the method comprising: reacting the bio-oil stream with hydrogen in a reactor in the presence of a catalyst and a stabilizing oil to produce a upgraded bio-oil stream; separating the catalyst from the upgraded bio-oil stream to provide a recirculated oil stream comprising the catalyst and a heavy upgraded bio-oil stream; and recycling the recirculated oil stream back to the reactor to provide the stabilizing oil. Embodiments of this disclosure are one, any, or all of the embodiments described in the preceding embodiments to the second embodiment described in this paragraph, wherein at least 50% by weight of the feed to the reactor is bio-derived. Embodiments of this disclosure are one, any, or all of the embodiments described in the preceding to the second embodiments of this paragraph, wherein the contents of the reactor comprise at least one or more of the following: aldehydes at a concentration of 0 mol%H to 3 mol%H, at least one of ketones and aldehydes at a concentration of 0 mol%C to 6 mol%C, at least one of carboxylic acids and esters at a concentration of 0 mol%C to 6 mol%C, and at least one of ethers, alcohols, phenylmethoxy groups, and carbohydrates at a concentration of 0 mol%C to 6 mol%C. Embodiments of this disclosure are one, any, or all of the embodiments described in the preceding to the second embodiments of this paragraph, wherein the contents of the reactor have an oxygen-containing compound ratio of 0 to 1.7: (CO) / C ratio, 0 to 0.5: (C=O) / C ratio, 0 to 2.5: OH / C ratio, and 0 to 1.7: O / C ratio. The embodiments of this disclosure are one, any, or all of the embodiments described in the preceding to the second embodiments of this paragraph, and the method further includes: passing the modified bio-oil stream to a thermal separator; and separating the modified bio-oil stream in the thermal separator to provide a thermal tower overhead stream and a thermal tower bottom stream comprising the stabilized oil. The embodiments of this disclosure are one, any, or all of the embodiments described in the preceding to the second embodiments of this paragraph, and the method further includes: separating a catalyst from the thermal tower bottom stream to provide a heavy oil stream and the recirculated oil stream comprising the catalyst.

[0165] A third embodiment of this disclosure is a method for upgrading a bio-oil stream, the method comprising: reacting the bio-oil stream with hydrogen in a reactor in the presence of a catalyst and a stabilizing oil to produce a upgraded bio-oil stream; separating the upgraded bio-oil stream in a separator to provide a light upgraded bio-oil stream and a bottoms stream; separating the catalyst from the bottoms stream to provide a heavy oil stream and a recycle oil stream including the catalyst; and recycling the recycle oil stream back to the reactor to provide the stabilizing oil.

[0166] Although no further detailed description has been provided, it is believed that those skilled in the art can make full use of this disclosure by employing the foregoing description and can readily determine the essential characteristics of this disclosure without departing from the spirit and scope of the invention, and can make various changes and modifications to this disclosure to suit various uses and conditions. Therefore, the foregoing preferred specific embodiments should be understood as illustrative only and not as limiting the remainder of this disclosure in any way, and are intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0167] In the foregoing, all temperatures are expressed in degrees Celsius, and all portions and percentages are by weight unless otherwise specified.

Claims

1. A method for upgrading a bio-oilseed stream, the method comprising: In a reactor, a bio-oil stream is reacted with hydrogen in the presence of a catalyst and stabilizing oil to produce a modified bio-oil stream. The recirculated oil stream is removed from the modified bio-oil stream; as well as The recirculated oil stream is recycled back to the reactor to provide the stabilized oil.

2. The method according to claim 1, further comprising removing fuel oil from the modified bio-oil stream.

3. The method according to claim 1, further comprising: The recycled oil stream is passed to the reactor to provide a mixture comprising the recycled oil stream and the bio-oil stream in the reactor, wherein the mass ratio of the mixture to the partially modified bio-oil stream in the reactor is 0:100 to 85:

15.

4. The method of claim 1, wherein the contents of the reactor comprise at least one or more of the following: aldehydes at a concentration of 0 mol%H to 3 mol%H, ketones at a concentration of 0 mol%C to 6 mol%C, carboxylic acids at a concentration of 0 mol%C to 6 mol%C, esters at a concentration of 0 mol%C to 6 mol%C, ethers, alcohols, phenylmethoxy groups, and carbohydrates at a concentration of 0 mol%C to 6 mol%C.

5. The method according to claim 1, wherein the contents of the reactor have one or more of the following oxygen-containing compound ratios: (CO) / C ratio of 0 to 0.7, (C=O) / C ratio of 0 to 0.5, OH / C ratio of 0 to 2.5, and O / C ratio of 0 to 1.

7.

6. The method according to claim 1, wherein the contents of the reactor are characterized in that the acid value does not exceed 60 mg KOH / g.

7. The method according to claim 1, further comprising: The modified bio-oil stream is then transferred to a thermal separator. as well as The modified bio-oil stream is separated in the thermal separator to provide a thermal tower overhead stream and a thermal tower bottom stream comprising at least a portion of the stabilized oil.

8. The method according to claim 7, further comprising: The hot column top feed stream is passed to a cold separator to separate gaseous components and to provide a light oil stream from the bottom of the column. as well as Water is separated from the light oil stream at the bottom of the tower to produce a light, modified bio-oil stream.

9. The method according to claim 7, further comprising: A catalyst-containing stream is separated from the bottom stream of the hot tower to provide a heavy oil stream and a recirculated oil stream including the catalyst.

10. The method according to claim 9, further comprising: Separate a catalyst-containing stream from the heavy oil stream to provide a heavy oil product stream and a concentrated catalyst stream; The concentrated catalyst feed stream is combined with the recirculated oil feed stream to provide a combined recirculated oil feed stream; as well as The combined recirculated oil stream is recycled back to the reactor to provide the stabilized oil.

Images