RU2818169C1 - Method and system for hydrotreating renewable raw materials - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention provides a method of producing one or more hydrocarbon products from renewable raw materials containing triglycerides, free fatty acids or combinations thereof. Method may include steps of mixing renewable material with a diluent to form diluted material; supplying or providing the supply of hydrogen gas to the diluted feedstock, due to which hydrogen gas can be dissolved in the diluted feedstock to form a diluted feedstock enriched with dissolved hydrogen; and feeding the diluted feedstock enriched with dissolved hydrogen into at least one reactor having at least a reaction zone comprising at least a catalyst bed, under preset conditions with formation as a result of output stream of reaction, which can be further processed with formation of one or more hydrocarbon products.

EFFECT: obtaining desired hydrocarbon products, including bio-naphtha, an industrial solvent, and materials with a variable phase state with high purity of n-paraffin.

14 cl, 9 ex, 14 tbl, 2 dwg

Description

Field of technology to which the invention relates

[0001] The present invention relates to a method and system for hydrotreating renewable feedstocks, in particular renewable feedstocks containing triglycerides, free fatty acids or combinations thereof.

BACKGROUND OF THE INVENTION

[0002] The following discussion of the prior art of the invention is intended to facilitate understanding of the present invention. It should be understood, however, that this discussion is not an endorsement or assumption that any material referred to was published, known, or part of common knowledge in any jurisdiction as of the priority date of the application.

[0003] Hydroprocessing generally refers to two separate processes, i.e. to hydrotreating and hydrocracking. Hydrotreating is a process that uses hydrogen gas or hydrogen-containing gas and a suitable catalyst or catalysts to break down complex petroleum molecules into smaller hydrocarbon molecules. Typically, the hydrotreating process is a three-phase process carried out in a trickle-bed reactor, which is configured in such a way that the selected renewable feedstock (such as animal oils, animal fats or vegetable oils) is in contact with a suitable catalyst or catalyst charged to the reactor , at elevated temperature and pressure and in the presence of hydrogen gas (which is continuously fed into the reactor).

[0004] In a reactor, when hydrogen gas is in contact with a renewable feedstock, the hydrogen gas will dissolve in the renewable feedstock under certain conditions (for example, at a temperature in the range of about 200°C to about 400°C and a pressure in the range of about 20 bar (2 MPa) to about 50 bar (5 MPa)) before any reaction can occur. However, the low solubility of hydrogen gas in renewable feedstocks places a limitation on the hydrotreating process, favoring a scenario in which insufficient hydrogen exists to react with the renewable feedstock.

[0005] To partially overcome the above limitation, the conventional hydrotreating process requires a large excess of hydrogen gas feed, which also results in a large amount of unused hydrogen gas leaving the reactor along with the product stream. Although unused hydrogen gas can be recovered and reused by reintroduction into the reactor, it must be compressed using a compressor to increase its pressure to a value at least equivalent to the reactor pressure, which increases the operating costs of the hydrotreating process.

[0006] In light of the above, there is a need to develop a hydrotreating process that overcomes at least one of the above disadvantages. There is also a need to develop a process for hydrotreating renewable feedstocks to produce desired hydrocarbon products, including bionaphtha, industrial solvent and high purity n-paraffin phase change materials.

The essence of the invention

[0007] One aspect of the present invention is the production of hydrotreated oil that can be further processed to form hydrocarbon products suitable for use in internal combustion engines, auto parts, construction, and other applications.

[0008] Another aspect of the present invention is to obtain hydrotreated oil from a hydrotreating process without using a petrochemical source as a starting material or raw material.

[0009] Another aspect of the invention is the production of high purity hydrotreated oil or the production of hydrotreated oil that can be further processed to form high purity hydrocarbon products.

[0010] Another aspect of the invention is to provide a process for hydrotreating feedstocks containing triglycerides, free fatty acids, or combinations thereof, without the presence of a large excess of hydrogen gas.

[0011] According to one aspect of the present invention, there is provided a method of producing one or more hydrocarbon products from a renewable feedstock containing 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 dilute feedstock with hydrogen gas and a sulfilating agent, causing the hydrogen gas to dissolve in the dilute feedstock to form a dilute feedstock enriched with dissolved hydrogen; directing the dilute feedstock enriched in dissolved hydrogen into a reactor containing a catalyst bed to form a reaction effluent stream enriched in dissolved hydrogen; further contacting the reaction effluent stream with hydrogen gas and a sulfilating agent, whereby the hydrogen gas dissolves in the reaction effluent stream to form a reaction effluent stream enriched in dissolved hydrogen; further directing the reaction effluent stream enriched in dissolved hydrogen to at least an additional reactor containing a catalyst bed, resulting in an additional reaction effluent stream that can be further processed to form one or more hydrocarbon products; and in which the volume fraction of undissolved hydrogen gas in the reactor is no more than 0.1-0.25.

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

[0013] In some embodiments, the method also includes the step of separating gaseous byproducts from the reaction effluent stream or from an additional reaction effluent stream using a high pressure hot separator.

[0014] In some embodiments, the dilution step and the contacting step can be performed simultaneously.

[0015] In some embodiments, the method also includes the step of recovering diluent from the reaction effluent stream or additional reaction effluent stream and reintroducing the recovered diluent to the diluent source.

[0016] In some embodiments, the method further comprises the steps of supplying the reaction effluent stream or additional reaction effluent stream to separators that are arranged in series to separate by-products from the reaction effluent stream or from the additional reaction effluent stream and to recover diluent from the reaction effluent stream or from the additional reaction effluent, resulting in a hydrotreated product; and feeding the hydrotreated product to one or more distillation columns and adsorption units to purify the hydrotreated product to obtain one or more purified hydrocarbon products.

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

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

[0019] In some embodiments, the renewable feedstock is tall oil, whale oil, fish oil, bleached palm oil (BPO), refined bleached deodorized palm oil (RBDP0), palm olein, palm stearin, palm fatty acid distillate, canola oil, corn oil, sunflower oil, soybean oil, jatropha oil, balanite oil, canola oil, tall oil, hemp oil, olive oil, flaxseed oil, mustard oil, peanut oil, castor oil, coconut oil or a combination of any two or more oils.

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

[0021] In some embodiments, the diluent contains n-paraffin.

[0022] In some embodiments, the diluent contains n-paraffin containing 12 carbon atoms.

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

[0024] In some embodiments, the ratio of hydrogen gas to volume of the catalyst bed in the reactor is in the range of 3-900 normal ^{m 3} /m ³ .

[0025] In some embodiments, the ratio of hydrogen gas to renewable feedstock ranges from about 10 normal ^{m 3} /m ³ to about 700 normal m ³ /m ³ (from about 0.001 g/g to about 0.054 g/g ).

[0026] In some embodiments, the catalyst is selected from the group consisting of NiMo, CoMo, NiCoMo and NiW.

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

[0028] In some embodiments, the catalyst further comprises another transition metal or Group V element.

[0029] In some embodiments, the catalyst is supported on a support.

[0030] In some embodiments, the support is an acidic porous solid support selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), silica (SiO ₂ ), and a mixture of alumina and silica (Al ₂ O ₃ -SiO ₂ ).

[0031] In some embodiments, the carrier is alumina fluoride, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-32, ZSM-35, ZSM-38, ZSM-48, ZSM-57, SAP0-11, SAPO-31, SAPO-41, MARO-11, MARO-31, Y zeolite, L zeolite or β-zeolite.

[0032] In some embodiments, a system is provided for producing one or more hydrocarbon products from renewable feedstocks containing triglycerides, free fatty acids, or combinations thereof, the system comprising a reactor comprising a catalyst bed; the reactor is designed to react a dilute feedstock enriched in dissolved hydrogen to form an effluent reaction stream that can be further processed to form one or more hydrocarbon products; dilute feedstock enriched with dissolved hydrogen is produced by diluting renewable feedstock containing triglycerides, free fatty acids or combinations thereof with a diluent to form a dilute feedstock, then adding a sulfilating agent and passing hydrogen gas through the dilute feedstock, causing the hydrogen gas to dissolve in the dilute feedstock raw materials with the formation of diluted raw materials enriched with dissolved hydrogen; further comprises at least an additional reactor containing layers of catalyst for further contacting the reaction effluent stream with hydrogen gas and a sulfilating agent to form a reaction effluent stream enriched in dissolved hydrogen, wherein the additional reactor is configured to react the effluent stream enriched in dissolved hydrogen to form an additional reaction effluent that can be further processed to form one or more hydrocarbon products; and the volume fraction of undissolved hydrogen gas in the reactor is no more than 0.1-0.25.

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

[0034] In some embodiments, a high-pressure hot separator is located after each reactor or additional reactor to separate gaseous by-products from the reaction effluent stream or additional reaction effluent stream.

[0035] In some embodiment, the system further comprises one or more separators that are arranged in series to separate by-products from the reaction effluent stream or from the additional reaction effluent stream and to recover diluent from the reaction effluent stream or from the additional reaction effluent stream, to obtain as a result of a hydrotreated product; and one or more distillation columns and adsorption units for purifying the hydrotreated product to obtain one or more purified hydrocarbon products.

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

[0037] In some embodiments, 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 embodiments, the renewable feedstock used in the system is tall oil, whale oil, fish oil, bleached palm oil (BPO), refined bleached deodorized palm oil (RBDPO), palm olein, palm stearin, palm fat distillate acids, canola oil, corn oil, sunflower oil, soybean oil, jatropha oil, balanite oil, canola oil, tall oil, hemp oil, olive oil, linseed oil, mustard oil, peanut oil, castor oil, coconut oil or a combination of any two or more oils.

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

[0040] In some embodiments, the diluent used in the system contains n-paraffin.

[0041] In some embodiments, the diluent used in the system contains n-paraffin containing 12 carbon atoms.

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

[0043] In some embodiments, the ratio of hydrogen gas to catalyst bed volume in the reactor used in the system is in the range of 3-900 normal ^{m 3} /m ³ .

[0044] In some embodiments, the ratio of hydrogen gas to renewable feedstock used in the system ranges from about 10 normal ^{m 3} /m ³ to about 700 normal ^{m 3} /m ³ (from about 0.001 g/g to approximately 0.054 g/g).

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

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

[0047] In some embodiments, the catalyst used in the system further comprises another transition metal or Group V element.

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

[0049] In some embodiments, the catalyst support used in the system is an acidic porous solid support selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), silica (SiO ₂ ), and a mixture of alumina and silica (Al ₂ O ₃ -SiO ₂ ).

[0050] In some embodiments, the catalyst support used in the system is alumina, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-32, ZSM-35, ZSM-38, ZSM- 48, ZSM-57, SAPO-11, SAPO-31, SAP0-41, MARO-11, MARO-31, Y zeolite, L zeolite or β-zeolite.

Brief description of drawings

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

[0052] Figure 1 is a schematic diagram illustrating a method for hydrotreating feedstocks containing triglycerides, free fatty acids, or combinations thereof, in accordance with one embodiment of the invention; And

[0053] FIG. 2 is a schematic diagram illustrating a process for hydrotreating feedstocks containing triglycerides, free fatty acids, or combinations thereof to produce products including phase change materials and industrial solvents, in accordance with one embodiment of the invention.

Detailed description

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

[0055] As used herein, the term “phase change material (PCM)” refers to a straight chain hydrocarbon compound containing substantially n-paraffin having 16 carbon atoms, 17 carbon atoms and 18 carbon atoms.

[0056] As used herein, the term is “substantially free,” “substantially free,” or a similar term, when used in the context of a byproduct (e.g., sulfur, olefins, aromatics, alcohols, or combinations thereof) in the compound ( e.g., hydrotreated product stream or phase change material) refers to an amount of less than 100 ppm by weight (ppmw), less than 50 wppm, less than 20 wppm, less than 10 wt. ppm, less than 5 ppm by weight or less than 1 ppm by weight in this compound.

[0057] Throughout the specification, unless the context otherwise requires, the word “comprise”, or variations thereof such as “comprises” or “comprising”, will be understood to imply the inclusion of the specified integer or group of integers, but not as the exclusion of any another integer or group of integers.

[0058] Throughout the specification, unless the context otherwise requires, the word “include,” or variations thereof such as “includes” or “including,” will be understood to imply the inclusion of the specified integer or group of integers, but not as the exclusion of any another integer or group of integers.

[0059] As used herein, the term “about” typically means +/- 5% of the specified value, more typically +/- 4% of the specified value, more typically +/- 3% of the specified value, more typically +/- 2 % of the specified value, even more typically +/- 1% of the specified value, and even more typically +/-0.5% of the specified value.

[0060] In the present description, some embodiments may be described in range format. It should be noted that the description in range format is provided for convenience and brevity only and should not be construed as a limitation on the scope of the ranges described. Accordingly, the description of a range should be considered to include all possible subranges, as well as the individual numerical values within that range. For example, a description of a range such as 1-6 should be considered to include specifically described sub-ranges such as 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, etc. , as well as individual numbers within that range, such as 1, 2, 3, 4, 5, and 6. Ranges are not limited to whole numbers and can include decimal values. This applies regardless of the band width.

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

[0062] The present invention provides a two-phase hydrotreating method, which is different from the traditional three-phase hydrotreating method. Specifically, a two-phase hydrotreating process includes at least a liquid phase renewable feedstock and a solid catalyst (or catalysts in some embodiments), wherein the liquid phase renewable feedstock is a continuous phase in the reactor. More specifically, the two-phase hydrotreating process involves at least: mixing the renewable feedstock with a diluent to form a dilute feedstock; adding a sulfilating agent to the diluted raw material; supplying or causing hydrogen gas to be supplied to the dilute feedstock, whereby the hydrogen gas can be dissolved in the dilute feedstock to form a dilute feedstock enriched with dissolved hydrogen; and supplying the diluted feed enriched in dissolved hydrogen to at least a reactor having at least a reaction zone containing at least a catalyst bed under predetermined conditions (eg, conditions favorable to hydrogenation), resulting in a reaction effluent stream , which are hydrocarbon compounds containing mainly n-paraffin. This reaction effluent stream may also be further processed (eg, 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 is understood that the reaction effluent from an upstream reactor (e.g., a second reactor) may be contacted with hydrogen gas and a sulfilating agent before being fed to a subsequent reactor (e.g., a third reactor) , whereby hydrogen gas can be dissolved in the reaction effluent to replenish the reacted hydrogen in the hydrotreating process, and the efficiency of the catalyst can be maintained.

[0063] In some embodiments, the renewable feedstock to be hydrotreated in the present invention may be any plant or animal oils, fats, free fatty acids, and the like. In particular, the renewable feedstock can be any oils, such as oils containing triglycerides or free fatty acids, where the main component contains aliphatic hydrocarbon chains having C ₁₂ -C ₂ o components.

[0064] In some preferred embodiments, the renewable feedstock may be an oil derived from plants and/or animals, and it may contain one or more triglycerides. Renewable feedstock may also contain a mixture of triglycerides. The renewable feedstock containing one or more triglycerides may be obtained from a plant selected from the group consisting of pine seeds, rapeseed, sunflower, jatropha, marina mallow and combinations of any two or more of these. The renewable feedstock containing one or more triglycerides may also be derived from a vegetable oil selected from the group consisting of canola oil, palm oil, coconut oil, palm kernel oil, sunflower oil, soybean oil, crude tall oil, and combinations of any two or more of them. Renewable feedstocks containing one or more triglycerides may also contain poultry fat, yellow fat, tallow, post-consumer vegetable oils or oils derived from biomass pyrolysis. Renewable feedstocks can also be seafood oils such as algal oils.

[0065] In some other preferred embodiments, the renewable feedstock may contain triglycerides, free fatty acids, or combinations thereof. Renewable raw materials may be oils of plant origin, oils of animal origin, or combinations thereof, where the oils may contain a main component comprising aliphatic hydrocarbon chains having C ₁₂ -C ₁₈ carbon atoms. Renewable feedstocks containing triglycerides, free fatty acids or combinations thereof may include, but are not limited to, animal oils such as tall oil, whale oil and fish oil; vegetable oils such as bleached palm oil (BPO), refined bleached deodorized palm oil (RBDPO), palm olein, palm stearin, palm fatty acid distillate, canola oil, corn oil, sunflower oil, soybean oil, desert plant oils (eg , jatropha oil and balanite oil), rapeseed oil, tall oil, hemp oil, olive oil, linseed oil, mustard oil, peanut oil, castor oil, coconut oil; or a combination of any two or more of them. The vegetable oils in the present invention may also be vegetable oils, which may be crude, refined or edible vegetable oils. In some embodiments, the renewable feedstock may be fresh oil, used oil, waste oil, or any combination thereof. In addition, the choice of renewable feedstock may depend on availability and cost, making the two-stage hydrotreating process flexible.

[0066] As mentioned in the description above, the present invention requires that a diluent be supplied or provided for mixing with the renewable feedstock to form a diluent feedstock. The formation of a dilute feed promotes the dissolution of hydrogen gas in the dilute feed before entering the reactor. The formation of a dilute feed also eliminates the need to feed a large excess of hydrogen gas into the reactor, since the hydrogen gas required for the hydrotreating process is present in the dilute feed as dissolved hydrogen.

[0067] In some embodiments, although hydrogen gas may be dissolved in the dilute feed before entering the reactor, the solubility of hydrogen in the dilute feed may remain low, as shown in Table 1. Accordingly, this may affect the efficiency of the hydrotreating process because the amount of hydrogen available for the hydrotreating process may be limited and insufficient.

[0068] To overcome this situation, the present invention may use more than one reactor, where each reactor may contain at least a reaction zone containing at least a catalyst bed. In particular, after receiving the reaction effluent from an upstream reactor (eg, the first reactor), it may be necessary to contact such effluent from the first reactor with hydrogen gas before feeding it to the downstream reactor (ie, the second reactor) to replenishment of reacted hydrogen during the hydrotreating process. Accordingly, this ensures that sufficient hydrogen is available throughout the hydrotreating process.

[0069] It should be understood that in some embodiments of the invention, the number of reactors may be determined based on the composition and amount of the renewable feedstock to be hydrotreated, as well as the diluent. The number of reactors can also be determined by the temperature and pressure required for the hydrotreating process. After determining these factors, the amount of hydrogen gas required to contact the dilute feedstock or reaction effluent, the ratio of hydrogen gas to renewable feedstock, the number of times required to add hydrogen gas to the reaction effluent, etc. can be determined accordingly .

[0070] In some embodiments, a two-phase hydrotreating process involves three main reactions, which include hydrogenation of fatty acid alkyl chain double bonds, decarboxylation and decarbonylation, and hydrogenation to form alkanes. As a result, a two-phase hydrotreating process can produce products including, but not limited to, n-aliphatic hydrocarbons of the corresponding fatty acids and propane from triglyceride molecules, and by-products including, but not limited to, carbon monoxide and carbon dioxide (due to the oxygen content of the triglycerides ) and water, which can be in the form of steam. Removing water from reactors is extremely important because the presence of water can affect the life of the catalyst and the solubility of hydrogen in renewable feedstocks.

[0071] In addition to the reactors, the two-phase hydrotreating process may also include at least one separator for removing generated byproducts from the target hydrotreated products. This differs from the traditional hydrotreating process, which requires heat exchangers, separators, and flash vessels to be provided downstream of each reactor to remove unwanted heat and byproducts, including water, from the hydrotreated product stream from each reactor.

[0072] In another preferred embodiment, the separator used in the two-phase hydrotreating process may be a high pressure hot separator (HHPS). The HHPS may be located at the outlet of the reactor to separate unwanted gaseous by-products from the reaction effluent stream obtained from the reactor before contacting the hydrotreated product stream with hydrogen gas. In some embodiments, the gaseous by-products to be separated from the reaction effluent stream may contain steam, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H ₂ S), a small amount of hydrogen gas, and a small amount of hydrotreated product gases.

[0073] In some other embodiments, the method of the present invention may further involve selecting a suitable catalyst. The catalyst may be selected from the group consisting of NiMo, CoMo, NiCoMo and NiW. In some embodiments, the catalyst may contain at least one of two transition metals selected from the group consisting of Ni and Mo. In some embodiments, the catalyst may further comprise another transition metal or group V element.

[0074] Before use, the catalyst may also be activated by a sulfidation process, which may be accomplished by loading the catalyst into a reaction zone and reacting the metal oxides with hydrogen sulfide (H ₂ S) in the presence of hydrogen at a temperature of from about 150° C. to about 400° C. C and pressures from about 1 bar to about 50 bar (0.1-5 MPa). The sulfilating agent may be selected from the group consisting of carbon disulfide, dicarbon disulfide, and a paraffin compound (CS-40) having at least one thiol, sulfide, or disulfide functional group. In some embodiments, the amount of sulfur in the sulfurizing agent used in activating the catalyst may be from about 0.10 wt% to 5 wt%, or about twice the amount required to convert the metal oxide to metal sulfide. In another aspect, the catalyst content can range 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 gas.

[0075] In some embodiments, the catalyst may be supported on a support. In some preferred embodiment, the support to which the catalyst is to be supported may be an acidic porous solid support such as aluminum oxide (Al ₂ O ₃ ), silica (SiO ₂ ), or a mixture of alumina and silica (Al ₂ O ₃ -SiO ₂ ). In some other preferred embodiments, the carrier on which the catalyst is to be loaded may be alumina, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-32, ZSM-35, ZSM-38, ZSM-48, ZSM-57, SAP0-11, SAPO-31, SAPO-41, MARO-11, MARO-31, Y zeolite, L zeolite or β-zeolite. By passing a dilute feedstock enriched in dissolved hydrogen through a supported catalyst, hydrogenation of the olefinic or unsaturated portions of the n-paraffin chains of the renewable feedstock can occur. In addition, since the support can act as a high surface area support for the catalyst, higher catalyst efficiency can be achieved. Accordingly, reactions such as hydrogenation, deoxygenation and isomerization can proceed with greater efficiency because the catalyst is better dispersed.

[0076] In some embodiments, the controlled rate of hydrogen gas added to at least one catalyst bed is determined to maximize the amount of hydrogen available for hydrogenation in all reaction zones and for all feedstocks, and to minimize or eliminate the amount hydrogen that exceeds the solubility limit. The ratio of hydrogen gas to catalyst bed volume can be in the range of 3, 20, 40, 50, 100, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800 or 900 normal m ³ /m ³ . The feedstock may range from about 10 to about 700 normal ^{m 3} /m ³ (from about 0.001 to about 0.054 g/g), from 10 to about 650 normal ^{m 3} /m ³ (from about 0.001 to about 0.050 g /g), from about 10 to about 600 normal ^{m 3} /m ³ (from about 0.001 to about 0.047 g/g), from about 10 to about 550 normal ^{m 3} /m ³ (from about 0.001 to about 0.044 g /g), from about 10 to about 500 normal ^{m 3} /m ³ (from about 0.001 to about 0.039 g/g), from about 10 to about 450 normal ^{m 3} /m ³ (from about 0.001 to about 0.035 g /g), from about 10 to about 400 normal ^{m 3} /m ³ (from about 0.001 to about 0.032 g/g), from about 10 to about 380 normal ^{m 3} /m ³ (from about 0.001 to about 0.030 g/g), from about 10 to about 350 normal ^{m 3} /m ³ (from about 0.001 to about 0.028 g/g), or from about 10 to about 320 normal ^{m 3} /m ³ (from about 0.001 to about 0.025 y/y). In some embodiments, it may be advantageous to provide a process for hydrotreating renewable feedstock 201 containing triglycerides, free fatty acids, or combinations thereof, illustrated in FIG. 1. In particular, the renewable feedstock to be hydrotreated may be animal oil or vegetable oil. The renewable feedstock to be hydrotreated may also be a combination of one or more animal oils and one or more vegetable oils. For example, the renewable feedstock to be hydrotreated may be tall oil, whale oil, fish oil, bleached palm oil (BPO), refined bleached deodorized palm oil (RBDPO), palm olein, palm stearin, palm fatty acid distillate, canola oil, corn oil , sunflower oil, soybean oil, jatropha oil, balanite oil, canola oil, tall oil, hemp oil, olive oil, flaxseed oil, mustard oil, peanut oil, castor oil, coconut oil or a combination of any two or more oils. In some embodiments, the renewable feedstock to be hydrotreated may be fresh oil, used oil, used oil, or any combination thereof.

[0077] As illustrated in FIG. 1, it may be preferable, prior to hydrotreating the renewable feedstock 201, for diluent 202 to be added to the renewable feedstock 201 to form a diluted feedstock 203. The diluent 202 added to the renewable feedstock 201 may be a fresh feed of n- paraffin, a portion of n-paraffin recovered from the process of this invention and reintroduced into the diluent feed stream or diluent source, or combinations thereof. In some preferred embodiments, this diluent 202 may contain n-paraffin having C ₁₀ -C ₂₀ carbon atoms. In particular, n-paraffin having C ₁₂ carbon atoms. The diluent composition can be in the range of 70-100 wt%. n-decane (C ₁₀ ), n-undecane (C ₁₁ ), n-dodecane (C ₁₂ ), n-tridecane (C ₁₃ ), n-tetradecane (C ₁₄ ) or mixtures thereof. The rest of the composition is a heavier fraction of n-paraffin. 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 (3.5 MPa) and also has a hydrogen solubility of at least 0.5 wt%, 1.0 wt%. , 2.0% wt. or 3% wt. under hydrotreating reaction conditions, which will be described below. In addition, if diluent 202 is a portion of n-wax recovered from the process of the present invention and reintroduced into the diluent feed stream or diluent source, it may be necessary to ensure that the relative volatility between diluent 202 and the light key components in the n- paraffin effluent was equivalent to or greater than 1.1.

[0078] It is further understood that in certain embodiments, the ratio of diluent 202 to renewable feedstock 201 (added to renewable feedstock 201) can range from about 99 wt% diluent/1 wt% feedstock to about 95 wt% feedstock. diluent/5% wt. raw materials, from about 95% by weight, diluent/5% by weight, raw materials to about 90% by weight. diluent/10% wt. raw materials, from approximately 80% by weight, diluent/20% by weight. raw materials to approximately 70% by weight, diluent/30% by weight. raw materials or from about 60% by weight, diluent/40% by weight. raw materials to approximately 50% wt, diluent/50% wt. raw materials. It should also be noted that in some embodiments, the raw material 201 and the diluent 202 may be mixed together at ambient temperature and atmospheric pressure, allowing the diluted raw material 203 to be prepared in advance and stored in storage.

[0079] Thereafter, the dilute feed 203 can be contacted with a sulfilating agent 235 and then with hydrogen gas 204, whereby a desired amount of hydrogen gas can be dissolved in the dilute feed 203 to obtain a dilute feed 205 enriched in dissolved hydrogen, and the effectiveness of the catalyst in the catalyst bed may persist. Hydrogen gas may be present in an amount capable of being dissolved in the feedstock, or present in excess. Undissolved hydrogen gas can form a gas phase in the reaction zone. The desired amount of hydrogen gas should then be sufficient for the reaction or reactions in the reaction zone (depending on the volume of feedstock required for the reaction in the reaction zone) and/or not produce too much gas phase. In particular, the gas phase arising at this stage will have a gas volume fraction (GVF) of from about 0.1 to about 0.25. The desired amount of sulfurizing agent to produce sulfur in an amount of 0-10,000 ppmw is preferably comparable to the volume of feed in the liquid stream. The operation or step of producing the dilute feedstock 205 enriched in dissolved hydrogen can be carried out in any suitable apparatus known in the art. However, to ensure the dissolution of hydrogen gas in the dilute feed 203, it must be carried out at a temperature of from about 200°C to about 400°C, from about 250°C to about 320°C, or from about 250°C to about 360°C , and at a pressure of from about 20 bar to about 100 bar (2-10 MPa), from about 25 bar to about 100 bar (2.5-10 MPa) or from about 30 bar to about 100 bar (3-10 MPa) . In some preferred embodiments, the ratio of hydrogen gas 204 (supplied to dilute feed 203) to dilute feed 203 may be from about 0.00046 to about 0.00233 g/g.

[0080] In some embodiments, the step of adding sulfylating agent 235 may be performed prior to the reaction step in the reaction zones. For example, the sulfylating agent 235 may be added to the renewable feed 201 during mixing with the diluent, or to the dilute feed before contact with hydrogen gas, or to the dilute feed 205 enriched with dissolved hydrogen before introduction into the reactor.

[0081] In some alternative embodiments, the diluted dissolved hydrogen-enriched feedstock 205 may be produced in a one-step operation, instead of a two-step operation as described in the description above. Specifically, the dilute feedstock 205 enriched with dissolved hydrogen can be produced by supplying the renewable feedstock 201, the diluent 202, and hydrogen gas 204 simultaneously. The ratio of diluent 202 to renewable feed 201 may range from about 99 wt% diluent/1 wt% feed to about 95 wt% diluent/5 wt% feed, from about 95 wt% diluent/5 wt% feed to about 90 wt% diluent/10 wt% feedstock, about 80 wt% diluent/20 wt% feedstock to about 70 wt% diluent/30 wt% feedstock or about 60 wt% diluent/40% wt. wt% feedstock to about 50 wt% diluent/50 wt% feedstock, while the ratio of hydrogen gas 204 to renewable feedstock 202 can be from about 10 to about 700 normal ^{m 3} /m ³ (from about 0.001 to about 0.054 g /g or from about 0.1% by weight, to about 5.4% by weight), from about 10 to about 650 normal ^{m 3} /m ³ (from about 0.001 to about 0.050 g/g or from about 0.1% by weight, up to about 5% by weight), from about 10 to about 600 normal ^{m 3} /m ³ (from about 0.001 to about 0.047 g/g or from about 0.1% by weight to about 4.7% by weight), from about 10 to about 550 normal m ³ /m ³ (from about 0.001 to about 0.044 g/g or from about 0.1% by weight to about 4.4% by weight), from about 10 to about 500 normal m ³ /m ³ (from about 0.001 to about 0.039 g/g or from about 0.1% by weight, to about 3.9% by weight), from about 10 to about 450 normal m ³ /m ³ (from about 0.001 to about 0.035 g/g or about 0.1 wt% to about 3.5 wt%), about 10 to about 400 normal ^{m 3} /m ³ (about 0.001 to about 0.032 g/g or from about 0.1% by weight, to about 3.2% by weight), from about 10 to about 380 normal m ³ /m ³ (from about 0.001 to about 0.030 g/g or from about 0.1% by weight, to about 3.0% by weight), from about 10 to about 350 normal ^{m 3} /m ³ (from about 0.001 to about 0.028 g/g or from about 0.1% by weight. to about 2.8% by weight) or from about 10 to about 320 normal ^{m 3} /m ³ (from about 0.001 to about 0.025 g/g or from about 0.1% by weight to about 2.5% mass).

[0082] In some embodiments, the selection of the ratio of hydrogen to renewable feedstock for continuous liquid phase hydrotreating depends primarily on the type of renewable feedstock. For example, in the case of RBDPO, the ratio of hydrogen to renewable feedstock is at least about 450 Nm 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 normal ^{m 3} /m ³ (at least 0.025 g/g or about 2.5% by weight). For refined soybean oil, the ratio of hydrogen to renewable feedstock is at least about 550 normal ^{m 3} /m ³ (at least 0.044 g/g) or at least 510 normal ^{m 3} /m ³ (at least 0.040 g /g or about 4.0% by weight) or at least 385 normal ^{m 3} /m ³ (at least 0.035 g/g or about 3.5% by weight). Each type of renewable feedstock uses a different amount of hydrogen to produce processed oil due to the chain length of its triglycerides and fatty acids and the degree of unsaturation. In particular, the hydrotreating of triglycerides containing shorter chain fatty acids and/or having a higher degree of unsaturation requires more hydrogen gas.

However, if a one-step operation is performed to prepare diluted feedstock 205 enriched with dissolved hydrogen, it will be understood that the one-step operation must be performed at a temperature of from about 200° C. to about 400° C., from about 250° C. to about 320° C., or from about 250°C to about 360°C, and at a pressure of from about 20 bar to about 100 bar (2-10 MPa), from about 25 bar to about 100 bar (2.5-10 MPa) or from about 30 bar to about 100 bar (3-10 MPa). Accordingly, it would be impractical to prepare diluted feedstock 205 enriched with dissolved hydrogen in advance and store it in storage.

[0083] Once the diluted feedstock 205, enriched in dissolved hydrogen, is obtained, it may then be fed to a first reactor 20 having at least a reaction zone containing at least a catalyst bed (which contains at least an activated hydrotreating catalyst). For ease of description, the following embodiments will be described in relation to a reactor having a catalyst reaction zone, however, it should be understood that the number of reaction zones in the reactor need not be limited by or because of this.

[0084] In particular, the diluted feed 205 enriched in dissolved hydrogen may be supplied to the first reactor 20, in which the diluted feed 205 enriched in dissolved hydrogen can be passed through a first catalyst bed containing an activated hydrotreating catalyst. When the dissolved hydrogen rich dilute feed 205 is in contact with an activated hydrotreating catalyst, the olefinic or unsaturated portions of the n-paraffin chains in the dissolved hydrogen rich dilute feed 205 are hydrotreated. The reaction effluent from the first reactor 20 may be further sent to a first high pressure hot separator (HHPS) 228 to separate unwanted gaseous by-products. For example, steam, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H ₂ S), a small amount of hydrogen gas and a small amount of hydrotreated product gases. Accordingly, the unwanted gaseous by-products exit the first HHPS 228 as a waste stream 207, which will be sent to a waste treatment unit (not shown), while the separated reaction effluent exits the first HHPS 228 as a first effluent stream 206 containing hydrotreated oil, unreacted raw material, unreacted diluent, small amount of hydrogen, small amount of unwanted by-product.

[0085] Subsequently, the first effluent stream 206 may be contacted with a desired amount of hydrogen gas 208 and a desired amount of sulfilating agent 236 before being supplied to the second reactor 21. The step of contacting the first effluent stream 206 with hydrogen gas 208 and sulfilating agent 236 is extremely important, since it helps to provide sufficient hydrogen gas for the subsequent hydrotreating reaction, and the efficiency of the catalyst can be maintained.

[0086] After supplying the first dissolved hydrogen-rich effluent stream 209 to the second reactor 21, the first dissolved hydrogen-rich effluent stream 209 may pass through a second catalyst bed containing the activated hydrotreating catalyst. When the first dissolved hydrogen-rich effluent stream 209 is in contact with an activated hydrotreating catalyst, the olefinic or unsaturated portions of the n-paraffin chains in the first dissolved hydrogen-rich effluent stream 209 are hydrotreated. The reaction effluent from the second reactor 21 can then be sent to a second HHPS 229 to separate unwanted gaseous by-products. For example, steam, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H ₂ S), a small amount of hydrogen gas and a small amount of hydrotreated product gases. Accordingly, the unwanted gaseous by-products exit the second HHPS 229 as a waste stream 211, which will be sent to a waste treatment unit (not shown), while the separated reaction effluent exits the second HHPS 229 as a second effluent stream 210 containing hydrotreated oil, unreacted raw material, unreacted diluent, small amount of hydrogen, small amount of unwanted by-product.

[0087] Likewise, before introducing the second effluent stream 210 into the third reactor 22, it is important to contact the second effluent stream 210 with a desired amount of hydrogen gas 212 and a desired amount of sulfylating agent 237 to dissolve the hydrogen gas and sulfurizing agent in the second effluent stream 210. This is done to ensure the availability of sufficient hydrogen gas for the subsequent hydrotreating reaction and maintain catalyst efficiency. After supplying the second dissolved hydrogen-rich effluent stream 213 to the third reactor 22, the second dissolved hydrogen-rich effluent stream 213 may pass through a third catalyst bed containing the activated hydrotreating catalyst. When the second dissolved hydrogen-rich effluent stream 213 is in contact with the activated hydrotreating catalyst, the olefinic or unsaturated portions of the n-paraffin chains in the second dissolved hydrogen-rich effluent stream 213 are hydrotreated. The reaction effluent from the third reactor 22 may be further sent to a third HHPS 230 to separate unwanted gaseous by-products. For example, steam, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H ₂ S), a small amount of hydrogen gas and a small amount of hydrotreated product gases. Respectively,

unwanted gaseous by-products exit the third HHPS 229 as a waste stream 215 that will be sent to a waste treatment unit (not shown), while the separated reaction effluent exits the third HHPS 230 as a third effluent stream 214 containing hydrotreated oil , unreacted raw material, unreacted diluent, small amount of hydrogen, small amount of unwanted by-product.

[0088] In some embodiments, the hydrogen gas added to the second reactor and/or the third reactor may be present in an amount capable of being dissolved in the feedstock, or may be present in an excess amount. Undissolved hydrogen gas may form a gas phase in the reaction zone along with gaseous by-products such as carbon monoxide, carbon dioxide, propane, hydrogen sulfide. The desired amount of hydrogen gas in such a case should be sufficient for the reaction or reactions in the reaction zone (depending on the volume of feedstock required for the reaction in the reaction zone) and/or should not form too much of a gas phase. In particular, the gas phase arising at this stage will have a gas volume fraction (GVF) of from about 0.1 to about 0.25. The desired amount of sulfiding agent to produce sulfur in an amount of 0-10,000 ppmw is preferably comparable to the volume of feed in the liquid stream.

[0089] Subsequently, a portion or preferably all of the third effluent stream 214 may be subjected to one or more separations 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 be fed first to flash tank 23 for separating gaseous pollutants present in the third effluent stream 214. In particular, gaseous pollutants containing water vapor, carbon dioxide, carbon monoxide, propane, hydrogen sulfide (H ₂ S), a small amount of hydrogen gas and a small amount of hydrotreated gases products may exit as a first overhead stream 218, while the remaining liquid mixture may exit as a first bottoms stream 219 containing hydrotreated oil, diluent, and water to be fed to a second separator 24. In some embodiments, the second separator 24 may be a low pressure separator 24 for separating aqueous components from the first bottoms stream 219. While unwanted aqueous components (separated from the first bottoms stream 219) may exit the second separator 24 as a second bottoms stream 221, the remaining liquid mixture may exit to as a second stream 220. It should be noted that upon exiting the second separator 24, the second stream 220 is substantially free of gaseous contaminants and aqueous components.

[0090] The second stream 220 may be further fed to a third separator 25, which may preferably be a distillation column. The presence of the third separator allows diluent 216 to be recovered from second stream 220 such that the recovered diluent 216 can be reused by being reinjected into the diluent feed stream or diluent source (prior to contact with hydrogen gas 204). Additionally, after the diluent is removed from the second stream 220, the remaining liquid mixture may exit the third separator 25 as a hydrotreated product stream 222. In a preferred embodiment, the hydrotreated product stream 222 of this invention may be a hydrotreated oil phase containing predominantly a mixture of straight chain n-alkane hydrocarbon compounds. In particular, hydrotreated product stream 222 may be bionaphtha hydrocarbon compounds. The bionaphtha hydrocarbon compound composition may contain at least 90 wt% n-paraffin and 0-10 wt% isoparaffin, with paraffins generally falling in the C ₇ -C ₁₈ range.

[0091] The hydrotreated product stream 222 may be further processed to form phase change materials (PCMs), industrial solvents, or both. In a more preferred embodiment, hydrotreated product stream 222 may be a hydrotreated oil phase containing a low volume of isoparaffin and a high volume of n-paraffin. The isoparaffin present in the hydrotreated product stream 222 may be substantially free of sulfur, olefins and aromatics, making the isoparaffin non-toxic, preventing the formation of unwanted harmful products.

[0092] It should be understood that the present invention helps to minimize the loss of hydrogen gas during the hydrotreating process, for example, from reactors 20, 21, 22 and separators 23, 24, 25. The present invention also does not require supplying a large excess of hydrogen gas to each of the reactors, unlike traditional methods. This is because a diluent 202 containing mainly n-paraffin having 12 carbon atoms is added and mixed with the renewable feedstock 201 to form a dilute feedstock 203, which allows hydrogen gas to easily dissolve in the dilute feedstock 203. By eliminating the need supplying excess hydrogen gas to the reactors while allowing the loss of hydrogen gas to be minimized throughout the hydrotreating process, the present invention offers greater economic benefits compared to conventional processes.

[0093] In some embodiments, the hourly fluid velocity may be in the range of about 0.5-10.0 h ^-1 , about 0.5-20.0 h ^-1 , about 0.5-30.0 h ^-1 , approximately 0.5-40.0 h ^-1 , approximately 0.5-50.0 h ^-1 , approximately 0.5-60.0 h ^-1 , approximately 0.5-70.0 h ^-1 , approximately 0.5-80.0 h ^-1 , approximately 0.5-90.0 h ^-1 , approximately 0.5-100.0 h ^-1 .

[0094] It should also be understood that although the catalyzed reaction that occurs in reactors 20, 21, 22 is an exothermic reaction or a reaction that releases heat, additional steps to remove heat from reactors 20, 21, 22 are not required since the heat produced by the catalyzed reaction is not large due to the desired ratio between the renewable feedstock and the diluent, in which the diluent can absorb the heat generated by the reaction.

[0095] In additional embodiments, it may also be advantageous to provide a process for hydrotreating renewable feedstocks containing triglycerides, free fatty acids, or combinations thereof to produce products including phase change materials and industrial solvents.

[0096] As shown in FIG. 2, the hydrotreated product stream 222 resulting from the hydrotreating process illustrated in FIG. 1 can be used and further processed through additional distillations and adsorptions to form products including phase change materials (PCMs). ) and industrial solvents. Because hydrotreated product stream 222 is substantially free of sulfur, olefins, and aromatics, the PCMs resulting from further processing of hydrotreated product stream 222 may also be substantially free of sulfur, aromatics, and alcohols, as shown in Table 2.

[0097] In particular, the hydrotreated product stream 222 resulting from the hydrotreating process shown in FIG. 1 may be fed to the first distillation column 26, resulting in a fourth overhead stream 224 containing n-paraffin having less than 16 carbon atoms. , and a fourth bottoms stream 223, which may be fed to a second distillation column 28. In some embodiments, the fourth overhead stream 224 may pass through the first adsorption unit 27, resulting in a first fraction 225 containing the desired industrial solvent.

[0098] In the second distillation column 28, the components in the fourth bottoms stream 223 are separated to form a fifth overhead stream 227 containing at least about 99.0 wt% n-hexadecane and a fifth bottoms stream 22 6, which may be fed to a third distillation column 30. In some embodiments, the fifth overhead stream 227 may be passed through a second adsorption unit 2 9 to result in a second fraction 228 containing purified hexadecane, or referred to herein as PCM #1.

[0099] In the third distillation column 30, the components in the fifth bottoms stream 226 are separated to form a sixth overhead stream 230 containing at least about 99.0 wt% n-heptadecane and a sixth bottoms stream 229, which may be fed to the fourth distillation column. distillation column 31. In some embodiments, the sixth overhead stream 230 may pass through a third adsorption unit 31, resulting in a third fraction 231 containing purified heptadecane, or referred to herein as PCM #2.

[00100] In the fourth distillation column 32, the components in the sixth bottoms stream 229 are separated to form a seventh overhead stream 233 containing at least about 99.0 wt% n-octadecane and a seventh bottoms stream 232 that can be used in as a petroleum fuel (or bunker oil) suitable for applications such as, but not limited to, automotive engine fuel. In some embodiments, the seventh overhead stream 233 may be passed through a fourth adsorption unit 33 to result in a fourth fraction 234 containing purified octadecane, or referred to herein as PCM #3.

[00101] In some other embodiments, a single fractional distillation column may

be used to produce multiple products, including industrial solvent, PCM #1, PCM #2, and PCM #3, rather than using multiple distillation columns 26, 28, 30, 32. It should also be understood that the presence of adsorption units 27, 29, 31, 33 for processing overhead streams 224, 227, 230, 233 helps improve the quality of these streams by eliminating unwanted impurities or contaminants contained in them. For example, adsorption units 27, 29, 31, 33 may function to remove undesirable components such as, but not limited to, volatile organic compounds, substances that may impart an unpleasant odor or color to the industrial solvent and/or PCM. Removing these undesirable components can minimize or substantially eliminate undesirable characteristics such as unpleasant odor or undesirable color of the industrial solvent and/or PCM. In addition, the adsorption unit can be operated at atmospheric pressure, a temperature of from about 30°C to about 70°C, and at a space velocity of from about 0.5 h ^-1 to 2.0 h ^-1 . Although the operating temperature of the respective adsorption units can be selected according to the feed streams, it is not necessary to maintain the operating temperature of the adsorption units, resulting in simplified operation.

[00102] In some embodiments, the adsorption unit of the present invention may comprise at least one adsorption column, each adsorption column containing at least one adsorbent selected from the group consisting of activated carbon, basic ion exchange resin, acid ion exchange resin, molecular sieve, basic chemical adsorbent and acid chemical adsorbent. In some embodiments, the molecular sieve may have a pore size ranging from about 3A to about 15A. In some other embodiments, it is preferable to use a primary chemical adsorbent.

[00103] Examples

[00104] Example 1: Palm Oil Hydrotreating Process

[00105] A commercially available NiMo/Al ₂ O ₃ catalyst was loaded into a reactor and then activated into the sulfided form at a temperature of from about 150° C. to about 34 0° C. and a pressure of about 35 bar (3.5 MPa) for a period of time of about 2 4 hours in the presence of carbon disulfide as a sulfylating agent. The amount of sulfides in the sulfidation agent fed to the reactor was twice the amount of catalyst required for the sulfidation reaction based on chemical equilibrium.

[00106] Refined bleached deodorized palm oil (RBDP0) was used as a renewable feedstock and mixed with dodecane as a diluent to obtain a diluted feedstock at room temperature and atmospheric pressure using a suitable mixing device known in the art. The ratio of diluent to renewable feedstock was approximately 90:10 by weight. A sulfilating agent was added to the diluted feed and the diluted feed was then heated to a temperature of about 340° C. and compressed to a pressure of from about 50 bar to about 75 bar (5.0-7.5 MPa). Thereafter, excess hydrogen gas was passed through the dilute feed, wherein the desired amount of hydrogen gas was dissolved in the dilute feed, thereby forming a dilute feed enriched in dissolved hydrogen. The amount of hydrogen gas supplied during this stage was approximately 30% of the total amount of hydrogen gas supplied during the entire hydrotreating process.

[00107] The diluted feedstock, enriched in dissolved hydrogen, is then fed to a first reactor having at least a reaction zone containing a catalyst bed at an operating temperature of about 340° C. and an operating pressure of about 50 bar to about 75 bar (5.0 - 7.5 MPa) to hydrogenate the effluent stream of olefinic or unsaturated portions of the n-paraffin chains. The amount of hydrogen gas relative to the volume of the catalyst bed in the first reactor was approximately 600 normal ^{m 3} /m ³ . The reaction mixture was then passed through a first HHPS to separate steam and gaseous components therefrom, resulting in a first reaction effluent.

[00108] Before introducing the first reaction effluent stream into the second reactor, the first reaction effluent stream was brought into contact with the desired amount of hydrogen gas (which was heated to a temperature of about 340°C and compressed to a pressure of from about 50 bar to about 75 bar (5.0 -7.5 MPa)) and with the desired amount of sulfylating agent to form the first reaction effluent stream enriched in dissolved hydrogen. The amount of hydrogen gas supplied during this stage was approximately 17.5% of the total hydrogen gas supplied during the entire hydrotreating process.

[00109] The first reaction effluent stream, enriched in dissolved hydrogen, is then introduced into a second reactor having at least a reaction zone containing a catalyst bed at an operating temperature of about 340°C and an operating pressure of from about 50 bar to about 75 bar (5.0 -7.5 MPa) for additional hydrogenation of olefinic or unsaturated portions of the n-paraffin chains in the first reaction effluent. The amount of hydrogen gas relative to the volume of the catalyst bed in the second reactor was approximately 400 normal ^{m 3} /m ³ . The reaction mixture was then passed through a second HHPS to separate steam and gaseous components therefrom, resulting in a second reaction effluent.

[00110] Before introducing the second reaction effluent stream into the third reactor, the second reaction effluent stream was brought into contact with the desired amount of hydrogen gas (which was heated to a temperature of about 340°C and compressed to a pressure of from about 50 bar to about 75 bar (5.0 -7.5 MPa)) and with the desired amount of sulfilating agent to form a second reaction effluent stream enriched in dissolved hydrogen. The amount of hydrogen gas supplied during this stage was approximately 17.5% of the total hydrogen gas supplied during the entire hydrotreating process.

[00111] The second reaction effluent, enriched in dissolved hydrogen, is then introduced into a third reactor having at least a reaction zone containing a catalyst bed at an operating temperature of about 340°C and an operating pressure of from about 50 bar to about 75 bar (5.0 -7.5 MPa) for additional hydrogenation of olefinic or unsaturated portions of the n-paraffin chains in the second reaction effluent. The amount of hydrogen gas relative to the volume of the catalyst bed in the third reactor was approximately 400 normal ^{m 3} /m ³ . The reaction mixture was then passed through a third HHPS to separate steam and gaseous components therefrom, resulting in a third reaction effluent.

[00112] Before introducing the third reaction effluent stream into the fourth reactor, the third reaction effluent stream was brought into contact with the desired amount of hydrogen gas (which was heated to a temperature of about 340° C. and compressed to a pressure of from about 50 bar to about 75 bar (5.0 -7.5 MPa)) and with the desired amount of sulfilating agent to form a third reaction effluent stream enriched in dissolved hydrogen. The amount of hydrogen gas supplied during this stage was approximately 17.5% of the total hydrogen gas supplied during the entire hydrotreating process.

[00113] The third reaction effluent, enriched in dissolved hydrogen, was then introduced into a fourth reactor having at least a reaction zone containing a catalyst bed at an operating temperature of about 340°C and an operating pressure of from about 50 bar to about 75 bar (5.0 -7.5 MPa) for additional hydrogenation of olefinic or unsaturated portions of the n-paraffin chains in the third reaction effluent. The amount of hydrogen gas relative to the volume of the catalyst bed in the third reactor was approximately 400 normal ^{m 3} /m ³ . The reaction mixture was then passed through a fourth HHPS to separate steam and gaseous components therefrom, resulting in a fourth reaction effluent stream.

[00114] The fourth reaction effluent stream (which was in the oil phase) was passed through a flash vessel to separate dissolved gaseous components therefrom, resulting in a first separated effluent stream. The first separated effluent stream was then introduced into a low pressure separator to separate water vapor therefrom, resulting in a second separated effluent stream. The second separated effluent stream was further passed through a distillation column to separate the diluent therefrom, resulting in the desired hydrotreated product, or more specifically, hydrotreated oil.

[00115] Table 2 shows the properties of hydrotreated oil obtained by the method described in example 1.

[00116] Example 2: Palm Oil Hydrotreating Process

[00117] A commercially available CoMo/Al ₂ O ₃ catalyst was loaded into a reactor and then activated into the sulfided form at a temperature of from about 150° C. to about 34 0° C. and a pressure of about 35 bar (3.5 MPa) for a period of time of about 2 4 hours in the presence of dimethyl disulfide as a sulfylating agent. The amount of sulfides in the sulfidation agent fed to the reactor was twice the amount of catalyst required for the sulfidation reaction based on stoichiometric demand.

[00118] Refined bleached deodorized palm oil (RBDPO) was used as a renewable feedstock and mixed with refined petroleum product as a diluent to produce a diluted feedstock at room temperature and atmospheric pressure using a suitable mixing device known in the art. The ratio of diluent to renewable feedstock was approximately 99:1 by weight. A sulfilating agent was added to the diluted feed and the diluted feed was then heated to a temperature of about 320°C and compressed to a pressure of from about 30 bar to about 40 bar (3.0-4.0 MPa). Thereafter, hydrogen gas was passed through the dilute feed, wherein a desired amount of hydrogen gas was dissolved in the dilute feed, thereby forming a dilute feed enriched in dissolved hydrogen. The amount of hydrogen gas supplied at this stage was approximately 50% of the total amount of hydrogen gas supplied during the entire hydrotreating process (the total amount of hydrogen was 3.0% by weight, based on the weight of the fresh feed).

[00119] The diluted feedstock, enriched in dissolved hydrogen, is then fed to a first reactor having at least a reaction zone containing a catalyst bed at an operating temperature of about 340° C. and an operating pressure of about 30 bar to about 40 bar (3.0- 4.0 MPa) to form purified oil. The hourly space velocity of the liquid was maintained at 25.0 h ^-1 . The reaction mixture was then passed through a first HHPS to separate steam and gaseous components therefrom, resulting in a first reaction effluent.

[00120] Before introducing the first reaction effluent stream into the second reactor, the first reaction effluent stream was brought into contact with the desired amount of hydrogen gas (which was heated to a temperature of about 320°C and compressed to a pressure of from about 30 bar to about 40 bar (3 ,0-4.0 MPa)) and with the desired amount of sulfilating agent to form the first reaction effluent stream enriched in dissolved hydrogen. The amount of hydrogen gas supplied during this stage was approximately 50% of the total amount of hydrogen gas supplied during the entire hydrotreating process.

[00121] The first reaction effluent enriched in dissolved hydrogen is then introduced into a second reactor having at least a reaction zone containing a catalyst bed at an operating temperature of about 320° C. and an operating pressure of from about 30 bar to about 40 bar (3. 0-4.0 MPa) to form purified oil. The hourly space velocity of the liquid was maintained at 25.0 h ^-1 . The reaction mixture was then passed through a second HHPS to separate steam and gaseous components therefrom, resulting in a second reaction effluent.

[00122] The second separated effluent was introduced into a low pressure separator to separate water vapor therefrom, resulting in the first separated effluent stream of hydrotreated oil. The properties of the refined oil obtained from Example 2 are shown in Table 3.

[00123] It should be noted that the refined oil obtained from Example 2 can be obtained without the step of separating the dissolved gaseous component using a flash tank, since the gaseous component can be substantially separated in the high pressure hot separator step. In addition, the refined oil obtained from Example 2 can also be obtained without the distillation step, however, the refined oil may have a lower flash point.

[00124] Table 3 shows the properties of hydrotreated oil obtained by the method described in example 2.

[00125] Example 3: Effect of Reduced Hydrogen Circulation Rate

[00126] In a traditional hydrotreating process, the reactor typically operates as a trickle bed where hydrogen gas is transported across the liquid-coated surface of the catalyst, providing a continuous gas phase throughout the reactor. As a result, the reaction in the irrigated layer requires a very large consumption of hydrogen (hydrogen circulation rate), greater than that required for the reaction (hydrogen consumption rate) to maintain a continuous gas phase. If a continuous gas phase cannot be maintained, this can lead to catalyst deactivation.

[00127] Typically, the hydrogen consumption rate used in RBDP0 hydrotreating is from about 2.5 wt% to about 3.5 wt%, while the hydrogen consumption rate used in conventional hydrotreating is about 200% by weight. these values of hydrogen consumption norms.

[00128] Hydrotreated oil was prepared in accordance with the method described in Example 2 using two reactors with the following reaction conditions:

- the raw material in this experiment was RBDP0;

- the reaction temperature was approximately 320°C;

- the reaction pressure was approximately 35 bar (3.5 MPa);

- purified oil was used as a diluent;

- the ratio of diluent to renewable raw material was approximately 99:1 by weight;

- the volumetric velocity of the liquid was approximately 25.0 h ^-1 ;

-CoMo/Al ₂ O ₃ in sulfided form was used as an activated catalyst loaded into each reactor;

-the ratio of hydrogen to renewable raw materials was approximately 3.5-6.0% by weight;

- hydrogen gas in an amount of 50% of the total amount of hydrogen gas supplied during the entire hydrotreating process was added to each reactor;

- HHPS was used to separate gaseous components and water vapor from the reaction effluent obtained from each reactor.

[00129] Table 4 shows the properties of hydrotreated oil obtained by the method described in example 3.

[00130] From Table 4, it is apparent that the product properties do not change even though the hydrogen circulation rate used in Example 3 was 3.5 wt%, or 4 wt%, or 5 wt%, or 6 wt%. That is, the present invention provides the advantage of using a hydrogen recycling rate in the range of more than 200%, or more than 175%, or more than 150%, or more than 125%, or more than 100% of the hydrogen consumption rate. The use of excess hydrogen gas is not required in the hydrotreating process of the present invention.

[00131] Example 4: Method for producing phase change materials (PCMs) from the hydrotreated oil obtained in Example 1

[00132] This example describes a method for producing PCM from hydrotreated oil obtained from the process described in Example 1. Specifically, the hydrotreated oil was fed to several distillation units and several adsorption units. The properties of RSM are given in Table 3.

[00133] Table 5 shows the properties of the PCM obtained from the method described in Example 4.

[00134] Example 5: Effect of Types of Renewable Feedstocks on the Received PCM

[00135] This example is provided to illustrate how the choice of renewable feedstock will affect the properties of the resulting PCM.

[00136] Hydrotreated oil was prepared in accordance with the method described in Example 1 using 5 reactors with the following reaction conditions:

- The reaction temperature was approximately 360°C;

- The reaction pressure was from about 50 bar to about 75 bar (5.0-7.5 MPa);

-N-undecane was used as a diluent;

-The ratio of diluent to renewable feedstock was approximately 90:10 by weight;

- The volumetric velocity of the liquid was approximately 10.0 h ^-1 ;

- CoMo/Al ₂ O ₃ in sulfided form was used as an activated catalyst loaded into each reactor;

- The ratio of hydrogen to renewable feedstock was approximately 3.5% by weight;

- Hydrogen gas in an amount of 20% of the total amount of hydrogen gas supplied during the entire hydrotreating process was added to each reactor;

- The amount of hydrogen relative to the volume of the catalyst layer in the first reactor was 600 normal ^{m 3} /m ³ ;

- The amount of hydrogen relative to the volume of the catalyst layer in the second reactor was 400 normal ^{m 3} /m ³ ;

- The amount of hydrogen relative to the volume of the catalyst layer in the third reactor was 200 normal ^{m 3} /m ³ ;

- The amount of hydrogen relative to the volume of the catalyst layer in the fourth reactor was 100 normal ^{m 3} /m ³ ;

- The amount of hydrogen relative to the volume of the catalyst layer in the fifth reactor was 50 normal ^{m 3} /m ³ ; And

- HHPS was used to separate gaseous components and water vapor from the reaction effluent obtained from each reactor.

[00137] Table 6 shows the properties of the PCM obtained from the method described in example 4

[00138] The results shown in Table 6 show that the RBDP0 hydrotreating process produces a large volume of n-paraffin containing 16 carbon atoms and 18 carbon atoms, which is similar to the hydrotreating process of palm fatty acids. On the other hand, hydrotreating processes of rapeseed oil, soybean oil and stearic acid result in the formation of a large volume of n-paraffin containing 17 carbon atoms and 18 carbon atoms. In this regard, it should be understood that raw materials containing fats and/or fatty acids can be used as renewable raw materials for the production of a wide range of n-paraffins, which then allows the production and production of a wide range of PCMs.

[00139] Example 6: Bionaphtha Production

[00140] This example describes a method for producing bionaphtha. Specifically, hydrotreated oil was prepared in accordance with the method described in Example 1, using palm kernel oil and lauric acid as renewable raw materials and using the following reaction conditions:

- Used 3 reactors;

- The reaction temperature was approximately 360°C;

- The reaction pressure was approximately 100 bar (10 MPa);

- Fresh bionaphtha and/or part of the bionaphtha obtained as a result of the method was used as a diluent;

- The ratio of diluent to renewable feedstock was approximately 85:15 by weight;

- The volumetric velocity of the liquid was approximately 10.0 h ^-1 ;

- Sulfided I1CoMo/Al ₂ O ₃ catalyst was used as an activated catalyst loaded into each reactor;

- The ratio of hydrogen to renewable feedstock was approximately 2.2% by weight;

- 40% of the total amount of hydrogen gas supplied to the hydrotreating process was supplied to the first reaction zone, 30% of the total amount of hydrogen supplied to the hydrotreating process was supplied to the second reaction zone, and 30% of the total hydrogen gas supplied to the hydrotreating process , was fed into the third reaction zone;

- The amount of hydrogen relative to the volume of the catalyst layer in the first reactor was 600 normal ^{m 3} /m ³ ;

- The amount of hydrogen relative to the volume of the catalyst layer in the second reactor was 300 normal ^{m 3} /m ³ ;

- The amount of hydrogen relative to the volume of the catalyst layer in the third reactor was 50 normal ^{m 3} /m ³ ;

- An HHPS was provided at the outlet of each reactor to separate gaseous by-products, including water vapor, from the reaction effluent obtained from each reactor.

[00141] Table 7 shows the properties of bionaphtha obtained by the method described in example 6.

[00142] Comparative Example 1

[00143] Comparative Example 1 is compared to Example 3. It was performed using a conventional hydrotreating process to produce hydrotreated oil, which was prepared in accordance with the method described in Example 2 using 1 reactor and the following reaction conditions:

-the raw material in this experiment was RBDPO;

- the reaction temperature was approximately 320°C;

- the reaction pressure was approximately 35 bar (3.5 MPa);

- purified oil was used as a diluent;

-the ratio of diluent to renewable raw material was approximately 70:30 by weight;

- the volumetric velocity of the liquid was approximately 1.0 h ^-1 ;

-CoMo/Al ₂ O ₃ in sulfided form was used as an activated catalyst loaded into each reactor;

-the ratio of hydrogen to renewable raw materials was varied at the level of 5.0 wt%, 5.5 wt% and 6.0 wt%; And

-HHPS was used to separate gaseous components and water vapor from the reaction effluent obtained from each reactor.

[00144] Table 8 shows the properties of hydrotreated oil obtained from the traditional hydrotreating process.

[00145] From Table 8 it can be seen that the use of a hydrogen recycling rate below 6 wt.%, i.e. 5.5% and 5% gave a high acid number in the resulting refined oil because the free fatty acid content in the refined oil is increased due to incomplete reaction and this causes the refined oil to become more acidic. In other words, the hydrogen recycling rate used in conventional hydrotreating must be at least 200% of the hydrogen consumption rate, while the hydrogen consumption rate in the case of RBDPO is in the range of 2.5-3.5% by weight.

[00146] Comparative Example 2

[00147] Yantao Bi et al. conducted a study of compositional changes during hydrodeoxygenation of pyrolysis oil from biomass. The study was conducted using pyrolysis oil obtained from logging waste 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 for stabilization, while the reaction temperature in the second reactor was maintained at 150°C, 210°C, 300°C, 360°C to produce upgraded pyrolysis oils, respectively called UPO -1, UPO-2, UP0-3 and UPO-4.

[00148] Table 9 shows the composition of pyrolysis oil, UPO-1, UPO-2, UP0-3 and UPO-4 obtained by hydrodeoxygenation of pyrolysis oil.

[00149] The results, as well as the table above, show that UPO-1, UPO-2, UPO-3 and UP04 obtained from pyrolysis oil do not contain n-paraffin, and therefore these compounds cannot be used to obtain phase change materials, unlike the present invention.

[00150] Comparative Example 3

[00151] Tables 10-14 show the solubility of hydrogen in renewable feedstocks containing mainly triglycerides and free fatty acid, and the solubility of hydrogen in various dilute feedstocks in which n-paraffin with different numbers of carbon atoms is used as a diluent to dilute the renewable feedstock , containing mainly triglycerides and free fatty acids. The tables also show that n-paraffin, having a lower number of carbon atoms, provides higher solubility of hydrogen in the dilute feed.

[00152] In some embodiments, diluents other than n-paraffin may also be used to facilitate hydrogen solubility in the dilute feedstock. However, if diluents other than n-paraffin are used, it may cause difficulty in separating the diluents from the hydrotreated oil products, resulting in additional production costs.

[00153] Table 10 shows the solubility of hydrogen in triolein as a feedstock.

[00154] Table 11 shows the solubility of hydrogen in a dilute feedstock prepared using n-octadecane as a diluent and triolein as a feedstock in a ratio of 90 wt% diluent to 10 wt%. raw materials.

[00155] Table 12 shows the solubility of hydrogen in a dilute feed prepared using n-tetradecane as a diluent and triolein as a feed in a ratio of 90 wt% diluent to 10 wt% feed.

[00156] Table 13 shows the solubility of hydrogen in a dilute feedstock prepared using n-dodecane as a diluent and triolein as a feedstock in a ratio of 90 wt% diluent to 10 wt%. raw materials.

[00157] Table 14 shows the solubility of hydrogen in a dilute feed prepared using n-undecane as a diluent and triolein as a feed in a ratio of 90 wt% diluent to 10 wt% feed.

[00158] The results from the tables above showed that if n-paraffin with a higher carbon number is used as a diluent, it gives lower hydrogen solubility. The results also showed that when used as a diluent, n-dodecane, which has 12 carbon atoms, provides the highest hydrogen solubility. However, it is not recommended to use n-paraffin having less than 10 carbon atoms as a diluent because it cannot remain in the liquid phase under reaction conditions.

[00159] It should be understood that various other modifications and adaptations of the invention will become apparent to one skilled in the art upon reading the foregoing description without departing from the spirit and scope of the invention. All such modifications and adaptations are intended to be within the scope of the appended claims.

[00160] Additionally, it should be appreciated that features from various embodiments may be combined to form one or more additional embodiments.

[00161] Links

[00162] 1. Yantao Bi, Gang Wang, Quan Shi, Chunming Xu and Jinsen Guo. Compositional Changes during Hydrodeoxygenation of Biomass Pyrolysis Oil, Energy Fuels, 2014, 28, pp.2571-2580.

Claims (24)

1. A method of producing one or more hydrocarbon products from a liquid phase of a renewable feedstock using multiple hydrotreating reactors, including a first reactor and at least an additional reactor, each of which provides a catalyst bed containing a hydrotreating catalyst that has been activated prior to use through a sulfidation process, wherein the renewable feedstock contains triglycerides, free fatty acids or combinations thereof, the method comprising the steps diluting the renewable raw material with a diluent to form a diluted raw material, the diluent containing n-paraffin having C ₁₀ -C ₂₀ carbon atoms; forming a dilute feedstock enriched in dissolved hydrogen by (a) contacting the dilute feedstock with hydrogen gas and then adding a sulfylating agent to the dilute feedstock that has been in contact with the hydrogen gas, or (b) adding a sulfurizing agent to the dilute feedstock and then contacting the dilute feedstock, to which a sulfilating agent was added, with hydrogen gas, before introducing the diluted feedstock enriched with dissolved hydrogen into the first reactor; directing the diluted feedstock enriched in dissolved hydrogen into a first reactor containing a first catalyst bed to form a reaction effluent stream enriched in dissolved hydrogen; further contacting the reaction effluent stream with hydrogen gas and a sulfilating agent, whereby the hydrogen gas is dissolved in the reaction effluent stream to form a dissolved hydrogen-enriched reaction effluent stream, before introducing the dissolved hydrogen-enriched reaction effluent stream into the additional reactor; further directing the reaction effluent stream enriched in dissolved hydrogen into an additional reactor containing an additional catalyst bed, resulting in an additional reaction effluent stream that can be further processed to form one or more hydrocarbon products, in which the gas volume fraction (GVF) of undissolved hydrogen in the additional reactor is 0.1-0.25. 2. The method according to claim 1, further comprising the step of passing a sulfilating agent and/or hydrogen gas through each reactor in a predetermined amount. 3. The method of claim 1, further comprising the step of separating gaseous by-products from the reaction effluent stream or from an additional reaction effluent stream using a high pressure hot separator. 4. The method according to claim 1, comprising the stages: feeding additional reaction effluent to several separators, which are arranged in series, to separate by-products, recover n-paraffin and obtaining a hydrotreated product; reintroducing the recovered n-paraffin for diluent use into the diluent source; And feeding the hydrotreated product to one or more distillation columns and adsorption units to purify the hydrotreated product to obtain one or more purified hydrocarbon products. 5. The method of claim 1, wherein the renewable feedstock is an animal oil, a vegetable oil, or a combination of one or more animal oils and one or more vegetable oils. 6. The method of claim 1, wherein the renewable feedstock is tall oil, whale oil, fish oil, bleached palm oil (BPO), refined bleached deodorized palm oil (RBDPO), palm olein, palm stearin, palm fatty acid distillate, canola oil, corn oil, sunflower oil, soybean oil, jatropha oil, balanite oil, canola oil, tall oil, hemp oil, olive oil, flaxseed oil, mustard oil, peanut oil, castor oil, coconut oil or a combination of any two or more oils 7. The method of claim 1, wherein the renewable feedstock is fresh oil, used oil, used oil, or any combination thereof. 8. The method according to claim 1, in which the diluent is 70-100% of the mass. n-decane (C ₁₀ ), n-undecane (C ₁₁ ), n-dodecane (C ₁₂ ), n-tridecane (C ₁₃ ), n-tetradecane (C ₁₄ ) or a mixture thereof. 9. The method according to claim 1, in which the ratio of diluent to renewable raw material is from about 99% of the mass. diluent/1% wt. raw materials up to approximately 50% wt. diluent/50% wt. raw materials. 10. The method according to claim 1, wherein the ratio of hydrogen gas to the volume of the catalyst bed in the reactor is in the range of 3-900 normal ^{m 3} /m ³ and/or the ratio of hydrogen gas to renewable feedstock is in the range of about 10 normal m ³ /m ³ to about 700 normal m ³ /m ³ (from about 0.001 g/g to about 0.054 g/g). 11. The method according to claim 1, wherein the catalyst contains at least one of two transition metals selected from the group consisting of Ni and Mo. 12. The method of claim 11, wherein the catalyst further comprises another transition metal or group V element and/or the catalyst is supported on a support. 13. The method of claim 12, wherein the support is an acidic porous solid support selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), silicon dioxide (SiO ₂ ) and a mixture of aluminum oxide and silicon dioxide (Al ₂ O ₃ -SiO ₂ ). 14. The method according to claim 13, in which the carrier is aluminum fluoride, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-32, ZSM-35, ZSM-38, ZSM-48, ZSM -57, SAPO-11, SAPO-31, SAP0-41, MARO-11, MARO-31, Y zeolite, L zeolite or β-zeolite.