Process and system for hydroprocessing renewable feedstocks

Abstract

A method for producing one or more hydrocarbon products from a renewable feedstock comprising triglycerides, free fatty acids, or a combination thereof is provided. The method can include the steps of mixing the renewable feedstock with a diluent to form a diluted feedstock; supplying or providing hydrogen to the diluted feedstock such that the hydrogen can dissolve in the diluted feedstock to form a diluted feedstock enriched with dissolved hydrogen; and feeding the diluted feedstock enriched with dissolved hydrogen to at least one reactor having at least one reaction zone comprising at least one catalyst bed under predetermined conditions, thereby producing a reaction effluent that can be further processed (e.g., by using one or more distillation units and one or more adsorption units) to form one or more hydrocarbon products.

Description

Technical Field

[0001] The present invention relates to a method and system for hydrotreating renewable feedstock, wherein the renewable feedstock comprises, in particular, triglycerides, free fatty acids or combinations thereof. Background Technology

[0002] The following discussion of the background of the invention is for the purpose of facilitating understanding of the invention. However, it should be understood that this discussion does not imply endorsement or acknowledgment that any material mentioned has been published, known, or is part of the general public in any jurisdiction at the priority date of this application.

[0003] Hydroprocessing typically refers to two separate processes: hydrotreating and hydrocracking. Hydrotreating is the process of using hydrogen or hydrogen-containing gases and one or more suitable catalysts to break down complex oil molecules into smaller hydrocarbon molecules. Generally, hydrotreating is a three-phase process carried out in a trickle bed reactor, which is configured such that a selected renewable feedstock (such as animal oil, animal fat, or vegetable oil) is contacted with one or more suitable catalysts packed in the reactor under increased temperature and pressure, and in the presence of hydrogen (flowing continuously within the reactor).

[0004] In a reactor, when hydrogen comes into contact with a renewable feedstock, it dissolves in the feedstock under certain conditions (e.g., at a temperature of about 200°C to about 400°C and a pressure of about 20 bar to about 50 bar) before any reaction can occur. However, the low solubility of hydrogen in renewable feedstocks limits the hydrogenation process, resulting in insufficient amounts of hydrogen reacting with the feedstock.

[0005] To mitigate these limitations, conventional hydrotreating methods require a large excess of hydrogen as feed, resulting in significant amounts of unused hydrogen leaving the reactor along with the product stream. While unused hydrogen can be recovered and reused by re-injecting it into the reactor, this requires compression using a compressor to increase its pressure to at least equivalent to the reactor's pressure, thereby increasing the operating costs of the hydrotreating method.

[0006] In view of the above, there is a need to develop a hydrotreating method that overcomes at least one of the aforementioned disadvantages. There is also a need to develop a method for hydrotreating renewable feedstocks to produce desired hydrocarbon products, including bio-naphtha, industrial solvents, and phase change materials containing high-purity n-paraffin hydrocarbons. Summary of the Invention

[0007] One aspect of the invention is the production of a hydrotreated oil that can be further processed to produce hydrocarbon products suitable for use in engines, automotive parts, buildings, and other applications.

[0008] Another aspect of the invention is the production of hydrotreated oil by a hydrotreatment method without using petrochemical sources as starting materials or raw materials.

[0009] Another aspect of the invention is the production of hydrotreated oils with high purity, or the production of hydrotreated oils that can be further processed to produce hydrocarbon products with high purity.

[0010] Another aspect of the present invention is to provide a method for hydrogenating a raw material comprising triglycerides, free fatty acids, or combinations thereof without requiring a large amount of excess hydrogen.

[0011] According to one aspect of the invention, a method is provided for producing one or more hydrocarbon products from a renewable feedstock comprising triglycerides, free fatty acids, or combinations thereof, the method comprising the steps of: diluting the renewable feedstock with a diluent to form a diluted feedstock; contacting the diluted feedstock with hydrogen and a sulfiding agent such that hydrogen dissolves in the diluted feedstock to form a hydrogen-enriched diluted feedstock; feeding the hydrogen-enriched diluted feedstock into a reactor comprising a catalyst bed to form a hydrogen-enriched reaction effluent; further contacting the reaction effluent with hydrogen and a sulfiding agent such that hydrogen dissolves in the reaction effluent to form a hydrogen-enriched reaction effluent; further feeding the hydrogen-enriched reaction effluent into at least one additional reactor comprising a catalyst bed to produce a further-reaction effluent, which may be further processed to form one or more hydrocarbon products; and wherein the gaseous volume fraction of undissolved hydrogen in the reactor is not more than 0.1 to 0.25.

[0012] In some embodiments, the method further includes the step of passing hydrogen through each reactor in a predetermined amount.

[0013] In some embodiments, the method further includes the step of separating gaseous byproducts from the reaction effluent or re-reaction effluent using a thermal high-pressure separator.

[0014] In some implementations, the dilution and contact steps can be performed simultaneously.

[0015] In some embodiments, the method further includes the steps of recovering diluent from the reaction effluent or re-reaction effluent and re-injecting the recovered diluent into a diluent source.

[0016] In some embodiments, the method further includes the steps of: feeding the reaction effluent or re-reaction effluent to separators arranged in sequence for separating byproducts from the reaction effluent or re-reaction effluent and for recovering diluents from the reaction effluent or re-reaction effluent to obtain a hydrogenated product; and feeding the hydrogenated product to one or more distillation columns and adsorption units for purifying the hydrogenated product to obtain one or more purified hydrocarbon products.

[0017] In some implementations, the renewable feedstock is animal oil, vegetable oil, or a combination thereof.

[0018] In some implementations, the renewable feedstock is a combination of one or more animal oils and one or more vegetable oils.

[0019] In some implementations, the renewable raw materials are tallow oil, train oil, fish oil, bleached palm oil (BPO), refined bleached and deodorized palm oil (RBDPO), palm olein, palm stearin, palm fatty acid distillate, canola oil, corn oil, sunflower oil, soybean oil, jatropha oil, balanites oil, rapeseed oil, tall oil, hempseed oil, olive oil, linseed oil, mustard oil, peanut oil, castor oil, coconut oil, or any combination of two or more oils.

[0020] In some implementations, the renewable feedstock is fresh oil, used oil, waste oil, or any combination thereof.

[0021] In some implementations, the diluent includes n-chain hydrocarbons.

[0022] In some implementations, the diluent includes an ortho-chain hydrocarbon containing 12 carbon atoms.

[0023] In some embodiments, the ratio of diluent to renewable raw material is from about 99% by weight of diluent / 1% by weight of raw material to about 50% by weight of diluent / 50% by weight of raw material.

[0024] In some implementations, the ratio of hydrogen to catalyst bed volume in the reactor is 3 or 900 Nm. 3 / m 3 Within the range.

[0025] In some implementations, the ratio of hydrogen to renewable feedstock is between approximately 10 and approximately 700 Nm. 3 / m3 The range is from about 0.001 to about 0.054 g / g.

[0026] In some implementations, the catalyst is selected from NiMo, CoMo, NiCoMo, and NiW.

[0027] In some embodiments, the catalyst comprises at least one of two transition metals selected from Ni and Mo.

[0028] In some implementations, the catalyst also includes another transition metal or a Group V element.

[0029] In some implementations, the catalyst is supported on a carrier.

[0030] In some embodiments, the support is an acidic porous solid support selected from alumina (Al2O3), silica (SiO2), and mixtures of alumina and silica (Al2O3-SiO2).

[0031] In some embodiments, the carrier is fluorinated alumina, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-32, ZSM-35, ZSM-38, ZSM-48, ZSM-57, SAPO-11, SAPO-31, SAPO-41, MAPO-11, MAPO-31, zeolite Y, zeolite L, or β-zeolite.

[0032] In some embodiments, a system for producing one or more hydrocarbon products from a renewable feedstock comprising triglycerides, free fatty acids, or combinations thereof, the system comprising a reactor containing a catalyst bed; wherein the reactor is used to react a diluted feedstock enriched with dissolved hydrogen to produce a reaction effluent that can be further processed to form one or more hydrocarbon products; wherein the diluted feedstock enriched with dissolved hydrogen is prepared by diluting the renewable feedstock comprising triglycerides, free fatty acids, or combinations thereof with a diluent to form a diluted feedstock, then adding a sulfurizing agent and passing hydrogen through the diluted feedstock such that the hydrogen dissolves in the diluted feedstock to form a diluted feedstock enriched with dissolved hydrogen; further comprising at least one additional reactor containing a catalyst bed to further contact the reaction effluent with hydrogen and a sulfurizing agent to form a reaction effluent enriched with dissolved hydrogen, the additional reactor being used to react the effluent enriched with dissolved hydrogen to produce a re-reaction effluent that can be further processed to form one or more hydrocarbon products; and wherein the gaseous volume fraction of undissolved hydrogen in the reactor is not more than 0.1 to 0.25.

[0033] In some embodiments, the reactor or the additional reactor is further used such that a sulfiding agent is added and hydrogen is passed through the reactor in a predetermined amount.

[0034] In some implementations, a thermal high-pressure separator is located after each reactor or additional reaction zone for separating gaseous byproducts from the reaction effluent or re-reaction effluent.

[0035] In some embodiments, the system further includes one or more separators arranged in sequence for separating byproducts from the reaction effluent or re-reaction effluent and for recovering diluents from the reaction effluent or re-reaction effluent to obtain the hydrogenated product; and one or more distillation columns and adsorption units for purifying the hydrogenated product to obtain one or more purified hydrocarbon products.

[0036] In some implementations, the renewable feedstock used in the system is animal oil, vegetable oil, or a combination thereof.

[0037] In some implementations, the renewable feedstock used in the system is a combination of one or more animal oils and one or more vegetable oils.

[0038] In some implementations, the renewable feedstock used in the system is tallow, whale oil, fish oil, bleached palm oil (BPO), refined bleached deodorized palm oil (RBDPO), palm oil extract, palm stearin, palm fatty acid distillate, canola oil, corn oil, sunflower oil, soybean oil, jatropha oil, Roche oak oil, rapeseed oil, tall oil, hemp seed oil, olive oil, flaxseed oil, mustard oil, peanut oil, castor oil, coconut oil, or any combination of two or more oils.

[0039] In some implementations, the renewable feedstock used in the system is fresh oil, used oil, waste oil, or any combination thereof.

[0040] In some implementations, the diluent used in the system includes n-chain hydrocarbons.

[0041] In some implementations, the diluent used in the system comprises an ortho-chain hydrocarbon containing 12 carbon atoms.

[0042] In some implementations, the ratio of diluent to renewable feedstock used in the system is from about 99% by weight of diluent / 1% by weight of feedstock to about 50% by weight of diluent / 50% by weight of feedstock.

[0043] In some implementations, the ratio of hydrogen used in the system to the catalyst bed volume in the reactor is 3 or 900 Nm. 3 / m 3 Within the range.

[0044] In some implementations, the ratio of hydrogen to renewable feedstock used in the system is between approximately 10 and approximately 700 Nm. 3 / m 3 The range is from about 0.001 to about 0.054 g / g.

[0045] In some embodiments, the catalyst used in the system is selected from NiMo, CoMo, NiCoMo, and NiW.

[0046] In some embodiments, the catalyst used in the system comprises at least one of two transition metals selected from Ni and Mo.

[0047] In some implementations, the catalyst used in the system also includes another transition metal or a Group V element.

[0048] In some implementations, the catalyst used in the system is supported on a carrier.

[0049] In some embodiments, the catalyst support used in the system is an acidic porous solid support selected from alumina (Al2O3), silica (SiO2), and mixtures of alumina and silica (Al2O3-SiO2).

[0050] In some embodiments, the catalyst support used in the system is fluorinated alumina, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-32, ZSM-35, ZSM-38, ZSM-48, ZSM-57, SAPO-11, SAPO-31, SAPO-41, MAPO-11, MAPO-31, zeolite Y, zeolite L, or β-zeolite. Attached Figure Description

[0051] The invention will now be described by way of example only with reference to the accompanying drawings, in which:

[0052] Figure 1 This is a schematic diagram illustrating a method for hydrogenating a feedstock comprising triglycerides, free fatty acids, or combinations thereof, according to an embodiment of the present invention; and

[0053] Figure 2 This is a schematic diagram illustrating a method according to an embodiment of the present invention for hydrogenating a feedstock comprising triglycerides, free fatty acids, or combinations thereof to produce a product comprising a phase change material and an industrial solvent. Detailed Implementation

[0054] Specific embodiments of the invention will now be described with reference to the accompanying drawings. The terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the scope of the invention. Furthermore, unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Where possible, for clarity and consistency, the same reference numerals are used throughout the drawings.

[0055] As used herein, the term "phase change material (PCM)" refers to a straight-chain hydrocarbon compound that primarily comprises ortho-chain hydrocarbons having 16, 17, and 18 carbon atoms.

[0056] As used herein, when the terms “substantially free of,” “significantly free of,” or similar terms are used in the context of byproducts (e.g., sulfur, olefins, aromatic compounds, alcohols, or combinations thereof) in a compound (e.g., a hydrogenated product stream or a phase change material), they mean in amounts less than 100 ppmw (parts per million by weight), less than 50 ppmw, less than 20 ppmw, less than 10 ppmw, less than 5 ppmw, or less than 1 ppmw.

[0057] Throughout this specification, unless the context otherwise requires, the word “comprise” or variations such as “comprises” or “comprising” shall be understood to mean including the stated integers or sets of integers, but not excluding any other integers or sets of integers.

[0058] Throughout this specification, unless the context otherwise requires, the word “include” or variations such as “includes” or “including” shall be understood to mean that the stated integer or set of integers is included, but not to exclude any other integer or set of integers.

[0059] As used herein, the term “about” typically refers to ±5% of the value, more typically ±4%, more typically ±3%, more typically ±2%, even more typically ±1%, and even more typically ±0.5%.

[0060] Throughout this disclosure, certain embodiments may be disclosed in the form of ranges. It should be understood that descriptions in the form of ranges are for convenience and brevity only and should not be construed as limiting the scope of the disclosure. Therefore, a description of a range should be considered as specifically disclosing all possible subranges and individual numerical values ​​within said range. For example, a description of a range such as 1 to 6 should be considered as specifically disclosing subranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., and individual numerical values ​​within said range, such as 1, 2, 3, 4, 5, and 6. Ranges are not limited to integers and may also include decimal measurements. This applies regardless of the width of the range.

[0061] Other aspects of the invention will become apparent to those skilled in the art after reviewing the following description of specific embodiments of the invention in conjunction with the accompanying drawings.

[0062] This invention provides a two-phase hydrogenation process that differs from conventional three-phase hydrogenation processes. Specifically, the two-phase hydrogenation process involves at least a liquid-phase renewable feedstock and a solid catalyst (or multiple catalysts in some embodiments), wherein the liquid-phase renewable feedstock is the continuous phase in the reactor. More specifically, the two-phase hydrogenation process includes at least: mixing the renewable feedstock with a diluent to form a diluted feedstock; adding a sulfiding agent to the diluted feedstock; supplying or providing hydrogen to the diluted feedstock such that the hydrogen dissolves in the diluted feedstock to form a diluted feedstock enriched with dissolved hydrogen; and feeding the diluted feedstock enriched with dissolved hydrogen to at least one reactor under predetermined conditions (such as conditions favorable to hydrogenation), said reactor having at least one reaction zone containing at least one catalyst bed, thereby producing a reaction effluent that is a hydrocarbon compound primarily comprising n-chain hydrocarbons. This reaction effluent can also be further processed (e.g., by using one or more distillation units and one or more adsorption units) to form an industrial solvent, a phase change material (PCM), or both. If more than one reactor is used in a two-phase hydrotreating process, it should be understood that the reaction effluent from the preceding reactor (e.g., the second reactor) can be contacted with hydrogen and sulfiding agent before being fed into the subsequent reactor (e.g., the third reactor). This allows the hydrogen to dissolve in the reaction effluent to replenish the hydrogen reacted in the hydrotreating process and maintain the efficiency of the catalyst.

[0063] In some embodiments, the renewable feedstock to be hydrogenated in this invention can be any oil, fat, and free fatty acid derived from plants or animals. In particular, the renewable feedstock can be any oil, such as those containing triglycerides or free fatty acids, wherein the main components include those with C... 12 To C20 Partial aliphatic hydrocarbon chain.

[0064] In some preferred embodiments, the renewable feedstock may be oils derived from plants and / or animals and may include one or more triglycerides. The renewable feedstock may also include mixtures of triglycerides. Renewable feedstocks containing one or more triglycerides may be derived from plants selected from pine, rapeseed, sunflower, jathropa, seashore mallow, and any combination of two or more thereof. Renewable feedstocks containing one or more triglycerides may also be vegetable oils selected from canola oil, palm oil, coconut oil, palm kernel oil, sunflower oil, soybean oil, crude tallow, and any combination of two or more thereof. Renewable feedstocks containing one or more triglycerides may also include poultry fat, yellow fat, tallow, used vegetable oil, or oil from biomass pyrolysis. Renewable feedstocks may also be marine oils such as algae oil.

[0065] In some other preferred embodiments, the renewable feedstock may comprise triglycerides, free fatty acids, or combinations thereof. The renewable feedstock may be plant-derived oils, animal-derived oils, or combinations thereof, wherein the oil may comprise a major component comprising an aliphatic hydrocarbon chain having 12 to 18 carbon atoms. Renewable feedstocks comprising triglycerides, free fatty acids, or combinations thereof may include, but are not limited to, animal oils such as tallow, whale oil, and fish oil; vegetable oils such as bleached palm oil (BPO), refined bleached deodorized palm oil (RBDPO), palm oil extract, palm stearin, palm fatty acid distillates, canola oil, corn oil, sunflower oil, soybean oil, oils from desert plants (such as jatropha oil and Rocher's quercetin oil), rapeseed oil, tall oil, hemp seed oil, olive oil, flaxseed oil, mustard oil, peanut oil, castor oil, coconut oil; or any combination of two or more thereof. The vegetable oils herein may also be vegetable oils, which may be crude, refined, or edible vegetable oils. In some implementations, the renewable feedstock can be fresh oil, used oil, waste oil, or any combination thereof. Furthermore, the choice of renewable feedstock can depend on availability and cost, thus making the two-stage hydrotreating process flexible.

[0066] As described above, this invention requires the supply or provision of a diluent for mixing with renewable feedstock to form a diluted feedstock. The formation of a diluted feedstock facilitates the dissolution of hydrogen in the diluted feedstock before it is fed into the reactor. The formation of a diluted feedstock also eliminates the need to supply large quantities of excess hydrogen to the reactor, since the hydrogen required for the hydrotreatment process is present in the diluted feedstock as dissolved hydrogen.

[0067] In some implementations, although hydrogen may be dissolved in the diluted feedstock before being fed to the reactor, the solubility of hydrogen in the diluted feedstock may still be very low, as shown in Table 1. Therefore, this can affect the performance of the hydrotreating method because the amount of hydrogen available for the hydrotreating process may be limited and insufficient.

[0068] Table 1: Solubility of hydrogen in diluted feedstock

[0069]

[0070] To overcome this situation, more than one reactor can be used in this invention, wherein each reactor may include at least one reaction zone containing at least one catalyst bed. In particular, after obtaining the reaction effluent from a preceding reactor (e.g., the first reactor), it may be necessary to contact this reaction effluent from the first reactor with hydrogen gas to replenish the hydrogen reacted in the hydrotreating process before feeding it into a subsequent reactor (i.e., the second reactor). Therefore, it ensures the presence of sufficient hydrogen throughout the hydrotreating process.

[0071] It should be understood that, in some implementations, the number of reactors can be determined based on the composition and amount of the renewable feedstock to be hydrotreated and the diluent. The number of reactors can also be determined by the temperature and pressure of the hydrotreatment process. Once these factors are determined, the amount of hydrogen required to contact the diluted feedstock or reaction effluent, the hydrogen-to-renewable feedstock ratio, and the number of times hydrogen needs to be added to the reaction effluent can be determined accordingly.

[0072] In some embodiments, the two-phase hydrogenation process comprises three main reactions: hydrogenation, decarboxylation and decarbonylation of double bonds in the alkyl chain of a fatty acid, and hydrogenation to produce an alkane. Therefore, the two-phase hydrogenation process may produce products including, but not limited to, aliphatic hydrocarbons of the corresponding fatty acid and propane from triglyceride molecules, as well as byproducts including, but not limited to, carbon monoxide and carbon dioxide (from the oxygen contents of triglycerides) and water, possibly in vapor form. Removal of water from the reactor is crucial because the presence of water can affect catalyst lifetime and the solubility of hydrogen in renewable feedstocks.

[0073] In addition to these reactors, the two-phase hydrotreating method may also involve at least one separator for removing byproducts formed from the desired hydrotreated product. This differs from conventional hydrotreating methods, which require heat exchangers, separators, and flash vessels after each reactor to remove unwanted heat and byproducts, including water, from the hydrotreated product stream from each reactor.

[0074] In some preferred embodiments, the separator used in the two-phase hydrogenation process may be a thermal high-pressure separator (HHPS). The HHPS may be located downstream of the reactor and is used to separate undesirable gaseous byproducts from the reaction effluent from the reactor before the hydrogenated product stream comes into contact with hydrogen. In some embodiments, the gaseous byproducts to be separated from the reaction effluent may include water vapor, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H2S), a small amount of hydrogen, and a small amount of gaseous hydrogenated product.

[0075] In some other embodiments, the method of the present invention may further include selecting a suitable catalyst. The catalyst may be selected from NiMo, CoMo, NiCoMo, and NiW. In some embodiments, the catalyst may include at least one of two transition metals selected from Ni and Mo. In some embodiments, the catalyst may also include another transition metal or a Group V element.

[0076] Prior to use, the catalyst can also be activated by a sulfidation process, which can be accomplished by loading the catalyst into a reaction zone and reacting the metal oxide with hydrogen sulfide (H2S) in the presence of hydrogen at a temperature of about 150°C to about 400°C and a pressure of about 1 bar to about 50 bar. The sulfiding agent can be selected from carbon disulfide, dicarbon disulfide, and paraffin compounds (CS-40) having at least one thiol, sulfide, or disulfide functional group. In some embodiments, the amount of sulfur in the sulfiding agent used to activate the catalyst can be from about 0.10 wt% to 5 wt%, or about twice the amount required to convert the metal oxide into a metal sulfide. In another aspect, the catalyst loading can be from about 0.5 wt% to about 20 wt%. The required amount of catalyst can be calculated based on the amount of renewable feedstock and hydrogen.

[0077] In some embodiments, the catalyst can be supported on a support. In some preferred embodiments, the support for the catalyst to be supported can be an acidic porous solid support such as alumina (Al₂O₃), silica (SiO₂), or a mixture of alumina and silica (Al₂O₃-SiO₂). In some other preferred embodiments, the support for the catalyst to be supported can be fluoride alumina, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-32, ZSM-35, ZSM-38, ZSM-48, ZSM-57, SAPO-11, SAPO-31, SAPO-41, MAPP-11, MAPP-31, zeolite Y, zeolite L, or β-zeolite. By passing a diluted feedstock enriched with dissolved hydrogen through the catalyst on the support, the alkene or unsaturated portion of the normal-chain hydrocarbon chain of the renewable feedstock can be hydrogenated. Furthermore, since the support can serve as a high surface area carrier for the catalyst, higher catalyst efficiency can be achieved. Therefore, reactions such as hydrogenation, deoxygenation, and isomerization may occur with higher efficiency because the catalyst is better dispersed.

[0078] In some embodiments, a controlled rate of hydrogen addition to at least one catalyst bed is determined to maximize the amount of hydrogen available for hydrogenation and for all feedstocks in all reaction zones, and to minimize or eliminate the amount of hydrogen exceeding the solubility limit. The hydrogen-to-catalyst bed volume ratio can be 3, 20, 40, 50, 100, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, or 900 Nm³. 3 / m 3 Within a range. The raw material can range from approximately 10 to approximately 700 Nm. 3 / m 3 (approximately 0.001 to approximately 0.054 g / g), 10 to approximately 650 Nm 3 / m 3 (approximately 0.001 to approximately 0.050 g / g), approximately 10 to approximately 600 Nm 3 / m 3 (approximately 0.001 to approximately 0.047 g / g), approximately 10 to approximately 550 Nm 3 / m 3 (approximately 0.001 to approximately 0.044 g / g), approximately 10 to approximately 500 Nm 3 / m 3 (approximately 0.001 to approximately 0.039 g / g or), approximately 10 to approximately 450 Nm 3 / m 3 (approximately 0.001 to approximately 0.035 g / g), approximately 10 to approximately 400 Nm 3 / m 3(approximately 0.001 to approximately 0.032 g / g), approximately 10 to approximately 380 Nm 3 / m 3 (approximately 0.001 to approximately 0.030 g / g), approximately 10 to approximately 350 Nm 3 / m 3 (approximately 0.001 to approximately 0.028 g / g), or approximately 10 to approximately 320 Nm 3 / m 3 The range is from about 0.001 to about 0.025 g / g. In some embodiments, a method for hydrogenating a renewable feedstock 201 comprising triglycerides, free fatty acids, or combinations thereof may be preferably provided, such as... Figure 1 As shown in the diagram. Specifically, the renewable feedstock to be hydrotreated can be animal or vegetable oils. The renewable feedstock to be hydrotreated can also be a combination of one or more animal oils and one or more vegetable oils. For example, the renewable feedstock to be hydrotreated can be tallow, whale oil, fish oil, bleached palm oil (BPO), refined bleached deodorized palm oil (RBDPO), palm oil extract, palm stearin, palm fatty acid distillate, canola oil, corn oil, sunflower oil, soybean oil, jatropha oil, Roche oak oil, rapeseed oil, tall oil, hemp seed oil, olive oil, flaxseed oil, mustard oil, peanut oil, castor oil, coconut oil, or any combination of two or more oils. In some embodiments, the renewable feedstock to be hydrotreated can be fresh oil, used oil, waste oil, or any combination thereof.

[0079] like Figure 1 As shown, before hydrotreating the renewable feedstock 201, a diluent 202 can preferably be added to the renewable feedstock 201 to form a diluted feedstock 203. The diluent 202 to be added to the renewable feedstock 201 can be a fresh n-chain hydrocarbon feed, a portion of the n-chain hydrocarbon recovered from the method of the present invention and reinjected into the diluent feed stream or diluent source, or a combination thereof. In some preferred embodiments, the diluent 202 can comprise n-chain hydrocarbons having 10-20 carbon atoms. In particular, n-chain hydrocarbons having 12 carbon atoms. The composition of the diluent can be 70-100% by weight of n-decane (C 10 ), n-Undecane (C 11 ), n-Dodecane (C 12 ), n-Tetane (C 13 ), n-Tetradecane (C 14( ), or mixtures thereof. The remainder of the composition is a heavier n-chain hydrocarbon fraction. In some other preferred embodiments, diluent 202 may have the ability to maintain its liquid phase at a temperature of about 400°C and a pressure of about 35 bar, and have a hydrogen solubility of not less than 0.5 wt%, 1.0 wt%, 2.0 wt%, or 3 wt% under the hydrotreating reaction conditions described below. Furthermore, if diluent 202 is a portion of the n-chain hydrocarbons recovered from and re-injected into the diluent feed stream or diluent source in the method of the present invention, it may be necessary to ensure that the relative volatility between diluent 202 and the light key components in the n-chain hydrocarbon effluent is greater than or equal to 1.1.

[0080] Furthermore, it should be understood that in some embodiments, the ratio of diluent 202 to renewable raw material 201 (added to renewable raw material 201) can be from about 99 wt% diluent / 1 wt% raw material to about 95 wt% diluent / 5 wt% raw material, from about 95 wt% diluent / 5 wt% raw material to about 90 wt% diluent / 10 wt% raw material, from about 80 wt% diluent / 20 wt% raw material to about 70 wt% diluent / 30 wt% raw material, or from about 60 wt% diluent / 40 wt% raw material to about 50 wt% diluent / 50 wt% raw material. It should also be understood that in some embodiments, raw material 201 and diluent 202 can be mixed with each other at ambient temperature and atmospheric pressure, thereby allowing for the preparation and storage of diluted raw material 203 in advance.

[0081] Subsequently, the diluted feedstock 203 can be contacted with the sulfurizing agent 235, and then with hydrogen 204, such that the required amount of hydrogen is dissolved in the diluted feedstock 203 to prepare a diluted feedstock 205 enriched with dissolved hydrogen, while maintaining the efficiency of the catalyst in the catalyst bed. The amount of hydrogen may be present in an amount that can dissolve in the feedstock or may be present in excess. Undissolved hydrogen may form a gas phase in the reaction zone. The required amount of hydrogen must be sufficient to carry out one or more reactions in the reaction zone (depending on the volume of the feedstock to be reacted in the reaction zone) and / or not to form an excessive gas phase. In particular, the gas volume fraction (GVF) of the gas phase occurring in this step is about 0.1 to about 0.25. The required sulfurizing agent dosage is preferably such that the sulfur relative to the volume of the feedstock in the liquid stream is 0-10,000 ppmw. The operation or step for preparing the diluted feedstock 205 enriched with dissolved hydrogen can be carried out in any suitable apparatus known in the art. However, to ensure the hydrogen dissolves in the diluted feedstock 203, the process needs to be carried out at temperatures of about 200°C to about 400°C, about 250°C to about 320°C, or about 250°C to 360°C, and at pressures of about 20 bar to about 100 bar, about 25 bar to about 100 bar, or about 30 bar to about 100 bar. In some preferred embodiments, the ratio of hydrogen 204 (to be fed into the diluted feedstock 203) to the diluted feedstock 203 can be about 0.00046 to about 0.00233 g / g.

[0082] In some embodiments, the step of adding the sulfiding agent 235 can be performed before the reaction steps in the reaction zone. For example, the sulfiding agent 235 can be added to the renewable feedstock 201 during mixing with the diluent, or to the diluted feedstock before contact with hydrogen, or to the diluted feedstock 205 enriched with dissolved hydrogen before being introduced into the reactor.

[0083] In some alternative embodiments, the diluted feedstock 205 enriched with dissolved hydrogen can be prepared in a single step, rather than in two steps as described above. Specifically, the diluted feedstock 205 enriched with dissolved hydrogen can be prepared by simultaneously feeding renewable feedstock 201, diluent 202, and hydrogen 204. The ratio of diluent 202 to renewable feedstock 201 can be approximately 99 wt% diluent / 1 wt% feedstock to approximately 95 wt% diluent / 5 wt% feedstock, approximately 95 wt% diluent / 5 wt% feedstock to approximately 90 wt% diluent / 10 wt% feedstock, approximately 80 wt% diluent / 20 wt% feedstock to approximately 70 wt% diluent / 30 wt% feedstock, or approximately 60 wt% diluent / 40 wt% feedstock to approximately 50 wt% diluent / 50 wt% feedstock, while the ratio of hydrogen 204 to renewable feedstock 202 can be approximately 10 to approximately 700 Nm. 3 / m 3(about 0.001 to about 0.054 g / g or about 0.1 wt% to about 5.4 wt%), 10 to about 650 Nm 3 / m 3 (about 0.001 to about 0.050 g / g or about 0.1% by weight to about 5% by weight), about 10 to about 600 Nm 3 / m 3 (about 0.001 to about 0.047 g / g or 0.1 wt% to about 4.7 wt%), about 10 to about 550 Nm 3 / m 3 (about 0.001 to about 0.044 g / g or about 0.1 wt% to about 4.4 wt%), about 10 to about 500 Nm 3 / m 3 (about 0.001 to about 0.039 g / g or 0.1 wt% to about 3.9 wt%), about 10 to about 450 Nm 3 / m 3 (about 0.001 to about 0.035 g / g or about 0.1 wt% to about 3.5 wt%), about 10 to about 400 Nm 3 / m 3 (about 0.001 to about 0.032 g / g or about 0.1 wt% to about 3.2 wt%), about 10 to about 380 Nm 3 / m 3 (about 0.001 to about 0.030 g / g or about 0.1 wt% to about 3.0 wt%), about 10 to about 350 Nm 3 / m 3 (about 0.001 to about 0.028 g / g or about 0.1 wt% to about 2.8 wt%) or about 10 to about 320 Nm 3 / m 3 (about 0.001 to about 0.025 g / g or about 0.1% by weight to about 2.5% by weight).

[0084] In some implementations, the choice of the hydrogen-to-renewable feedstock ratio for continuous liquid-phase hydrogenation depends primarily on the type of renewable feedstock. For example, in the case of RBDPO, the hydrogen-to-renewable feedstock ratio is approximately 450 Nm³. 3 / m 3 (at least 0.035 g / g or about 3.5% by weight) or at least 385 Nm 3 / m 3 (at least 0.030 g / g or about 3.0% by weight) or at least 320 Nm 3 / m 3 (At least 0.025 g / g or about 2.5% by weight). In the case of refined soybean oil, the ratio of hydrogen to renewable feedstock is approximately 550 Nm. 3 / m3 (at least 0.044 g / g) or at least 510 Nm 3 / m 3 (at least 0.040 g / g or about 4.0% by weight) or at least 385 Nm 3 / m 3 (At least 0.035 g / g or about 3.5% by weight). The amount of hydrogen consumed in producing processed oils varies for each type of renewable feedstock due to the length and degree of unsaturation of their triglyceride and fatty acid chains. Specifically, hydrogenation processes containing triglycerides with shorter fatty acid chains and / or higher degrees of unsaturation require a higher amount of hydrogen.

[0085] However, if a single-step operation is to be performed to prepare the diluted feedstock 205 enriched with dissolved hydrogen, it should be understood that the single-step operation needs to be carried out at temperatures of about 200°C to about 400°C, about 250°C to about 320°C, or about 250°C to about 360°C, and pressures of about 20 bar to about 100 bar, about 25 bar to about 100 bar, or about 30 bar to about 100 bar. Therefore, it is not feasible to prepare the diluted feedstock 205 enriched with dissolved hydrogen in advance and store it in a warehouse.

[0086] After obtaining a diluted feedstock 205 enriched with dissolved hydrogen, it can be fed into a first reactor 20 having at least a reaction zone, which includes at least a catalyst bed (which includes at least an activated hydrotreating catalyst). For ease of description, the following embodiments will be described with respect to a reactor having one catalyst reaction zone, but it should be understood that the number of reaction zones in a reactor should not be limited to or restricted by this.

[0087] Specifically, a diluted feedstock 205 enriched with dissolved hydrogen can be fed into a first reactor 20, wherein the diluted feedstock 205 passes through a first catalyst bed comprising an activated hydrotreating catalyst. When the diluted feedstock 205 enriched with dissolved hydrogen comes into contact with the activated hydrotreating catalyst, the alkene or unsaturated portion of the n-chain hydrocarbon chain in the diluted feedstock 205 is hydrotreated. The reaction effluent from the first reactor 20 can then be directed to a first hot high-pressure separator (HHPS) 228 for the separation of undesirable gaseous byproducts, such as water vapor, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H2S), a small amount of hydrogen, and a small amount of gaseous hydrotreated products. Therefore, the undesirable gaseous byproducts leave the first HHPS 228 as waste stream 207, which is directed to a waste treatment unit (not shown), while the separated reaction effluents leave the first HHPS 228 as first effluent stream 206, which contains hydrotreated oil, unreacted feedstock, unreacted diluent, a small amount of hydrogen, and a small amount of undesirable byproducts.

[0088] Subsequently, the first effluent stream 206 can be contacted with the required amount of hydrogen 208 and the required amount of sulfurizing agent 236 before being fed into the second reactor 21. The step of contacting the first effluent stream 206 with hydrogen 208 and sulfurizing agent 236 is crucial because it helps ensure that there is sufficient hydrogen available for the subsequent hydrotreating reaction and that the efficiency of the catalyst can be maintained.

[0089] After the first effluent 209 enriched with dissolved hydrogen is fed into the second reactor 21, it can be passed through a second catalyst bed containing an activated hydrotreating catalyst. When the first effluent 209 contacts the activated hydrotreating catalyst, the alkene or unsaturated portion of the n-chain hydrocarbon chain in the first effluent 209 is hydrotreated. The reaction effluent from the second reactor 21 can then be directed to a second HHPS 229 to separate unwanted gaseous byproducts such as water vapor, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H2S), trace amounts of hydrogen, and trace amounts of gaseous hydrotreating products. Therefore, the undesirable gaseous byproducts leave the second HHPS 229 as waste stream 211, which is directed to a waste treatment device (not shown), while the separated reaction effluents leave the second HHPS 229 as second effluent stream 210, which contains hydrotreated oil, unreacted feedstock, unreacted diluent, a small amount of hydrogen, and a small amount of undesirable byproducts.

[0090] Similarly, before feeding the second effluent 210 into the third reactor 22, it is necessary to contact the second effluent 210 with a required amount of hydrogen 212 and a required amount of sulfiding agent 237 to dissolve the hydrogen and sulfiding agent in the second effluent 210. This is to ensure that there is sufficient hydrogen available for the subsequent hydrotreating reaction and to maintain the efficiency of the catalyst. After feeding the hydrogen-enriched second effluent 213 into the third reactor 22, the hydrogen-enriched second effluent 213 can be passed through a third catalyst bed containing an activated hydrotreating catalyst. When the hydrogen-enriched second effluent 213 contacts the activated hydrotreating catalyst, the alkene or unsaturated portion of the n-chain hydrocarbon chain in the hydrogen-enriched second effluent 213 is hydrotreated. The reaction effluent from the third reactor 22 can then be directed to the third HHPS 230 to separate unwanted gaseous byproducts, such as water vapor, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H2S), a small amount of hydrogen, and a small amount of gaseous hydrotreating products. Thus, the unwanted gaseous byproducts exit the third HHPS 229 as waste stream 215, which is directed to a waste treatment unit (not shown), while the separated reaction effluent exits the third HHPS 230 as third effluent stream 214, which contains hydrotreated oil, unreacted feedstock, unreacted diluent, a small amount of hydrogen, and a small amount of unwanted byproducts.

[0091] In some embodiments, the amount of hydrogen to be added to the second and / or third reactor may be soluble in the feed amount or may be present in excess. Undissolved hydrogen may form a gaseous phase in the reaction zone along with gaseous byproducts such as carbon monoxide, carbon dioxide, propane, and hydrogen sulfide. The required amount of hydrogen must be sufficient to carry out one or more reactions in the reaction zone (depending on the volume of feedstock to be reacted in the reaction zone) and / or not to form an excessive gaseous phase. In particular, the gas volume fraction (GVF) of the gaseous phase occurring in this step is from about 0.1 to about 0.25. The required sulfide dosage is preferably 0-10,000 ppmw of sulfur relative to the volume of feedstock in the liquid stream.

[0092] Subsequently, a portion or preferably all of the third effluent stream 214 may be separated once or multiple times to separate impurities or gaseous contaminants that may be present or dissolved in the third effluent stream 214. In some embodiments, the third effluent stream 214 may first be fed into a flash evaporator 23 to separate gaseous contaminants present in the third effluent stream 214. In particular, gaseous contaminants comprising water vapor, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H2S), a small amount of hydrogen, and a small amount of gaseous hydrotreated products may exit as a first top stream 218, while the remaining liquid mixture may exit as a first bottom stream 219 comprising hydrotreated oil, diluent, and water, which will be fed into a second separator 24. In some embodiments, the second separator 24 may be a low-pressure separator 24 to separate the water component from the first bottom stream 219. While the undesirable water component (separated from the first bottom stream 219) can exit the second separator 24 as the second bottom stream 221, the remaining liquid mixture can exit as the second stream 220. It should be understood that the second stream 220 is substantially free of gaseous contaminants and water components when it exits the second separator 24.

[0093] The second stream 220 can be further fed to a third separator 25, preferably a distillation column. The presence of the third separator ensures the recovery of diluent 216 from the second stream 220, and the recovered diluent 216 can be reused by reinjecting it into the diluent feed stream or a diluent source (before contact with hydrogen 204). Furthermore, after the diluent is recovered from the second stream 220, the remaining liquid mixture can exit the third separator 25 as a hydrotreated product stream 222. In a preferred embodiment, the hydrotreated product stream 222 can be a hydrotreated oil phase comprising a mixture mainly of straight-chain n-alkane hydrocarbons. In particular, the hydrotreated product stream 222 can be bio-naphtha hydrocarbons. The composition of the bio-naphtha hydrocarbons can include at least 90% by weight of n-chain hydrocarbons and 0-10% by weight of iso-paraffin hydrocarbons, wherein the hydrocarbons are mainly C7-C6. 18 Within the range.

[0094] The hydrotreated product stream 222 can be further processed to form a phase change material (PCM), an industrial solvent, or both. In a more preferred embodiment, the hydrotreated product stream 222 can be a hydrotreated oil phase comprising small volumes of isomeric hydrocarbons and large volumes of normal-chain hydrocarbons. The isomeric hydrocarbons present in the hydrotreated product stream 222 can be substantially free of sulfur, olefins, and aromatic compounds, thereby making the isomeric hydrocarbons non-toxic and preventing the formation of undesirable harmful products.

[0095] It should be understood that the present invention is advantageous in minimizing hydrogen loss during the hydrotreating process, such as from reactors 20, 21, 22 and separators 23, 24, 25. Unlike conventional methods, the present invention also eliminates the need to feed large amounts of excess hydrogen into each reactor. This is because a diluent 202, primarily comprising a normal-chain hydrocarbon having 12 carbon atoms, is added and mixed with renewable feedstock 201 to form a diluted feedstock 203, in which hydrogen is readily dissolved. By eliminating the need to feed excess hydrogen into the reactors while minimizing hydrogen loss throughout the hydrotreating process, the present invention offers greater economic benefits compared to conventional methods.

[0096] In some implementations, the liquid time space velocity can be from approximately 0.5 to 10.0 hr. -1 Approximately 0.5 to 20.0 hours -1 Approximately 0.5 to 30.0 hr -1 Approximately 0.5 to 40.0 hr -1 Approximately 0.5 to 50.0 hr -1 Approximately 0.5 to 60.0 hr -1 Approximately 0.5 to 70.0 hr -1 Approximately 0.5 to 80.0 hr -1 Approximately 0.5 to 90.0 hr -1 Approximately 0.5 to 100.0 hr -1 Within the range.

[0097] It should also be understood that although the catalytic reactions occurring in reactors 20, 21, and 22 are exothermic reactions, i.e., reactions that release heat, no additional steps are required to remove heat from reactors 20, 21, and 22 because the desired ratio between the renewable feedstock and the diluent results in low heat generation from the catalytic reaction and the diluent can absorb the heat generated by the reaction.

[0098] In another embodiment, a method for hydrogenating a renewable feedstock comprising triglycerides, free fatty acids, or combinations thereof to produce a product comprising a phase change material and an industrial solvent may also be provided.

[0099] like Figure 2 As shown, it can be obtained from Figure 1 The hydrotreated product stream 222 of the illustrated hydrotreatment method is further processed by additional distillation and adsorption to produce products including phase change materials (PCMs) and industrial solvents. Since the hydrotreated product stream 222 is substantially free of sulfur, olefins, and aromatics, the PCM obtained from the further processed hydrotreated product stream 222 can also be substantially free of sulfur, aromatics, and alcohols, as shown in Table 2.

[0100] In particular, it can be obtained from Figure 1 The hydrotreated product stream 222 of the illustrated hydrotreating method is fed to a first distillation column 26, thereby producing a fourth top stream 224 and a fourth bottom stream 223 containing n-chain hydrocarbons with fewer than 16 carbon atoms. The fourth bottom stream 223 can be fed to a second distillation column 28. In some embodiments, the fourth top stream 224 can pass through a first adsorption unit 27, thereby producing a first fraction 225 containing the desired industrial solvent.

[0101] In the second distillation column 28, the components in the fourth bottom stream 223 are separated to produce a fifth top stream 227, which contains at least about 99.0% by weight of n-hexadecane, and a fifth bottom stream 226, which can be fed to the third distillation column 30. In some embodiments, the fifth top stream 227 can pass through a second adsorption unit 29 to produce a second fraction 228 containing purified hexadecane, or PCM#1 herein.

[0102] In the third distillation column 30, the components in the fifth bottom stream 226 are separated to produce a sixth top stream 230, which contains at least about 99.0% by weight of n-heptadecane and a sixth bottom stream 229, which can be fed to the fourth distillation column 31. In some embodiments, the sixth top stream 230 can pass through a third adsorption unit 31 to produce a third fraction 231 containing purified heptadecane, or PCM#2 herein.

[0103] In the fourth distillation column 32, the components in the sixth bottom stream 229 are separated to produce a seventh top stream 233, which contains at least about 99.0% by weight of n-octadecane and the seventh bottom stream 232. The seventh bottom stream 232 can be used as fuel oil (or bunker oil) suitable for applications such as, but not limited to, mobile engine fuel. In some embodiments, the seventh bottom stream 233 can pass through the fourth adsorption unit 33 to produce a fourth fraction 234 containing purified octadecane, or PCM#3 herein.

[0104] In some other embodiments, a single fractionation distillation column can be used instead of multiple distillation columns 26, 28, 30, 32 to obtain a variety of products, including industrial solvents, PCM#1, PCM#2, and PCM#3. It should also be understood that by providing adsorption units 27, 29, 31, 33 to treat the topstreams 224, 227, 230, 233, the quality of these streams is improved by eliminating unwanted impurities or contaminants contained therein. For example, adsorption units 27, 29, 31, 33 can be used to remove unwanted components such as, but not limited to, volatile organic compounds, substances that may impart unpleasant odors or colors to the industrial solvents and / or PCM. After removing these unwanted components, unpleasant properties such as unpleasant odors or unpleasant colors from the industrial solvents and / or PCM can be minimized or substantially eliminated. Furthermore, the adsorption units can be used at atmospheric pressure, a temperature of about 30°C to about 70°C, and for about 0.5 hours. -1 Up to 2.0h -1 It operates at air velocity. Although the operating temperature of the adsorption unit can be selected according to the feed flow, it is not necessary to maintain the operating temperature of the adsorption unit, thus simplifying operation.

[0105] In some embodiments, the adsorption unit may include at least one adsorption column, each column comprising at least one adsorbent selected from activated carbon, basic ion exchange resins, acidic ion exchange resins, molecular sieves, basic chemisorbents, and acidic chemisorbents. In some embodiments, the pore size of the molecular sieve is approximately... to approximately Within the specified range. In some other embodiments, alkaline chemisorbents may be preferred.

[0106] Example

[0107] Example 1: Method for Hydrotreating Palm Oil

[0108] A commercially available NiMo / Al2O3 catalyst was loaded into a reactor and then activated into a sulfide form in the presence of carbon disulfide as a sulfiding agent at a temperature of approximately 150°C to approximately 340°C and a pressure of approximately 35 bar for approximately 24 hours. The amount of sulfide in the sulfiding agent fed into the reactor was twice the amount of catalyst required for the sulfidation reaction based on chemical equilibrium.

[0109] At room temperature and atmospheric pressure, using a suitable mixing apparatus known in the art, refined bleached and deodorized palm oil (RBDPO) is used as a renewable feedstock and mixed with dodecane as a diluent to form a diluted feedstock. The ratio of diluent to renewable feedstock is approximately 90:10 (by weight). A vulcanizing agent is added to the diluted feedstock, which is then heated to approximately 340°C and pressurized to approximately 50 to approximately 75 bar. Subsequently, excess hydrogen is passed through the diluted feedstock, where the required amount of hydrogen dissolves, thus forming a diluted feedstock enriched with dissolved hydrogen. The amount of hydrogen to be fed at this stage is approximately 30% of the total amount of hydrogen to be fed throughout the entire hydrotreating process.

[0110] Next, the diluted feedstock enriched with dissolved hydrogen is fed into a first reactor operating at an operating temperature of about 340°C and an operating pressure of about 50 to about 75 bar. The first reactor has at least one reaction zone including a catalyst bed for hydrogenating the effluent of the alkene or unsaturated portion of the n-chain hydrocarbon chain. The amount of hydrogen relative to the volume of the catalyst bed in the first reactor is about 600 Nm³. 3 / m 3 The reaction mixture is then passed through a first HHPS to separate water vapor and gaseous components, thereby obtaining the first reaction effluent.

[0111] Before the first reaction effluent is introduced into the second reactor, it is contacted with a required amount of hydrogen (heated to approximately 340°C and pressurized to approximately 50 to approximately 75 bar) and a required amount of sulfiding agent to form a first reaction effluent enriched with dissolved hydrogen. The amount of hydrogen to be fed at this stage is approximately 17.5% of the total hydrogen to be fed throughout the entire hydrotreating process.

[0112] The first reaction effluent, enriched with dissolved hydrogen, is then introduced into a second reactor operating at an operating temperature of about 340°C and an operating pressure of about 50 to about 75 bar. The second reactor has at least one reaction zone including a catalyst bed to further hydrogenate the alkene or unsaturated portion of the n-chain hydrocarbon chain in the first reaction effluent. The amount of hydrogen relative to the volume of the catalyst bed in the second reactor is about 400 Nm³. 3 / m 3 The reaction mixture is then passed through a second HHPS to separate water vapor and gaseous components, thereby obtaining a second reaction effluent.

[0113] Before the second reaction effluent is introduced into the third reactor, it is contacted with a required amount of hydrogen (heated to approximately 340°C and pressurized to approximately 50 to 75 bar) and a required amount of sulfiding agent to form a second reaction effluent enriched with dissolved hydrogen. The amount of hydrogen to be fed at this stage is approximately 17.5% of the total hydrogen fed throughout the entire hydrotreating process.

[0114] The second reaction effluent, enriched with dissolved hydrogen, is then introduced into a third reactor operating at an temperature of approximately 340°C and an operating pressure of approximately 50 to approximately 75 bar. The third reactor has at least one reaction zone comprising a catalyst bed for further hydrogenation of the alkene or unsaturated portion of the n-chain hydrocarbon chain in the second reaction effluent. The amount of hydrogen relative to the catalyst bed volume in the third reactor is approximately 400 Nm³. 3 / m 3 The reaction mixture is then passed through a third HHPS to separate water vapor and gaseous components, thereby obtaining a third reaction effluent.

[0115] Before the third reaction effluent is introduced into the fourth reactor, it is contacted with a required amount of hydrogen (heated to approximately 340°C and pressurized to approximately 50 to 75 bar) and a required amount of sulfiding agent to form a third reaction effluent enriched with dissolved hydrogen. The amount of hydrogen to be fed at this stage is approximately 17.5% of the total hydrogen fed throughout the entire hydrotreating process.

[0116] The third reaction effluent, enriched with dissolved hydrogen, is then introduced into a fourth reactor operating at an temperature of approximately 340°C and an operating pressure of approximately 50 to approximately 75 bar. The fourth reactor has at least one reaction zone including a catalyst bed for further hydrogenation of the alkene or unsaturated portion of the n-chain hydrocarbon chain in the third reaction effluent. The ratio of hydrogen to the catalyst bed volume in the third reactor is approximately 400 Nm³. 3 / m 3 The reaction mixture is then passed through a fourth HHPS to separate water vapor and gaseous components, thereby obtaining a fourth reaction effluent.

[0117] The fourth reaction effluent (which is in the oil phase) is passed through a flash evaporator to separate the dissolved gaseous components, thereby obtaining a first separated effluent. The first separated effluent is then introduced into a low-pressure separator to separate water vapor, thereby obtaining a second separated effluent. The second separated effluent is further passed through a distillation column to separate the diluent, thereby obtaining the desired hydrotreated product or more specifically, a hydrotreated oil.

[0118] Table 2 shows the properties of the hydrotreated oil obtained from the method described in Example 1.

[0119]

[0120]

[0121] Example 2: Method for Hydrotreating Palm Oil

[0122] A commercially available CoMo / Al2O3 catalyst was loaded into a reactor and then activated into a sulfide form in the presence of dimethyl disulfide as a sulfiding agent at a temperature of approximately 150°C to approximately 340°C and a pressure of approximately 35 bar for approximately 24 hours. The amount of sulfide in the sulfiding agent fed into the reactor was twice the amount of catalyst required for the stoichiometric sulfidation reaction.

[0123] Refined bleached and deodorized palm oil (RBDPO) is used as a renewable feedstock and mixed with treated oil products as a diluent at room temperature and atmospheric pressure using suitable mixing equipment known in the art to form a diluted feedstock. The ratio of diluent to renewable feedstock is approximately 99:1 (by weight). A vulcanizing agent is added to the diluted feedstock, which is then heated to approximately 320°C and pressurized to approximately 30 to approximately 40 bar. Subsequently, hydrogen is passed through the diluted feedstock, whereby the required amount of hydrogen dissolves in the diluted feedstock, thereby forming a diluted feedstock enriched with dissolved hydrogen. The amount of hydrogen to be fed at this stage is approximately 50% of the total amount of hydrogen to be fed throughout the entire hydrotreating process (total hydrogen is 3.0% by weight of the fresh feedstock).

[0124] Next, the diluted feedstock enriched with dissolved hydrogen is fed into a first reactor operating at an operating temperature of approximately 340°C and an operating pressure of approximately 30 to approximately 40 bar. The first reactor has at least one reaction zone including a catalyst bed to form the treated oil. The liquid hourly space velocity is maintained at 25.0 hr. -1 The reaction mixture is then passed through a first HHPS to separate water vapor and gaseous components, thereby obtaining the first reaction effluent.

[0125] Before introducing the first reaction effluent into the second reactor, the first reaction effluent is contacted with a desired amount of hydrogen (heated to approximately 320°C and pressurized to approximately 30 to 40 bar) and a desired amount of sulfiding agent to form a first reaction effluent enriched with dissolved hydrogen. The amount of hydrogen to be fed at this stage is approximately 50% of the total hydrogen to be fed during the entire hydrotreating process.

[0126] The first reaction effluent, enriched with dissolved hydrogen, is then introduced into a second reactor operating at approximately 320°C and approximately 30 to approximately 40 bar. The second reactor has at least one reaction zone including a catalyst bed to form the treated oil. The liquid hourly space velocity is maintained at 25.0 hr. -1 The reaction mixture is then passed through a second HHPS to separate water vapor and gaseous components, thereby obtaining a second reaction effluent.

[0127] The second reaction effluent is introduced into a low-pressure separator to separate water, thereby obtaining the first separated effluent of the hydrotreated oil. Table 3 shows the properties of the treated oil obtained from Example 2.

[0128] It should be understood that the treated oil obtained from Example 2 can be achieved without the step of separating the dissolved gaseous components using a flash evaporator, because the gaseous components can be separated primarily in the hot high-pressure separator step. Furthermore, the treated oil obtained from Example 2 can also be achieved without a distillation step, but the treated oil may exhibit a lower flash point.

[0129] Table 3 shows the properties of the hydrotreated oil obtained from the method described in Example 2.

[0130]

[0131] Example 3: The effect of reduced hydrogen circulation rate

[0132] In traditional hydrotreating methods, the reactor typically operates as a trickle bed, where hydrogen is transferred through the surface of a liquid-covered catalyst, forming a continuous gas phase throughout the reactor. Therefore, trickle bed reactions require a very high volumetric hydrogen flow rate (hydrogen recirculation rate), exceeding the hydrogen flow rate required for the reaction (hydrogen consumption rate) to maintain the continuous gas phase. Failure to maintain a continuous gas phase can lead to catalyst deactivation.

[0133] Typically, the hydrogen consumption rate used in the hydrotreating of RBDPO is from about 2.5% to about 3.5% by weight, while the hydrogen consumption rate used in conventional hydrotreating is about 200% of these hydrogen consumption rates.

[0134] Hydrogenated oil was prepared using two reactors according to the method described in Example 2, under the following reaction conditions;

[0135] The raw material used in this experiment is RBDPO;

[0136] The reaction temperature is approximately 320°C;

[0137] The reaction pressure is approximately 35 bar.

[0138] • The treated oil is used as a diluent;

[0139] • The ratio of diluent to renewable raw materials is approximately 99:1 (by weight);

[0140] • Liquid hourly space velocity is approximately 25.0 hr -1 ;

[0141] • The sulfidated form of CoMo / Al2O3 was used as an activation catalyst loaded in each reactor;

[0142] • The amount of hydrogen relative to the renewable feedstock is approximately 3.5-6.0% by weight;

[0143] • Add hydrogen to each reactor in an amount equal to 50% of the total amount of hydrogen to be fed into the entire hydrogenation process;

[0144] HHPS is used to separate gaseous components and water vapor from the reaction effluent obtained from each reactor.

[0145] Table 4 shows the properties of the hydrotreated oil obtained from the method described in Example 3.

[0146]

[0147] As can be seen from Table 4, even when the hydrogen recycling rate used in Example 3 was 3.5% by weight, or 4% by weight, or 5% by weight, or 6% by weight, the product performance remained unchanged. That is, the present invention provides the advantage of using hydrogen recycling rates in the range of 200%, 175%, 150%, 125%, or 100% of hydrogen consumption rates. According to the present invention, excessive amounts of hydrogen are not required during the hydrotreating process.

[0148] Example 4: Method for producing phase change material (PCM) from hydrotreated oil obtained in Example 1

[0149] This embodiment describes a method for producing PCM from hydrotreated oil obtained from the method described in Example 1. Specifically, the hydrotreated oil is introduced into multiple distillation units and multiple adsorption units. The performance of the PCM is shown in Table 5.

[0150] Table 5 shows the performance of the PCM obtained from the method described in Example 4.

[0151]

[0152] Example 5: The impact of the type of renewable feedstock on the PCM produced

[0153] This example is conducted to demonstrate how the choice of renewable feedstock will affect the performance of the produced PCM.

[0154] Hydrogenated oils were prepared using five reactors and the following reaction conditions, according to the method described in Example 1:

[0155] The reaction temperature is approximately 360°C;

[0156] The reaction pressure is approximately 50 to approximately 75 bar;

[0157] • Use n-undecane as a diluent;

[0158] • The ratio of diluent to renewable raw materials is approximately 90:10 (by weight);

[0159] • Liquid hourly space velocity is approximately 10.0 hr -1 ;

[0160] • Sulfated CoMo / Al2O3 was used as an activation catalyst and loaded into each reactor;

[0161] • The amount of hydrogen relative to the renewable feedstock is approximately 3.5% by weight;

[0162] • Add hydrogen to each reactor in an amount equal to 20% of the total amount of hydrogen to be fed during the entire hydrogenation process;

[0163] • The amount of hydrogen relative to the catalyst bed volume in the first reactor is 600 Nm³. 3 / m 3 ;

[0164] • The amount of hydrogen relative to the catalyst bed volume in the second reactor is 400 Nm³. 3 / m 3 ;

[0165] • In the third reactor, the amount of hydrogen relative to the catalyst bed volume is 200 Nm³. 3 / m 3 ;

[0166] • In the fourth reactor, the amount of hydrogen relative to the catalyst bed volume is 100 Nm³. 3 / m 3 ;

[0167] • In the fifth reactor, the amount of hydrogen relative to the catalyst bed volume is 50 Nm³. 3 / m 3 ;as well as

[0168] HHPS is used to separate gaseous components and water vapor from the reaction effluent obtained from each reactor.

[0169] Table 6 shows the performance of the PCM obtained from the method described in Example 4.

[0170]

[0171] The results in Table 6 show that the hydrogenation process of RBDPO produces a large amount of normal-chain hydrocarbons with 16 and 18 carbon atoms, similar to the process of hydrogenating palm fatty acids. On the other hand, the hydrogenation processes of rapeseed oil, soybean oil, and stearic acid produce a large amount of normal-chain hydrocarbons with 17 and 18 carbon atoms. Therefore, it should be understood that feedstocks containing fats and / or fatty acids can be used as renewable feedstocks for the production of various normal-chain hydrocarbons, which can then be used to produce and obtain various PCMs.

[0172] Example 6: Preparation of bio-naphtha

[0173] This embodiment describes a method for producing bio-naphtha. Specifically, according to the method described in Example 1, palm kernel oil and lauric acid are used as renewable feedstocks, and the following reaction conditions are employed to prepare the hydrogenated oil:

[0174] • Use three reactors;

[0175] The reaction temperature is approximately 360°C;

[0176] The reaction pressure is approximately 100 bar.

[0177] • Fresh bio-naphtha and / or a portion of the bio-naphtha recovered from the process are used as a diluent;

[0178] • The ratio of diluent to renewable raw materials is approximately 85:15 (by weight);

[0179] • Liquid hourly space velocity is approximately 10.0 hr -1 ;

[0180] • Sulfated NiCoMo / Al2O3 catalyst was used as the activation catalyst loaded in each reactor;

[0181] • The amount of hydrogen relative to the renewable feedstock is approximately 2.2% by weight;

[0182] • 40% of the total hydrogen fed into the hydrotreating process is supplied to the first reaction zone, 30% of the total hydrogen fed into the hydrotreating process is supplied to the second reaction zone, and 30% of the total hydrogen fed into the hydrotreating process is supplied to the third reaction zone.

[0183] • The amount of hydrogen relative to the catalyst bed volume in the first reactor is 600 Nm³. 3 / m 3 ;

[0184] • The amount of hydrogen relative to the catalyst bed volume in the second reactor is 300 Nm³. 3 / m 3 ;

[0185] • In the third reactor, the amount of hydrogen relative to the catalyst bed volume is 50 Nm³. 3 / m 3 ;

[0186] • HHPS is provided downstream of each reactor to separate gaseous byproducts, including water vapor, from the reaction effluents obtained from each reactor.

[0187] Table 7 shows the properties of the bio-naphtha obtained from the method described in Example 6.

[0188]

[0189]

[0190] Comparative Example 1

[0191] Comparative Example 1 is compared with Example 3. Comparative Example 1 was carried out using a conventional hydrotreating method to produce a hydrotreated oil, which was prepared using a reactor and the following reaction conditions according to the method described in Example 2:

[0192] The raw material used in this experiment is RBDPO;

[0193] The reaction temperature is approximately 320°C;

[0194] The reaction pressure is approximately 35 bar.

[0195] • The treated oil is used as a diluent;

[0196] • The ratio of diluent to renewable raw materials is approximately 70:30 (by weight);

[0197] • Liquid hourly space velocity is approximately 1.0 hr -1 ;

[0198] • Sulfated CoMo / Al2O3 was used as an activation catalyst and loaded into each reactor;

[0199] • The amount of hydrogen relative to the renewable feedstock varied at 5.0, 5.5, and 6.0% by weight; and

[0200] HHPS is used to separate gaseous components and water vapor from the reaction effluent obtained from each reactor.

[0201] Table 8 shows the properties of hydrotreated oils obtained from conventional hydrotreating methods.

[0202]

[0203] As shown in Table 8, using a hydrogen recirculation rate below 6% by weight (i.e., 5.5% and 5% hydrogen recirculation rates) results in high acid values ​​in the treated oil. This is because the free fatty acid content in the treated oil increases due to incomplete reaction, making the treated oil more acidic. In other words, the hydrogen recirculation rate used in conventional hydrotreating must be at least 200% of the hydrogen consumption rate, which is in the range of 2.5-3.5% by weight in the case of RBDPO.

[0204] Comparative Example 2

[0205] Yantao Bi et al. investigated the compositional changes during hydrodeoxygenation of biomass pyrolysis oil. The study was conducted using pyrolysis oil prepared from forestry residues at a pyrolysis temperature of approximately 500 °C. Hydrodeoxygenation was carried out continuously in two fixed-bed reactors. The reaction temperature in the first reactor was maintained at 100 °C to ensure stability, while the reaction temperatures in the second reactor were maintained at 150, 210, 300, and 360 °C to produce upgraded pyrolysis oils, designated UPO-1, UPO-2, UPO-3, and UPO-4, respectively.

[0206] Table 9 shows the composition of pyrolysis oil and UPO-1, UPO-2, UPO-3 and UPO-4 obtained from the hydrodeoxygenation of pyrolysis oil.

[0207]

[0208] The results and the table above show that UPO-1, UPO-2, UPO-3 and UPO4 obtained from processed pyrolysis oil do not contain normal-chain hydrocarbons. Therefore, these compounds cannot be used to produce phase change materials, which is different from the present invention.

[0209] Comparative Example 3

[0210] Tables 10-14 show the solubility of hydrogen in renewable feedstocks primarily composed of triglycerides and free fatty acids, as well as the solubility of hydrogen in different diluted feedstocks, where n-chain hydrocarbons with different carbon numbers are used as diluents to dilute the renewable feedstocks primarily composed of triglycerides and free fatty acids. These tables also show that n-chain hydrocarbons with fewer carbon atoms provide better hydrogen solubility in the diluted feedstocks.

[0211] In some implementations, diluents that are not n-chain hydrocarbons may be used to increase the solubility of hydrogen in the diluted feedstock. However, using other diluents that are not n-chain hydrocarbons may lead to difficulties in separating the diluent from the hydrotreated oil products, thus incurring additional costs to production.

[0212] Table 10 shows the solubility of hydrogen in tri-oil as a raw material.

[0213]

[0214] Table 11 shows the solubility of hydrogen in a diluted feedstock prepared using n-octadecane as a diluent and triolein as a raw material at a ratio of 90% by weight of diluent to 10% by weight of feedstock.

[0215]

[0216] Table 12 shows the solubility of hydrogen in a diluted feedstock prepared using n-tetradecane as a diluent and triolein as a raw material at a ratio of 90% by weight of diluent to 10% by weight of feedstock.

[0217]

[0218]

[0219] Table 13 shows the solubility of hydrogen in a diluted feedstock prepared using n-dodecane as a diluent and triolein as a raw material at a ratio of 90% by weight of diluent to 10% by weight of feedstock.

[0220]

[0221] Table 14 shows the solubility of hydrogen in a diluted feedstock prepared using n-undecane as a diluent and triolein as a raw material at a ratio of 90% by weight of diluent to 10% by weight of feedstock.

[0222]

[0223] The tables above show that hydrogen solubility is low when using n-chain hydrocarbons with a high number of carbon atoms as diluents. The results also indicate that n-dodecane, with 12 carbon atoms, has the highest hydrogen solubility when used as a diluent. However, the use of n-chain hydrocarbons with fewer than 10 carbon atoms as diluents is not recommended because they cannot maintain their liquid phase under reaction conditions.

[0224] Having read the foregoing disclosure, various other modifications and adjustments will be apparent to those skilled in the art without departing from the spirit and scope of the invention. All such modifications and adjustments are within the scope of the appended claims.

[0225] Furthermore, it should be understood that features of various implementation schemes can be combined to form one or more additional implementation schemes.

[0226] References

[0227] 1.Yantao Bi, Gang Wang, Quan Shi, Chunming Xu and Jinsen Guo. CompositionalChanges during Hydrodeoxygenation of Biomass Pyrolysis Oil, Energy Fuels, 2014, 28, pages 2571-2580.

Claims

1. A method for producing one or more hydrocarbon products from a liquid-phase renewable feedstock via a plurality of hydrotreating reactors, said plurality of hydrotreating reactors comprising a first reactor and at least one additional reactor, each reactor having a catalyst bed supported on a hydrotreating catalyst, said catalyst having been activated by a sulfidation process prior to use, said renewable feedstock comprising triglycerides, free fatty acids, or combinations thereof, said method comprising the following steps: The renewable raw material is diluted with a diluent to form a diluted raw material; Before introducing the diluted feedstock enriched with dissolved hydrogen into the first reactor, the diluted feedstock enriched with dissolved hydrogen is formed by: (a) contacting the diluted feedstock with hydrogen and then adding a sulfiding agent to the diluted feedstock that has been contacted with hydrogen, or (b) adding a sulfiding agent to the diluted feedstock and then contacting the diluted feedstock with the added sulfiding agent with hydrogen. The diluted feedstock enriched with dissolved hydrogen is fed into a first reactor comprising a first catalyst bed. The reaction mixture is then passed through a high-pressure thermal separator (HHPS) located downstream of the first reactor to obtain a hydrogen-enriched reaction effluent. The catalyst bed in the first reactor is operated at a temperature of 340°C, an operating pressure of 30 to 40 bar, and a liquid hourly space velocity maintained at 25.0 Hr. -1 ; Before introducing the hydrogen-enriched reaction effluent into another reactor, the reaction effluent is further contacted with hydrogen and a sulfiding agent, so that the hydrogen dissolves in the reaction effluent to form a hydrogen-enriched reaction effluent. The hydrogen-enriched reaction effluent is further fed into the additional reactor, which includes a separate catalyst bed. The reaction mixture is then passed through a separate high-pressure thermal separator (HHPS) located downstream of the additional reactor to produce a re-reaction effluent, which can be further processed to form one or more hydrocarbon products. The additional catalyst bed in the additional reactor operates at a temperature of 320°C, an operating pressure of 30 to 40 bar, and a liquid hourly space velocity (LHSV) maintained at 25.0 Hr. -1 , The gaseous volume fraction (GVF) of undissolved hydrogen in the additional reactor is 0.1 to 0.

25. The ratio of hydrogen to the raw material is 3.5-6 by weight.

2. The method of claim 1, further comprising the step of passing a vulcanizing agent and / or hydrogen through each reactor in a predetermined amount.

3. The method of claim 1, further comprising the step of separating gaseous byproducts from the reaction effluent or the re-reaction effluent using the thermal high-pressure separator.

4. The method according to claim 1, comprising the following steps: The re-reaction effluent is fed into a plurality of separators arranged in sequence for separating byproducts, recovering n-chain hydrocarbons, and obtaining hydrogenated products; The normal-chain hydrocarbons used for the recovery of the diluent are reinjected into the diluent source; and The hydrogenated product is fed into one or more distillation columns and adsorption units to purify the hydrogenated product to obtain one or more purified hydrocarbon products.

5. The method according to claim 1, wherein the renewable raw material is animal oil, vegetable oil, or a combination of one or more animal oils and one or more vegetable oils.

6. The method according to claim 1, wherein the renewable raw material is tallow, whale oil, fish oil, bleached palm oil (BPO), refined bleached and deodorized palm oil (RBDPO), palm oil extract, palm stearin, palm fatty acid distillate, canola oil, corn oil, sunflower oil, soybean oil, jatropha oil, Roche oak oil, rapeseed oil, tall oil, hemp seed oil, olive oil, flaxseed oil, mustard oil, peanut oil, castor oil, coconut oil, or any combination of two or more oils.

7. The method according to claim 1, wherein the renewable raw material is fresh oil, used oil, waste oil, or any combination thereof.

8. The method according to claim 1, wherein the diluent is 70-100% by weight of n-decane (C 10 ), n-Undecane (C 11 ), n-Dodecane (C 12 ), n-Tetane (C 13 ), n-Tetradecane (C 14 ), or mixtures thereof.

9. The method of claim 1, wherein the ratio of the diluent to the renewable raw material is from 99% by weight diluent / 1% by weight raw material to 50% by weight diluent / 50% by weight raw material.

10. The method of claim 1, wherein the ratio of hydrogen to the volume of the catalyst bed in the reactor is between 3 and 900 Nm. 3 / m 3 Within the range, and / or the ratio of hydrogen to the renewable feedstock is between 10 and 700 Nm. 3 / m 3 The range is from 0.001 to 0.054 g / g.

11. The method of claim 1, wherein the catalyst comprises at least one selected from two transition metals, Ni and Mo.

12. The method of claim 11, wherein the catalyst further comprises another transition metal or a group V element, and / or the catalyst is supported on a support.

13. The method according to claim 12, wherein the support is an acidic porous solid support selected from alumina (Al2O3), silicon dioxide (SiO2), and a mixture of alumina and silicon dioxide (Al2O3-SiO2).

14. The method according to claim 13, wherein the carrier is fluorinated alumina, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-32, ZSM-35, ZSM-38, ZSM-48, ZSM-57, SAPO-11, SAPO-31, SAPO-41, MAPO-11, MAPO-31, zeolite Y, zeolite L, or β-zeolite.

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