Method for treating renewable feedstock

Abstract

Non-petroleum or renewable feedstock containing oxygen and contaminants of metals, gums, resins is treated by introducing the feedstock into a reactor at a flow rate of at least 6 m / sec. The feedstock is heated and cooled within the reactor to form a cooled reactor product. At least a portion of the cooled reactor product is passed to a hydroprocessing reactor containing a hydrotreating catalyst to form a hydrotreated product. The hydrotreated product is cooled and the non-condensable gases, metals, and water are separated and removed, thereby forming a final product. The oxygen content of the final product is 60% or less of the oxygen content of the feedstock, and wherein the final product comprises 25 wt% or less of any triglyceride, monoglyceride, diglyceride, free fatty acids, phospholipids, sterols, tocopherols, tocotrienols, and fatty alcohols, from 5 wt% to 30 wt% naphtha, and 50 wt% or more diesel.

Description

Background Art

[0001] Renewable diesel feedstocks that have not been pretreated (such as distilled corn oil, refined bleachable tallow, used cooking oil, etc.) contain many components that are harmful to the hydroprocessing reactor or equipment used to produce renewable diesel, as well as other products. These components can cause serious plugging problems in the reactor used to form renewable diesel. Therefore, almost all feedstocks must be pretreated before being processed into renewable diesel.

[0002] Conventional pretreatment of renewable diesel feedstocks typically requires two stages of pretreatment. The first stage utilizes a centrifuge to remove gums and resins by adding water and then centrifuging to separate out the "hydratable" gums. This is followed by acid washing and centrifugation to remove the "non-hydratable" gums. In the second stage, "bleaching" is used to remove metals and colored materials via "filtration" through an adsorbent. The "spent" adsorbent must be regenerated or disposed of in a landfill. The process is labor and capital intensive, in addition to the solid waste material that must be disposed of. In addition, such pretreatment processes do not address the high oxygen content that is typically present in the feedstock.

[0003] Once the renewable diesel feedstock is pretreated, the pretreated feedstock is hydrotreated in a renewable diesel unit. Renewable diesel units are typically built for harsh operations and operate at high pressures (e.g., 900psi or 6200kPA or higher) with the release of high heat. This increases the construction cost of renewable diesel plants because plants configured for higher operating pressures are more expensive than those operating at lower pressures. Traditional renewable diesel units also have a high demand for hydrogen. This is due to the high oxygen content (e.g., 10% or higher) of traditional renewable diesel feedstocks. Hydrogen reacts with oxygen in renewable diesel feedstocks to form water. Water can be particularly harmful to the hydrogenation process catalysts of renewable diesel units. Water can deactivate the catalyst and reduce the solubility of hydrogen, significantly reducing the overall productivity of the unit.

[0004] In addition, even after hydrotreatment, the hydrotreated product still contains a large amount of wax or normal alkanes, resulting in the hydrotreated product having a very high pour point (e.g., a pour point of 70°F or 21°C). The high pour point may make renewable diesel unsuitable for use in colder climates. Therefore, the hydrotreated product usually needs to be isomerized to reduce the amount of normal alkanes, thereby forming isoparaffins and lowering the pour point of the renewable diesel product to a desired level.

[0005] In recent years, increasing attention has been paid to the greenhouse gases produced by the combustion of specific fuels. This includes not only the amount of GHG produced by simply burning the fuel itself, but also the amount of greenhouse gases (GHG) produced during the production and supply of the fuel. This evaluation is often referred to as a life cycle assessment (LCA), which is a methodology used to assess the environmental impact of a commercial product or process. Standards such as the US EPA's revised national Renewable Fuel Standard (RFS2) and California's Low Carbon Fuel Standard (LCFS) have been implemented to try to reduce GHG emissions. These standards are expressed in terms of the carbon dioxide emissions intensity or carbon intensity (CI) score or value for a specific fuel. CI is expressed in terms of CO2 emissions (CO 2e ) / MJ of fuel (i.e., gCO 2e CI is measured in g / MJ or g / MJ). For example, conventional petroleum diesel can have a CI of 100 g / MJ or higher. In contrast, renewable diesel can have a CI of about 20 g / MJ. While the CI values ​​of conventional renewable diesel are much lower than those of petroleum diesel, it would be beneficial to reduce the CI values ​​even further. Lowering the CI value of renewable diesel would not only reduce fuel-related GHG emissions, but fuels with lower CI scores could potentially be assigned a higher monetary value, making their production more profitable.

[0006] Therefore, improvements in the processing of renewable diesel feedstocks and the production of renewable fuels are needed to overcome the deficiencies currently encountered in these materials and their processing. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] For a more complete understanding of the specific embodiments of the present invention and its advantages, reference is now made to the accompanying drawings. Figure 1 The following descriptions are considered in conjunction with each other, in which:

[0008] Figure 1 is a schematic flow diagram of a processing system for processing a feedstock of fats and / or oils of animal origin and / or vegetable origin;

[0009] Figure 2 is a schematic flow diagram of an alternative embodiment of a processing system for processing a feedstock of fats and / or oils of animal origin and / or vegetable origin, using a recycle stream;

[0010] Figure 3 is a schematic flow diagram of another embodiment of a processing system comprising a hydrogenation process reactor, a feedstock of fats and / or oils of animal origin and / or vegetable origin for processing; and

[0011] Figure 4is a schematic flow diagram of another embodiment of a processing system for processing feedstocks of fats and / or oils of animal and / or vegetable origin utilizing both a recycle stream and a hydrogenation process reactor. DETAILED DESCRIPTION

[0012] In the present invention, the treatment process for processing non-petroleum raw materials or renewable raw materials is used to produce products (such as renewable diesel fuel) with higher value, and these raw materials are derived from the biogenic source containing one or more pollutants in oxygen, metals, gums and resins. These raw materials are usually fats and oils of animal origin and / or plant origin. Such fats and oils are mainly composed of: triglycerides, together with a small amount of monoglycerides and diglycerides, free fatty acids, phospholipids, sterols, tocopherols and tocotrienols and fatty alcohols. These fats and oils can be used for the raw materials of renewable diesel raw materials and other products. The source of such raw materials can include but is not limited to distilled corn oil, refined bleachable tallow (fancybleachable tallow), used cooking oil, animal fat, oil of plant origin, etc. These raw materials can also include pyrolysis oil (such as pyrolysis oil derived from cellulosic materials) with usually very high oxygen content and other oils with high metal and / or oxygen content.

[0013] In certain embodiments, non-petroleum or renewable raw materials can have at least one or more of triglycerides, monoglycerides, diglycerides, free fatty acids, phospholipids, sterols, tocopherols and tocotrienols and fatty alcohols in an amount of 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 80wt%, 85wt%, 90wt% and 95wt% or more by the gross weight of raw material. These are oxygenates that can be found in fats and oils of animal and / or plant origin. The majority of raw materials will be triglycerides, and their amount can be up to 95wt% or more by the gross weight of raw material. In certain embodiments, the total triglycerides, monoglycerides, diglycerides, free fatty acids, phospholipids, sterols, tocopherols and tocotrienols, and fatty alcohols can be at least, equal to, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, based on the total weight of the raw material. , 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt% and 99wt% and / or an amount ranging between any two of the above values ​​is present in the raw material.

[0014] It should be noted in the description that if a value, concentration or range is presented, each value should be understood once as modified by the term "about" (unless it has been explicitly modified), and then once again as not so modified, unless the context indicates otherwise. In addition, in the description, it should be understood that the range of quantities listed or described as useful, suitable, etc. means that any and every value (including endpoints) within the range is considered to have been explicitly indicated. For example, "a range from 1 to 10" should be understood to indicate every possible number in the continuous interval between about 1 and about 10. Therefore, even if a specific point in the range or even a point within the range is not explicitly identified or mentioned, it should be understood that the inventors recognize and understand that any and all points within the range are considered to have been specified, and the inventors own the entire range and all points within the range.

[0015] Compared with petroleum, these non-petroleum or renewable raw materials generally have high oxygen content. In many cases, the oxygen content of the raw material can be from 8wt% or higher based on the total weight of the raw material. In certain embodiments, the oxygen content can be at least, equal to 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt% based on the total weight of the raw material. %, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, and 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt% and 50 wt% and / or an amount ranging between any two of the above values ​​is present in the feedstock. As discussed previously, during the hydrogenation process or hydrotreating process, oxygen in the feedstock reacts with hydrogen to form water. This water may be harmful to renewable diesel or hydrogenation process reactors and catalysts, as well as reduce the solubility of hydrogen.

[0016] Non-petroleum or renewable feedstocks may also contain undesirable substances or "contaminants" (such as metals, gums and resins) which may cause serious plugging or other problems within reactors or processing equipment. These substances may be naturally present in the fats and oils as they are initially formed, or may be formed or added during their subsequent use or processing and prior to use as a renewable feedstock.

[0017] The metals may include, but are not limited to, phosphorus (P), sodium (Na), potassium (K), copper (Cu), iron (Fe), calcium (Ca) and magnesium (Mg), lead (Pb), cadmium (Cd), nickel (Ni), vanadium (V), manganese (Mn), zinc (Zn), etc. Such metals may be present in the feedstock in amounts ranging from a few parts per million by weight (ppm) of the feedstock (e.g., 0.1 ppm) to several thousand ppm (e.g., 5,000 ppm or more) based on the total weight of the feedstock.In certain embodiments, the total metal contaminants can be at least, equal to, 0.1 ppm, 0.5 ppm, 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, m, 800ppm, 850ppm, 900ppm, 950ppm, 1000ppm, 1050ppm, 1100ppm, 1150ppm, 1200ppm, 1200ppm, 1250ppm, 1300ppm, 1350ppm, 1400ppm, 1450ppm, 1500 ppm, 1550ppm, 1600ppm, 1650ppm, 1700ppm, 1750ppm, 1800ppm, 1850ppm, 1900ppm, 1950ppm, 2000ppm, 2050ppm, 2100ppm, 2150ppm, 2200ppm, 2200ppm , 2250ppm, 2300ppm, 2350ppm, 2400ppm, 2450ppm, 2500ppm, 2550ppm, 2600ppm, 2650ppm, 2700ppm, 2750ppm, 2800ppm, 2850ppm, 2900ppm, 2950ppm, 3 000ppm、3050ppm、3100ppm、3150ppm、3200ppm、3200ppm、3250ppm、3300ppm、3350ppm、3400ppm、3450ppm、3500ppm、3550ppm、3600ppm、3650ppm、3700 ppm, 3750ppm, 3800ppm, 3850ppm, 3900ppm, 3950ppm, 4000ppm, 4050ppm, 4100ppm, 4150ppm, 4200ppm, 4200ppm, 4250ppm, 4300ppm, 4350ppm, 4400ppm, 4450ppm, 4500ppm, 4550ppm, 4600ppm, 4650ppm, 4700ppm, 4750ppm, 4800ppm, 4850ppm, 4900ppm, 4950ppm and 5000ppm and / or an amount ranging between any two of the above values.

[0018] Gums and resins, as well as carbohydrates and proteins, may account for several percentage points (e.g., from 1 wt% to 10 wt%) by weight of the feedstock. If these undesirable components are not removed or converted before processing, they can cause serious blockages and other harmful problems in reactors and processing equipment. In certain embodiments, the total gums and resins may be at least, equal to, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, 3.0 wt%, 3.1 wt%, 3.2 wt%, 3.3 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.7 wt%, 3.8 wt%, 3.9 wt%, 4.0 wt%, 4.1 wt%, 4.2 wt%, 4.3 wt%, 4.4 wt%, 4.5 wt%, 4.6 wt%, 4.7 wt%, 4.8 wt%, 4.9 wt%, 4.0 wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, and 4.0wt%, 4.1wt%, 4.2wt %, 4.3wt%, 4.4wt%, 4.5wt%, 4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, 5.0wt%, 5.1wt%, 5.2wt%, 5.3wt%, 5.4wt%, 5 .5wt%, 5.6wt%, 5.7wt%, 5.8wt%, 5.9wt%, 6.0wt%, 6.1wt%, 6.2wt%, 6.3wt%, 6.4wt%, 6.5wt%, 6.6wt%, 6.7w t%, 6.8wt%, 6.9wt%, 7.0wt%, 7.1wt%, 7.2wt%, 7.3wt%, 7.4wt%, 7.5wt%, 7.6wt%, 7.7wt%, 7.8wt%, 7.9wt%, 8.0wt%, 8.1wt%, 8.2wt%, 8.3wt%, 8.4wt%, 8.5wt%, 8.6wt%, 8.7wt%, 8.8wt%, 8.9wt%, 9.0wt%, 9.1wt%, 9.2wt%, 9.3wt%, 9.4wt%, 9.5wt%, 9.6wt%, 9.7wt%, 9.8wt%, 9.9wt% and 10.0wt% and / or an amount ranging between any two of the above values ​​is present in the raw material.

[0019] refer to Figure 1 , a system 10 is shown for forming products from a fresh or initial non-petroleum or renewable feedstock 12, which may be fats and / or oils of animal and / or vegetable origin containing contaminants of oxygen and one or more of metals, gums, and resins. The system 10 includes a treatment system 14 for removing oxygen and undesirable materials (including metals, gums, and resins) from the feedstock 12 prior to any hydrogenation process or hydrotreating, such as in a renewable diesel unit.

[0020] The feedstock 12 is ultimately heated to a temperature of 390°C to 600°C in an externally heated tubular or plug flow reactor 16. The reactor 16 is catalyst-free or does not contain or utilize a hydrogenation process catalyst. In certain embodiments, the useful operating or processing temperature range of the reactor 16 can be at least, equal to, and / or range between any two of the following values: 390°C, 395°C, 400°C, 405°C, 410°C, 415°C, 420°C, 425°C, 430°C, 435°C, 440°C, 445°C, 450°C, 455°C, 460°C, 465°C, 470°C, 475°C, 480°C, 485°C, 490°C, 495°C, 500°C, 505°C, 510°C, 515°C, 520°C, 525°C, 530°C, 535°C, 540°C, 545°C, 550°C, 555°C, 560°C, 565°C, 570°C, 575°C, 580°C, 585°C, 590°C, 595°C and 600°C. In the following discussion, for illustration purposes, a temperature of 510°C may be used to heat the feedstock within the reactor 16. The reactor 16 may be a fired heater, electrically heated, steam heated, hot gas heated, oil heated, etc. The heating may also be provided as waste heat from other processes.

[0021] In some embodiments, the treatment system 14 may be provided with one or more optional secondary reactors 18, 20, which are located downstream and receive the reactor discharge stream 22 from the reactor 16, which can be considered a primary reactor. These secondary reactors 18, 20 can be configured in parallel or in series, and can also be heated or flame reactors for continuing to heat the discharge stream 22 to maintain the elevated reaction temperature. In other embodiments, the reactors 18, 20 are not heated, and the reactors 18, 20 are used only as vessels to increase the residence time before cooling, where the reaction can continue to occur from the heated discharge stream 22 from the reactor 16. The reactors 16, 18, 20 and their inlets are configured in conjunction with the fluid flow of the feed to provide a tubular flow or plug flow through the reactor to eliminate or reduce backflow and backmixing. The primary reactor 16 and the secondary reactors 18, 20 can be sized and configured to provide a selected residence time for the introduced feedstock at a selected reactor temperature to ensure that the feedstock is fully reacted before being discharged from the reactor. The residence time in the reactor portion of system 14 is typically on the order of only a few seconds (eg, 5 seconds or less).

[0022] The pressure within the reactors 16, 18, 20 will typically range from 0 kPag to 7000 kPag. In specific applications, the operating pressure of the reactor(s) may be at least, equal to, and / or range between any two of the following values: 0 kPag, 50 kPag, 100 kPag, 150 kPag, 200 kPag, 250 kPag, 300 kPag, 350 kPag, 400 kPag, 450 kPag, 500 kPag, 550 kPag, 600 kPag, 650 kPag, 700 kPag, 750 kPag, 760 kPag, 800 kPag, 850 kPag, 900 kPag, 950 kPag, 1000 kPag, 1100 kPag, 1150 kPag, 1200 kPag, 1250 kPag, 1300 kPag, 1350 kPag, 1400 kPag, 1450 kPag, 1500 kPag, 1600 kPag, 1650 kPag, 1700 kPag, 1750 kPag, 1760 kPag, 1800 kPag, 1850 kPag, 1900 kPag, 1950 kPag, 1900 kPag, 2000 kPag, 2100 kPag, 2200 kPag, 2300 kPag, 2400 kPag, 2500 kPag 0kPag、1200kPag、1250kPag、1300kPag、1350kPag、1400kPag、1450kPag、1500kPag、1550kPag、1600kPag、1650kPag、1700kPag、1750kPag、1760k Pag, 1800kPag, 1850kPag, 1900kPag, 1950kPag, 2000kPag, 2100kPag, 2150kPag, 2200kPag, 2250kPag, 2300kPag, 2350kPag, 2400kPag, 2450kPag , 2500kPag, 2550kPag, 2600kPag, 2650kPag, 2700kPag, 2750kPag, 2760kPag, 2800kPag, 2850kPag, 2900kPag, 2950kPag, 3000kPag, 3100kPag, 3 150kPag, 3300kPag, 3350kPag, 3300kPag, 3350kPag, 3400kPag, 3450kPag, 3500kPag, 3550kPag, 3600kPag, 3650kPag, 3700kPag, 3750kPag, 3760 kPag, 3800kPag, 3850kPag, 3900kPag, 3950kPag, 4000kPag, 4100kPag, 4150kPag, 4200kPag, 4250kPag, 4300kPag, 4350kPag, 4400kPag, 4450kP ag, 4500kPag, 4550kPag, 4600kPag, 4650kPag, 4700kPag, 4750kPag, 4760kPag, 4800kPag, 4850kPag, 4900kPag, 4950kPag, 5000kPag, 5100kPag,5150 kPag, 5200 kPag, 5250 kPag, 5300 kPag, 5350 kPag, 5400 kPag, 5450 kPag, 5500 kPag, 5550 kPag, 5600 kPag, 5650 kPag, 5700 kPag, 5750 kPag, 5760 kPag, 5800 kPag, 5850 kPag, 5900 kPag, 5950 kPag, 6000 kPag, 6100 kPag, 6150 kPag, 6200 kPag, 6250 kPag, 6300 kPag, 6350 kPag, 6400 kPag, 6450 kPag, 6500 kPag, 6550 kPag, 6600 kPag, 6650 kPag, 6700 kPag, 6750 kPag, 6760 kPag, 6800 kPag, 6850 kPag, 6900 kPag, 6950 kPag and 7000 kPag.,

[0023] At the above temperatures, the reactions in reactor 16 and reactors 18, 20 occur very quickly without significant yield loss. All or most of the gums and resins react in the thermal cracking reaction in reactor 16 to form smaller, lower molecular weight components (such as non-condensable gases, naphtha, jet fuel and diesel compounds) that can be removed as an exhaust gas or passed through a renewable diesel hydrotreater or other hydroprocessing equipment to make useful products without causing fouling problems. In specific embodiments, the gum and resin content of the initial feedstock can be reduced to 10% to 100% by weight of the initial gum and resin content in the feedstock 12. In certain embodiments, the gum and resin content of the feedstock 12 can be reduced by at least, or by equal to, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%, 111 94%, 95%, 96%, 97%, 98%, 99%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%, 111%, 112%, 113%, 114%, 115%, 116%, 117%, 118%, 119%, 120%, 121%, 122%, 123%, 124%, 125%, 126%, 127%, 128%, 129%, 130%, 131%, 132%, 133%, 134%, 135%, 136%, 137%, 138%, 139%, 240%, 241%, 242%, 243%, 244%, 245%, 246%, 247%, 248%, 249%, 250%, 251%, 252%, 253%, 254%,

[0024] In addition, oxygenated compounds (e.g., triglycerides, monoglycerides and diglycerides, free fatty acids, etc.) in the feedstock can also react to form water, CO2, CO and other small oxygenated compounds. The oxygen present in the feedstock transported to the renewable diesel unit or other hydrogenation process unit will react with hydrogen to form water. Therefore, before this hydrogenation process, removing the oxygen in the treatment system 14 can reduce the hydrogen demand of the renewable diesel unit or other downstream treatment units. During the treatment process, 10% to 100% of the oxygen in the initial feedstock can be removed. For example, at a reaction temperature of 510°C, 40% to 60% of the oxygen can be removed very quickly from the feedstock. At higher temperatures and / or longer reaction times, all oxygen can be removed. Triglycerides and monoglycerides and diglycerides in the feedstock 12 also react or "split" to form free fatty acids, alkanes, olefins and other various compounds.

[0025] The high temperature reactor product 24 from the primary tubular reactor 16 and any secondary reactors 18, 20 is cooled to form a cooled reactor product. In certain applications, the heat of the high temperature reactor product 24 is recovered and can be used to heat the feed 26 in the first stage cross heat exchanger. In the first stage of cross heat exchange, the feed 26 is used to cool the hot reactor product 24 from the reactor 16 and any reactors 18, 20 in the heat exchanger 28. The temperature of the hot reactor product 24 is typically from 400°C to 595°C, and will typically be at a temperature 25°C to 300°C higher than the feed 26. This typically results in the feed 26 introduced into the reactor 16 being heated (ΔT) from 12.5°C to 300°C, and the heated product 24 being cooled or reduced in temperature (ΔT) from 12.5°C to 300°C. The feed 26 may initially be at a temperature of from 90°C to 320°C before entering the heat exchanger 28. The heated feedstock 30 discharged from the exchanger 28 and introduced into the reactor 16 is typically at a temperature of from 370°C to 540°C.

[0026] In addition, the desuperheated reactor product 32 discharged from the heat exchanger 28 can be at a temperature of from 120° C. to 540° C. For example, where the hot reactor product 24 is at 510° C. and the feed 26 is at 345° C., the feed 26 can be heated to approximately 480° C. to form the heated feed 30, and the product 24 is cooled to a temperature of approximately 370° C. to form the desuperheated reactor product 32. In certain embodiments, the reactor product 24 may be cooled to at least, or equal to, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C, 255°C, 260°C, 265°C, 270°C, 275°C, 280°C, 285°C, 290°C, 295°C, 300°C, 305°C, 310°C, 315°C, 320°C, 325°C, 330°C, 335°C , 350°C, 355°C, 360°C, 365°C, 370°C, 375°C, 380°C, 385°C, 390°C, 395°C, 400°C, 405°C, 410°C, 415°C, 420°C, 425°C, 430°C, 435°C, 440°C, 445°C, 450°C, 455°C, 460°C, 465°C, 470°C, 475°C, 480°C, 485°C, 490°C, 495°C, 500°C, 505°C, 510°C, 515°C, 520°C, 525°C, 530°C, 535°C and 540°C and / or a temperature range between any two of the above values ​​to form a cooled reactor product 32.

[0027] At a temperature where the heated feed 30 is heated at or above 370° C., the reaction of the feed 26 begins in the heat exchanger 28, so that it can be considered part of the overall reactor system 34 for processing the feedstock. In other embodiments where the feed 30 is not heated at or above 370° C., only the primary reactor 16 and any secondary reactors 18, 20 can be considered part of the overall reactor system 34.

[0028] In certain embodiments, a second cross heat exchanger 36 may be provided for further cooling the reduced temperature reactor product 32 from the heat exchanger 28 at a ΔT from 12.5°C to 300°C. The heat exchanger 36 may use all or part of the fresh feed 12 to further cool the product 32 to a temperature of 20°C to 95°C. This typically results in the initial or fresh feed 12 being heated from 12.5°C to 300°C (ΔT). The temperature of the initial feed 12 may vary, but may range from room temperature (e.g., 20°C to 23°C) or ambient atmospheric temperature (e.g., 18°C ​​to 38°C) to 70°C. In some embodiments, it may be heated to a temperature of from 90°C to 345°C in the heat exchanger 36. Where the feed 12 contains oil or fat that is solid at room temperature, it may be necessary to preheat the fresh feed 12 to above room temperature or ambient temperature so that the oil and fat are in a flowable liquid form. In the example where the temperature-reduced reactor product 32 is at 370°C, the product 32 is further cooled to provide a cooled reactor product 38 having a temperature of about 90°C to 95°C, wherein the initial feed 12 is heated to 345°C to form the feed 26. At the temperature at which the fresh feed 12 is heated in the heat exchanger 36 at or above 370°C, the reaction of the fresh feed 12 begins in the heat exchanger 36 so that it can be considered as part of the overall reactor system 34 for processing the feedstock.

[0029] In some cases, the cooled reactor product 38 may be further cooled in an additional heat exchanger 40 that does not utilize feedstock 12 as a cooling fluid. Heat exchanger 40 may be used instead of or in addition to heat exchanger 36. The final cooled reactor product 42 will typically be at a temperature of from 35°C to 95°C.

[0030] The final cooled reactor product 42 is then introduced into one or more separators 44. Non-condensable waste gases 46 (such as CO2, CO and light hydrocarbons (i.e., C1 to C5 hydrocarbons)) produced in the reactor system 34 are separated from the cooled reactor product 42. In one example, at a reaction temperature of 510°C, the non-condensable gases can be 75% to 80% CO2 and some CO, 1% to 2% methane, 6% to 8% ethane, 4% to 6% propane, 4% to 5% butane, and 4% to 5% pentane. Carbon dioxide and CO produced in the reaction can reduce the final liquid hydrocarbon product yield. However, if the product is further hydrotreated, the loss of oxygen from these compounds will result in lower hydrogen consumption because it is no longer available to react with hydrogen to ultimately become water.

[0031] Liquid water 48 is also separated from the liquid hydrocarbon or oil phase of the reactor product 42. The metals stripped from the reactor walls of the reactor 16 and the reactors 18, 20 and carried into the cooled reactor product 42 are mainly distributed in the water phase 48, and therefore most of the metals are removed with the water 48. Some metals may also be present with the waste gas slag formed in the reactor, which is carried into the reactor product. The residual liquid hydrocarbons 50 from the separator 44 can then be introduced into another stripping device 52, where a stripping gas 53 is used to remove additional light waste gas 54 separated from the liquid hydrocarbons 56. The composition and amount of the non-condensable gas or waste gas depends on the reaction temperature. In addition, the amount of waste gas depends on the temperature and pressure of the separator. In the separators 44, 52, higher pressures and lower temperatures will result in less waste gas because these gases still remain in the liquid.

[0032] The separated liquid hydrocarbons 56 are introduced and pressurized in pump 58. The pressurized liquid hydrocarbons 60 are then filtered in a filtration device 62, such as a cartridge filter or sand filter, to remove the waste gas residue and any remaining metals and other solids to form a final treated product 64.

[0033] At high reaction temperatures, the waste gas slag (coke) formed during the reaction and the metal present in the initial raw material 12 may tend to be deposited on the walls of the reactor 16 and the reactors 18, 20. To prevent the reactors 16, 18, 20 from coking and plugging due to such substances, a high speed is maintained in the reactor system 34 by combining the pipe size to maintain a high speed, and a high-speed oxygen-free gas (i.e., no O2) (such as steam, nitrogen, CO2, hydrogen, etc.) is added to increase the speed to a greater extent. In most cases, the gas will be steam or nitrogen. In a specific embodiment, in the reactor 16, 18, 20 or reactor tube, the gas is added together with the raw material to provide a flow rate from 6m / sec to 35m / sec, more specifically from 9m / sec to 22m / sec, and still more specifically from 6m / sec to 16m / sec. As shown in 66 and 68, a high-speed gas can be added to the feed stream 12 and / or 26. If added to heated feed stream 26, the gas may be heated to about (e.g., a feed temperature of <= 30°C) or above the temperature of feed 26 to prevent a significant drop in the temperature of feed 26. In other embodiments, high velocity gases 66 and / or 68 are not preheated.

[0034] This high velocity heated feed 30 from the heat exchanger 28 is introduced into the reactors 16, 18, 20, and the walls of the reactors are kept clean due to the erosion of any waste gas slag and metal deposited on the walls by the high velocity fluid flow. Therefore, the waste gas slag and metals do not adhere to the reactor walls and are removed and carried into the reactor product stream. As previously described, the waste gas slag and metals carried into the reactor product stream are ultimately removed in the water phase 48 and / or by the filtering device 62.

[0035] The disclosed processing systems and methods can be used to remove from 50% to 99% or more to 100% by weight of metals in fresh or raw feedstock. More specifically, the disclosed methods can be used to remove from 90% to 99% or more by weight of metals in feedstock. In certain embodiments, the metal content of the initial feedstock 12 can be reduced by at least, equal to, and / or 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, and 100% by weight of the initial metal content, and / or an amount ranging between any two of the above values.

[0036] refer to Figure 2 Another processing system 70 for forming a product from a fresh or virgin non-petroleum or renewable feedstock, which feedstock may be the same or similar to feedstock 12. As shown, this may include fats and / or oils of animal and / or vegetable origin containing contaminants of oxygen and one or more of metals, gums, and resins. System 70 is similar to Figure 1 1 and 10, wherein like components are labeled with the same reference numerals. System 70 includes a treatment system 74 for removing oxygen and undesirable materials (including metals, gums, and resins) from feedstock 72 prior to any hydroprocessing or hydrotreating, such as in a renewable diesel unit. System 70 differs from system 10 in that it utilizes a recycle stream, which may allow for better control of the process, as well as facilitate higher oxygen removal.

[0037] In processing system 74, feedstock 72 is ultimately heated to a temperature of from 400°C to 595°C, or similar temperatures as previously described for system 10, in externally heated tubular reactor 16. Reactor pressures may also be the same. Figure 2Reactor 16 in is also catalyst-free, or does not contain or use a hydrogenation process catalyst.

[0038] The processing system 74 may also be provided with Figure 1 One or more secondary reactors 18, 20 that are identical or similar are located downstream and receive all or a portion of the reactor effluent stream 76 from the reactor 16. Figure 2 In the treatment system 74 of FIG. 1 , a bypass line 78 is provided for bypassing the secondary reactors 18, 20 and directing all or a portion of the reactor discharge stream 76 to the reactor product stream 80. A control valve 82 allows for selective control of the reactor product stream through the bypass line 76, such that the amount of product passing through the line 76 can be varied, wherein only a portion (e.g., from 10% to 90%) of the product discharge 76 is directed through the bypass line 78, wherein the remainder of the reactor product discharge 76 through lines 84, 86 is directed to the reactors 18, 20. In some embodiments, the valve 82 may be maintained closed during operation, such that the entire discharge product stream 22 is directed to the secondary reactors 18, 20 through lines 84, 86, respectively. In other cases, the entire product stream 22 may be directed through the bypass line 78, wherein no product stream is sent to the reactors 18, 20. Although not shown, Figure 1 A similar bypass line may be used with system 10 .

[0039] In certain applications, the heat of the high temperature reactor product 80 is also recovered and can be used to heat the feed 84 in the first stage cross heat exchanger. In the first stage of the cross heat exchanger, the feed 84 is used to cool the hot reactor product 80 from the reactor 16 and any secondary reactors 18, 20 in the heat exchanger 28. The temperature of the hot reactor product 24 is typically in the range of 400°C to 595°C and will typically be at a temperature 12.5°C to 300°C higher than the temperature of the feed 84. The heated feedstock 86 discharged from the exchanger 28 and introduced into the reactor 16 is typically at a temperature of from 370°C to 540°C.

[0040] like Figure 1 In the processing system 14, the reaction of the feed 84 begins in the heat exchanger 28 after the heated feed 86 is heated at a temperature equal to or greater than 370° C., so that it can be considered as part of the overall reactor system 90 for processing the feedstock. In other embodiments in which the feed 84 is not heated at a temperature equal to or greater than 370° C., only the primary reactor 16 and any secondary reactors 18, 20 can be considered as part of the overall reactor system 90.

[0041] In addition, the reduced temperature reactor product 88 discharged from the heat exchanger 28 can be at a temperature of from 150° C. to 370° C., wherein some, but not all, of the reactor product is condensed. The reduced temperature product 88 is generally at a temperature and condition where water is maintained in a steam or superheated state. The reduced temperature reactor product 88 is then introduced into a first "hot" separator where the condensed liquid hydrocarbons from the product stream 88 are separated from other gases into a hot liquid stream 94, such as low boiling hydrocarbons, steam and other gases (such as CO, CO2, etc.), which are discharged as a "hot" gas stream 96.

[0042] The separated liquid stream 94 passes through one or more filter devices 98, 100. These devices can be used with Figure 1 The filter devices 98 and 100 may be configured in series or in parallel. The filter devices 98 and 100 are used to filter out the waste gas slag and any entrained metals and other solids present in the liquid of the stream 94 to form a filtered liquid stream 102.

[0043] A portion (e.g., from 10% to 90%) of the filtered liquid stream 102 is used to form a recycle stream 104. The recycle stream 104 is combined with a fresh or virgin non-petroleum or renewable feedstock 106, which may be the same or similar to the feedstock 12 previously described. The combined fresh feedstock 106 and recycle stream 104 are delivered to a pumping device 108 where feedstock 72 is formed, which is a combined feedstock of fresh feedstock and recycled product. Since the recycle stream 104 is at an elevated temperature, this also aids in the heating of the fresh feedstock 106.

[0044] If necessary, the combined feedstock 72 may also be passed through a heat exchanger 110. The heat exchanger 110 may be configured as a cross heat exchanger where the separated "hot" product gas stream 96 from the separator 92 is used to heat the combined feedstock 72 to form the feed stream 84. Similarly, the combined feed stream 72, which is at a lower temperature than the product gas stream 96, may be used to further cool the gas stream 96 to form a cooled product stream 112 in which some, but not all, of the reactor products are condensed.

[0045] Such as using Figure 1 The high velocity gas described with respect to system 10 may also be added to feed streams 72 and / or 84, as shown at 66 and 68, to keep reactors 16, 18, 20 from coking and plugging with metals that would otherwise deposit on the reactor walls.

[0046] Further cooling of the cooled reactor product 112 may be performed in an additional heat exchanger 114 to form a cooled reactor product 116. The final cooled reactor product 116 will typically be at a temperature of from 35°C to 95°C.

[0047] The final cooled reactor product 116 is then introduced into one or more separators 118. Non-condensable waste gases 120 (such as CO2, CO and light hydrocarbons (i.e., C1 to C5 hydrocarbons)) generated in the reactor system 90 are separated from the cooled reactor product 116. Liquid water 122 is also separated from the liquid hydrocarbon or oil phase of the reactor product 116. The metals stripped from the reactor walls of the reactor 16 and the reactors 18, 20 and carried into the cooled reactor product 116 are mainly distributed in the water phase 122, and thus most of the metals are removed with the water 122. The residual liquid hydrocarbons 124 are introduced and pressurized in the pump 126. Although not shown, before the liquid hydrocarbons are introduced into the pump 126, a stripping device (such as Figure 1 A stripping device 53) may also be used with system 70 to remove additional light gases from stream 124. The pressurized liquid hydrocarbons 128 may then be filtered in a filtration device 130, such as a cartridge filter or a sand filter, to remove any waste gas residues and residual metals and other solids in product stream 128, thereby forming a filtered liquid product stream 132.

[0048] The portion of filtered liquid product stream 102 that is not recycled as recycle stream 104 may be combined with liquid stream 132 as liquid product stream 134 to form a final treated product 136 .

[0049] The use of recycle stream 104 in system 70 helps to further remove oxygen from the feedstock. For example, when system 10 is operated under conditions where the oxygen in the feedstock is reduced by 50%, recovering a portion of the reaction product, such as using recycle stream 104, can result in a further reduction in oxygen under similar reaction conditions. This can result in a further reduction in the oxygen content of the feedstock of 20% to 70%, allowing system 70 to remove 60% to 85% of the oxygen from the feedstock under the same reaction conditions.

[0050] In some cases, the products 64, 136 from the systems 10, 70 may be used as feedstock for further processing. Thus, each system 10, 70 may include an additional stabilization device, such as stabilization device 140, Figure 1 and 2 The intermediate products 64, 136 are stabilized here to form a stabilized product 142. This may include a hydrogenation process, wherein the stabilizer 140 includes a reactor containing a hydrogenation process catalyst, which is contacted with the products 64, 136 in the presence of hydrogen under conditions suitable for the hydrogenation process. As used herein, unless otherwise specified or obvious from the context, the term "hydrogenation process" is intended to include hydrotreating, hydrofining, hydrorefining, hydrocracking, hydroisomerization, and hydrodemetallization. The stabilizer 140 can be used to remove residual oxygen and / or olefins.

[0051] In a specific embodiment, all or a portion of the stabilized product 142 may be conveyed to a separate isomerization unit 144, with which the system 10, 70 may be provided, under conditions suitable for isomerizing the normal paraffins to isoparaffins to provide an isomerized product 146 having a selected pour point.

[0052] In some embodiments, all or a portion of the unisomerized stabilized product 142 may be directed to a fractionation unit 148 of each system 10, 70, where the product 142 may be fractionated into various products, such as a naphtha fraction 150, a renewable jet fuel fraction 152, and a renewable diesel fraction 154. Similarly, all or a portion of the isomerized product 146 may be sent to a fractionation unit 156 of each system 10, 70, where the isomerized product 146 may be fractionated into various products, such as a naphtha fraction 158, a renewable jet fuel fraction 160, and a renewable diesel fraction 162.

[0053] refer to Figure 3 , shows another embodiment of a processing system 170 for forming a product from a fresh or virgin non-petroleum or renewable feedstock, which feedstock may be the same or similar to feedstock 12. As shown, this may include fats and / or oils of animal and / or vegetable origin containing contaminants of oxygen and one or more of metals, gums, and resins. System 170 is similar to Figure 1 1 and 1 . The system 170 is similar to the system 10 in which like parts are labeled with the same reference numerals. The system 170 includes a treatment system 172 for removing oxygen, sulfur, and undesirable substances (including metals, gums, and resins) from the feedstock 12. Unless otherwise specified, the process conditions (such as flow, pressure, temperature, etc.) are the same or similar to the conditions of the system 10.

[0054] System 170 differs from system 10 in that it includes a hydroprocessing reactor 174 used within treatment system 172. Hydroprocessing reactor 174 facilitates further saturation of olefins and further reduction of the oxygen and sulfur content of the cooled reactor product 32 exiting heat exchanger 28. It also facilitates reduction or elimination of unpleasant odors that may be released from the products of reactors 16, 18, 20 without further treatment. Use of hydroprocessing reactor 174 within treatment system 170 may also eliminate the need for a stabilization unit and / or isomerization unit, such as with Figure 1 and 2 implementation scheme.

[0055] Unlike reactors 16, 18, 20, reactor 174 contains a hydrogenation process catalyst, which may be contained in a catalyst bed 176. The hydrogenation process catalyst used in reactor 174 may be those catalysts commonly used in hydrogenation process reactors to remove oxygen and other heteroatoms (such as sulfur and nitrogen) from organic compounds and for hydrogenation of unsaturated bonds. Such catalysts may be catalysts containing metals of Mo, W, Co, Ni, Pt and Pd and combinations of these, and these catalysts may be supported or unsupported catalysts. Non-limiting examples of such hydrogenation process catalysts may include MO / Al2O3, CoMo / Al2O3, CoMo / SiO2, NiMo / Al2O3, NiMo / SiO2 and NiW / Al2O3 catalysts.

[0056] The hydroprocessing reactor 174 can be configured and operated as a conventional hydroprocessing reactor. However, in other cases, the hydroprocessing reactor 174 can be a uniquely configured and operated reactor, such as the hydroprocessing reactor described in U.S. Pat. No. 10,981,142, which is hereby incorporated by reference in its entirety for all purposes. Such reactors are configured and operated to accommodate high-contaminant petroleum and non-petroleum feedstocks.

[0057] The feed to the hydroprocessing reactor 174 is the reduced temperature reactor product 32 discharged from the heat exchanger 28, which may be at a temperature of from 120° C. to 540° C. In certain embodiments, a cyclone separator or solid separator 178 may be used to remove any entrained solids transferred from the reactors 16, 18, 20 from the reduced temperature reactor product stream 32 as a solid stream 180. The remaining separated reactor product 182 is then introduced into the hydroprocessing reactor 174. The hydrogen necessary for the hydroprocessing reaction may be residual hydrogen contained in the product stream 182 from hydrogen introduced as or with the high velocity gas streams 66 and / or 68. In other embodiments, a separate hydrogen feed 184 for the hydroprocessing reaction may be introduced directly into the reactor 174 to facilitate the hydroprocessing reaction.

[0058] The hydroprocessed product 186 discharged from the reactor 174 is then introduced into the second cross heat exchanger 36 to provide further cooling to form a cooled hydroprocessed product 188. In some cases, the cooled hydroprocessed product 188 may be further cooled in another heat exchanger 40 that does not utilize the feedstock 12 as a coolant. The heat exchanger 40 may be used instead of or in addition to the heat exchanger 36. The final cooled hydroprocessed product 190 will typically be at a temperature of from 35°C to 95°C.

[0059] The final cooled hydroprocessed product 190 is then introduced into one or more separators 44. Non-condensable waste gases 192 (such as CO2, CO, H2S and light hydrocarbons (i.e., C1 to C5 hydrocarbons)) generated in the treatment system 172 are separated from the cooled hydroprocessed product 190. In one example, at a reaction temperature of 510°C, the non-condensable gases can be 75% to 80% CO2 and some CO, 1% to 2% methane, 6% to 8% ethane, 4% to 6% propane, 4% to 5% butane, and 4% to 5% pentane. The carbon dioxide and CO produced in the reaction can reduce the final liquid hydrocarbon product yield, but also reduce the amount of water formed.

[0060] Liquid water 194 is also separated from the liquid hydrocarbon or oil phase of the hydrotreated product 190. Any metals that have been stripped from the reactor walls of reactor 16 and reactors 18, 20, not removed by separator 178 and carried into the cooled hydrotreated product 190 are mainly distributed in the water phase 194, so most of the metals are removed with the water 194. Some metals may also be present with the waste gas slag formed in the reactor, which is carried into the reactor product. The residual liquid hydrocarbons 196 from separator 44 can then be introduced into another stripping device 52, where a stripping gas 198 is used to remove additional light waste gas 200 separated from the liquid hydrocarbons 202. The composition and amount of non-condensable gases or waste gases depend on the reaction temperature. At the same time, the amount of waste gas also depends on the temperature and pressure of separator 52. In separators 44, 52, higher pressures and lower temperatures will result in less waste gas because the gas still remains in the liquid.

[0061] The separated liquid hydrocarbons 202 are introduced and pressurized in pump 58. The pressurized liquid hydrocarbons 204 are then filtered in a filtration device 62, such as a cartridge filter or sand filter, to remove the waste gas residue and any remaining metals and other solids to form a final hydroprocessed product 206.

[0062] In some embodiments, all or a portion of the final hydrotreated product 206 may be conveyed to a fractionation unit 208 where the product 206 may be fractionated into various products, such as a naphtha fraction 210 , a renewable jet fuel fraction 212 , and a renewable diesel fraction 214 .

[0063] Figure 4 Another processing system 220 is shown for forming a product from a fresh or virgin non-petroleum or renewable feedstock, which may be the same or similar to feedstock 12. As previously described, this may include animal-derived and / or vegetable-derived fats and / or oils containing oxygen and contaminants of one or more of metals, gums, and resins. System 220 is similar to Figure 2220 is similar to system 70 in that like components are labeled with the same reference numerals. System 220 includes a treatment system 222 for removing oxygen, sulfur, and undesirable materials (including metals, gums, and resins) from feedstock 72. Unless otherwise specified, process conditions (e.g., flow rates, pressures, temperatures, etc.) are the same or similar to those of system 70. System 220 differs from system 70 in that it includes a hydrogenation process reactor 220 used within treatment system 222. Figure 3 The system 170 of the present invention can eliminate the need for a stabilizer and / or isomerization unit by using a hydrogenation process reactor 224 in the treatment system 222, such as using Figure 1 and 2 The hydroprocessing reactor 224 saturates the olefins and also greatly reduces the final oxygen and sulfur content in the final hydroprocessed product. It also helps to reduce or eliminate the unpleasant odors that may be emitted from the products of the reactors 16, 18, 20 without further treatment.

[0064] The hydrogenation process reactor 224 includes a catalyst bed 226 containing a hydrogenation process catalyst. The reactor 224 may be Figure 3 The reactors 174 in are configured and operated identically or similarly, contain the same catalyst, and operate under the same or similar reaction conditions.

[0065] The feed to the hydrogenation process reactor 224 is formed from the cooled reactor product 88 of the reactors 16, 18, 20, which may be at a temperature of from 120° C. to 540° C. In certain embodiments, a cyclone separator or solids separator 230 may be used to remove any entrained solids 232 transferred from the reactors 16, 18, 20 from the product stream 88.

[0066] The reactor product 234 separated from the cyclone separator 230 is then introduced into the liquid / vapor separator 92. Figure 4 In the embodiment of the present invention, the still hot liquid stream 238 separated from the separator 92 can be passed through another heat exchanger 240. The separated liquid stream 238 can be cooled to a temperature of 35° C. to 95° C. in the heat exchanger 240. The cooled stream 242 is then introduced into one or more separators 244, where non-condensable waste gases 246 and liquid water 248 are separated from liquid hydrocarbons, which are discharged from the separator 244 as stream 250.

[0067] The separated liquid hydrocarbon stream 250 then passes through filter devices 98, 100 arranged in series or in parallel. The filter devices 98, 100 are used to filter out the waste gas residue and any entrained metals and other solids still present in the liquid of stream 250 to form a filtered liquid stream 252.

[0068] A portion (e.g., from 10% to 90%) of the filtered liquid stream 252 is used to form a recycle stream 254. The recycle stream 254 is combined with a fresh or virgin non-petroleum or renewable feedstock 106, which may be the same or similar to the previously described feedstock 12. The combined fresh feedstock 106 and recycle stream 254 are delivered to a pumping device 108 where feedstock 72 is formed, which is a combination of fresh feedstock and recycled product.

[0069] The separated vapor phase 260 from the product stream 234 separated in the separator 92 is introduced into the hydrogenation process reactor 224 under reaction conditions suitable for the hydrogenation process. The hydrogen necessary for the hydrogenation process reaction may be residual hydrogen contained in the vapor product stream 260 from the hydrogen introduced as or with the high velocity gas streams 66 and / or 68. In other embodiments, a separate hydrogen feed 262 for the hydrogenation process reaction may be introduced directly into the reactor 224.

[0070] The hydrotreated product 264 from the reactor 224 is then introduced into the second crossover heat exchanger 110 to provide further cooling to form a cooled hydrotreated product 268. The combined fresh and recycled feedstock 72 may be passed through the heat exchanger 110. The heat exchanger 110 may be configured as a crossover heat exchanger, wherein the "hot" hydrotreated product stream 264 is used to heat the combined feedstock 72 to form the feed stream 84. Similarly, the combined feed stream 72, which is at a lower temperature than the hydrotreated product stream 264, may be used to further cool the hydrotreated stream 264 to form a cooled hydrotreated product stream 268, wherein some, but not all, of the reactor products may be condensed.

[0071] In some cases, the cooled reactor hydroprocessed product 268 may be further cooled in an additional heat exchanger 114 that does not utilize feedstock 72 as a cooling fluid. Heat exchanger 114 may be used in place of or in addition to heat exchanger 110. The final cooled hydroprocessed product 268 will typically be at a temperature of from 35°C to 95°C.

[0072] The final cooled hydroprocessed product 268 is then introduced into one or more separators 118. Non-condensable waste gases 270 (such as CO2, CO, H2S and light hydrocarbons (i.e., C1 to C5 hydrocarbons)) generated in the treatment system 222 are separated from the cooled hydroprocessed product 268. In one example, at a reaction temperature of 510°C, the non-condensable gases can be 75% to 80% CO2 and some CO, 1% to 2% methane, 6% to 8% ethane, 4% to 6% propane, 4% to 5% butane, and 4% to 5% pentane. Carbon dioxide and CO generated in the reaction can reduce the final liquid hydrocarbon product yield.

[0073] Liquid water 272 is also separated from the liquid hydrocarbon or oil phase of the cooled hydrotreated product 268. Metals that have been stripped from the reactor walls of reactor 16 and reactors 18, 20 and carried into the cooled product 268 without being removed by separators 230, 244 are mainly distributed in the water phase 272, so most of the metals are removed with the water 272. The remaining liquid hydrocarbons 274 are introduced and pressurized in pump 126. Although not shown, a stripping device (such as a stripping device) is provided before the liquid hydrocarbons are introduced into pump 126. Figure 3 The stripping device 198 of the system 220 can also be used with the system 220 to remove additional light gases from the stream 274. The pressurized liquid hydrocarbons 276 can then be filtered in the filtering device 130 (such as a cartridge filter or a sand filter) to remove any waste gas residues and residual metals and other solids in the product stream 276, thereby forming a filtered liquid product stream 278.

[0074] The portion of the filtered liquid product stream 252 that is not recycled as the recycle stream 254 may be combined with the liquid hydrotreated product stream 278 as a liquid product stream 280 to form a final treated product 282 .

[0075] In some embodiments, all or a portion of the final processed product 282 may be conveyed to the fractionation unit 208 where the product 282 may be fractionated into various products, such as a naphtha fraction 210 , a renewable jet fuel fraction 212 , and a renewable diesel fraction 214 .

[0076] From Figure 1-4 The final processed products 64, 136, 206 and 282 of each treatment system 10, 70, 170 and 220 in the present invention have unique characteristics. As previously mentioned, the gum and resin content in the initial raw material is significantly reduced or completely eliminated, wherein the gum and resin are converted into useful products or other harmless compounds. In most cases, in the final product, almost no detectable solids indicating the presence of gums and resins in the final product are found. In addition, the product can be further processed in a renewable diesel device without causing clogging problems.

[0077] Metal is also removed so that the metal from 90% to 99.9% or even to 100% is removed in the initial raw material.Therefore, the final product can only contain a very small amount of metal or be metal-free.If any metal really remains in the final product, such residual metal contaminants can be present in the final product with the amount of only from 0.00001ppm to 100ppm by the total product weight.In certain embodiments, total metal contaminants can be present in the final product with the amount and / or scope of at least, equal to 0ppm, 0.00001ppm, 0.0001ppm, 0.001ppm, 0.01ppm, 0.1ppm, 0.5ppm, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 15ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm and 100ppm by the total product weight in any two amounts between the above numerical values.

[0078] The final products 64, 136, 206, 282 may have a specific gravity of from 0.73 to 0.85 and a viscosity of from 0.5 cSt (5 x 10 -7 m 2 / s) to 5cSt(5x10 -6 m 2 In certain embodiments, the final product may have a specific gravity of at least or equal to 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, and 0.85 and / or a specific gravity ranging between any two of the above values. And the final product may have a viscosity of at least or equal to 0.5 cSt (5x10 -7 m 2 / s)、0.6cSt(6x10 -7 m 2 / s)、0.7cSt(7x10 -7 m 2 / s)、0.8cSt(8x10 -7 m 2 / s)、0.9cSt(9x10 -7 m 2 / s)、1.0cSt(1x10 -6 m 2 / s), 1.1cSt(1.1x10 -6 m 2 / s), 1.2cSt(1.2x10 -6 m 2 / s), 1.3cSt(1.3x10 -6 m2 / s)、1.4cSt(1.4x10 -6 m 2 / s)、1.5cSt(1.5x10 -6 m 2 / s)、1.6cSt(1.6x10 -6 m 2 / s)、1.7cSt(1.7x10 - 6 m 2 / s)、1.8cSt(1.8x10 -6 m 2 / s)、1.9cSt(1.9x10 -6 m 2 / s)、2.0cSt(2.0x10 -6 m 2 / s)、2.1cSt(2.1x10 -6 m 2 / s)、2.2cSt(2.2x10 -6 m 2 / s)、2.3cSt(2.3x10 -6 m 2 / s)、2.4cSt(2.4x10 -6 m 2 / s)、2.5cSt(2.5x10 -6 m 2 / s)、2.6cSt(2.6x10 -6 m 2 / s)、2.7cSt(2.7x10 -6 m 2 / s)、2.8cSt(2.8x10 -6 m 2 / s)、2.9cSt(2.9x10 -6 m 2 / s)、3.0cSt(3.0x10 -6 m 2 / s)、3.1cSt(3.1x10 -6 m 2 / s)、3.2cSt(3.2x10 - 6 m 2 / s)、3.3cSt(3.3x10 -6 m 2 / s)、3.4cSt(3.4x10 -6 m 2 / s)、3.5cSt(3.5x10 -6 m2 / s), 3.6cSt(3.6x10 -6 m 2 / s), 3.7cSt(3.7x10 -6 m 2 / s), 3.8cSt(3.8x10 -6 m 2 / s), 3.9cSt(3.9x10 -6 m 2 / s)、4.0cSt(4.0x10 -6 m 2 / s), 4.1cSt(4.1x10 -6 m 2 / s), 4.2cSt(4.2x10 -6 m 2 / s), 4.3cSt(4.3x10 -6 m 2 / s), 4.4cSt(4.4x10 -6 m 2 / s), 4.5cSt(4.5x10 -6 m 2 / s), 4.6cSt(4.6x10 -6 m 2 / s), 4.7cSt(4.7x10 - 6 m 2 / s), 4.8cSt(4.8x10 -6 m 2 / s), 4.9cSt(4.9x10 -6 m 2 / s) and 5.0cSt(5.0x10 -6 m 2 / s) and / or a viscosity ranging between any two of the above values.

[0079] In the case of products 206, 282 that have been subjected to a hydrogenation process, the final products 209, 282 may have a specific gravity of from 0.75 to 0.80 and a viscosity of from 0.5 cSt to 2 cSt. The pour point of the hydrotreated products 206, 282 may be 35°F (1.67°C) or lower. In certain embodiments, the hydrotreated products 206, 282 may have a specific gravity of at least, equal to, 0.75, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, and 0.80 and / or a specific gravity ranging between any two of the above values. And the hydrotreated products 209, 282 may have a specific gravity of at least, equal to, 0.5 cSt (5x10 -7 m 2 / s)、0.6cSt(6x10 -7 m 2 / s)、0.7cSt(7x10 -7 m 2 / s)、0.8cSt(8x10 -7 m 2 / s)、0.9cSt(9x10 -7 m 2 / s)、1.0cSt(1x10 -6 m 2 / s), 1.1cSt(1.1x10 -6 m 2 / s), 1.2cSt(1.2x10 -6 m 2 / s), 1.3cSt(1.3x10 -6 m 2 / s), 1.4cSt(1.4x10 -6 m 2 / s), 1.5cSt(1.5x10 -6 m 2 / s), 1.6cSt(1.6x10 -6 m 2 / s), 1.7cSt(1.7x10 -6 m 2 / s), 1.8cSt(1.8x10 - 6 m 2 / s), 1.9cSt(1.9x10 -6 m 2 / s), 2.0cSt(2.0x10 -6 m 2 / s) and / or a viscosity ranging between any two of the above values.

[0080] The final oxygen content of the final product 64, 136, 206, 282 is typically 6%, 5%, 4%, 3%, 2%, 1%, 0.5% or less based on the total weight of the final product. In certain embodiments, the oxygen content can be at least, equal to, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, based on the total weight of the final product. t%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3.0wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3. 8wt%, 3.9wt%, and 4.0wt%, 4.1wt%, 4.2wt%, 4.3wt%, 4.4wt%, 4.5wt%, 4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, 5.0wt%, 5.1wt%, 5.2wt%, 5.3wt%, 5.4wt%, 5.5wt%, 5.6wt%, 5.7wt%, 5.8wt%, 5.9wt%, 6.0wt%, 6.1wt%, 6.2wt%, 6.3wt%, 6.4wt%, 6.5wt %, 6.6wt%, 6.7wt%, 6.8wt%, 6.9wt%, 7.0wt%, 7.1wt%, 7.2wt%, 7.3wt%, 7.4wt%, 7.5wt%, 7.6wt%, 7.7wt%, 7.8wt%, 7.9w %, 8.0wt%, 8.1wt%, 8.2wt%, 8.3wt%, 8.4wt%, 8.5wt%, 8.6wt%, 8.7wt%, 8.8wt%, 8.9wt%, 9.0wt%, 9.1wt%, 9.2wt%, 9.3wt%, 9.4wt%, 9.5wt%, 9.6wt%, 9.7wt%, 9.8wt%, 9.9wt% and 10.0wt% and / or an amount ranging between any two of the above values ​​is present in the final products 64, 134, 206, 282.

[0081] The final product 64, 136, 206, 282 can also be composed of: 25wt%, 20wt%, 15wt%, 10wt%, or 5wt% or less of any triglycerides, monoglycerides, diglycerides, free fatty acids, phospholipids, sterols, tocopherols, tocotrienols, and fatty alcohols, from 5wt% to 30wt% naphtha, 50wt% or more diesel, and 5wt% or less olefins. In specific embodiments, the total amount of triglycerides, monoglycerides, diglycerides, free fatty acids, phospholipids, sterols, tocopherols, tocotrienols and fatty alcohol compounds can be present in the final product in an amount of at least, equal to, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, and 25 wt%, based on the total weight of the final product, and / or an amount ranging between any two of the above values.

[0082] Naphtha can be present in the final product in an amount from 5 wt% to 30 wt% based on the total weight of the final product 64, 136, 206, 282. As used herein, unless otherwise specified, "naphtha" is generally defined as a hydrocarbon fraction having a Reid vapor pressure of 70 kPa or less at 1 atmosphere and a final boiling point of 166° C. or less. In certain applications, naphtha may be present in the final product 64, 136, 206, 282 in an amount of at least, equal to, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, and 30wt%, based on the total weight of the final product and / or an amount ranging between any two of the above values.

[0083] Renewable jet fuel (i.e., sustainable aviation fuel) can be present in the final product 64, 136, 206, 282 in an amount from 5 wt% to 50 wt%. In certain instances, the renewable jet fuel fraction can be present in an amount of at least, equal to, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 9wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt% and 50wt% and / or an amount ranging between any two of the above values ​​is present in the final products 64, 136, 206, 282.

[0084] Diesel fuel can be present in the final product 64, 136, 206, 282 in an amount of 50 wt% or more based on the total weight of the final product. As used herein, unless otherwise specified, "diesel fuel" is generally defined as a hydrocarbon fraction having a flash point below 52° C. at 1 atmosphere, wherein 90% of the components have a boiling point of 338° C. or less. In some embodiments, the diesel fuel can be present in an amount of at least, equal to, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 100 wt%, 101 wt%, 102 wt%, 103 wt%, 104 wt%, 105 wt%, 106 wt%, 107 wt%, 108 wt%, 109 wt%, 110 %, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt% and 90wt% and / or an amount ranging between any two of the above values ​​is present in the final products 64, 136, 206, 282.

[0085] The olefin may be present in the final product 64, 136, 206, 282 in an amount of 5 wt% or less. In certain instances, the olefin may be present in an amount of at least, equal to, 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, 3.0 wt%, 3.1 wt%, 3.2 wt%, 3.3 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.7 wt%, 3.8 wt%, 3.9 wt%, 4.0 wt%, 4.1 wt%, 4.2 wt%, 4.3 wt%, 4.4 wt%, 4.5 wt%, 4.6 wt%, 4.7 wt%, 4.8 wt%, 4.9 wt%, 4. %, 4.8wt%, 4.9wt%, and 5.0wt% and / or an amount ranging between any two of the above values ​​is present in the final product 64 or 136.

[0086] In many cases, the final products 64, 136, 206, 282 from each processing system 10, 70, 170, 220, respectively, can meet the requirements of ASTM D975 for renewable diesel without further processing (such as hydroprocessing or isomerization). In other cases, whether or not the requirements of ASTM D975 for renewable diesel are met, the final product can undergo a hydroprocessing and / or isomerization.

[0087] In some cases, the product 64, 136, 206, 282 from any system 10, 70, 170, 220 can be used as a feedstock for further processing. Therefore, each of the systems 10, 70, 170, 220 can include additional stabilization devices, such as stabilization device 140, Figure 1 and 2 The intermediate product 64, 136 is stabilized here to form a stabilized product 142. This may include a hydrogenation process, wherein the stabilizer 140 includes a reactor containing a hydrogenation process catalyst, which is contacted with the product 64, 136 in the presence of hydrogen under conditions suitable for the hydrogenation process.

[0088] The stabilized product 142 may have a specific gravity of from 0.75 to 0.80, from 0.5 cSt (5 x 10 -7 m 2 / s) to 2cSt(2x10 -6 m 2 / s) viscosity, and 0.2 wt% or less oxygen content. The pour point of the stable product can be 35 ° F (1.67 ° C) or less. In certain embodiments, the stable product 142 can have a specific gravity of at least, equal to, 0.75, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79 and 0.80 and / or a specific gravity ranging between any two of the above values. And the stable product 142 can have at least, equal to, 0.5 cSt (5x10 -7 m 2 / s)、0.6cSt(6x10 -7 m 2 / s)、0.7cSt(7x10 -7 m 2 / s)、0.8cSt(8x10 -7 m 2 / s)、0.9cSt(9x10 -7 m 2 / s)、1.0cSt(1x10 -6 m 2 / s), 1.1cSt(1.1x10 -6 m 2 / s), 1.2cSt(1.2x10 -6 m 2 / s), 1.3cSt(1.3x10 -6 m 2 / s), 1.4cSt(1.4x10 -6 m 2 / s), 1.5cSt(1.5x10 -6 m 2 / s), 1.6cSt(1.6x10 - 6 m 2 / s), 1.7cSt(1.7x10 -6 m 2 / s), 1.8cSt(1.8x10 -6 m 2 / s), 1.9cSt(1.9x10 -6 m 2 / s), 2.0cSt(2.0x10 -6 m 2 / s) and / or a viscosity ranging between any two of the above values.

[0089] In certain embodiments, all or a portion of the stabilized product 142 may be conveyed to a separate isomerization unit 144, with which the system 10, 70 may be provided, under conditions suitable for isomerizing the normal paraffins to isoparaffins to provide an isomerized product 146 having a selected pour point.

[0090] In some embodiments, all or a portion of the unisomerized stable product 142 may be directed to a fractionation unit 148 of each system 10, 70, where the product 142 may be fractionated into various products, such as a naphtha fraction 150, a renewable jet fuel fraction 152, and a renewable diesel fraction 154. Similarly, all or a portion of the isomerized product 146 may be sent to a fractionation unit 156 of each system 10, 70, where the isomerized product 146 is fractionated into various products, such as a naphtha fraction 158, a renewable jet fuel fraction 160, and a renewable diesel fraction 162.

[0091] exist Figure 3 and 4 In the case of systems 170, 220, these systems utilize a hydrogenation process reactor to form final products 206, 282, respectively, which may not undergo further stabilization or isomerization. Products 206, 282 may have similar properties to products 64, 136 of systems 10, 70 that have undergone stabilization and / or isomerization.

[0092] As in conventional renewable diesel processes, while the product may undergo hydroprocessing, stabilization, and / or separation isomerization, this should be distinguished from the hydroprocessing and isomerization utilized in conventional renewable diesel processing systems.

[0093] Since the product of the treatment system 10, 70, 170, 220 has a significantly lower oxygen content than conventional renewable diesel feedstocks, the amount of hydrogen required for further hydrogenation processes is significantly lower. For example, in conventional renewable diesel hydroprocessing systems, the typical amount of hydrogen (H2) required for a given feedstock may be between 1,500 scf / bbl and 4,000 scf / bbl (675 SCM / m 3 Up to 1801SCM / m 3 ). Using products 64, 136, 206, 282 from the same initial feedstock as the feedstock for the hydrogenation process, the amount of hydrogen required can be reduced from 30% to 90%. Thus, for example, 3000 scf / bbl (1351 SCM / m 3 ) When hydrogen is used to process a given feedstock, the amount of hydrogen required to stabilize products 64, 136, 206, 282 from the same initial feedstock may be 300 scf / bbl to 1500 scf / bbl (127 SCM / m3 Up to 675SCM / m 3 ) to form similar or comparable products. In addition, the operating pressure for the hydrogenation process in a conventional renewable diesel plant may be much higher, around 6200 kPa or higher. In order to form comparable products in the stabilizer 140 using the treated initial feedstock, the operating pressure may be around 2,000 kPa. Since plant costs increase linearly with operating pressure, reducing the operating pressure of a given process can greatly reduce plant construction costs.

[0094] In some embodiments, the stabilizer 140 for the hydroprocessed products 64, 136 can be a liquid phase hydrogenation process reactor system that utilizes a liquid diluent combined with a feedstock for dissolving the hydrogen required for the reaction. Such hydrogenation process systems and methods are described in U.S. Patent Nos. 9,096,804; 9,828,552; 10,487,268; 10,961,463 and 10,981,142, each of which is hereby incorporated by reference in its entirety for all purposes. Alternatively, the stabilizer 140 can be configured as a conventional hydrogenation process unit, similar to a conventional renewable diesel unit, in which a large amount of hydrogen is circulated in the reactor with the feedstock. Compared to conventional hydrogenation processes or hydrotreating units, the stabilizer 140 will generally require significantly less hydrogen and significantly lower reactor pressures than conventional processing equipment.

[0095] Additionally, since a large portion of the oxygen is removed from the products 64, 136, 206, 282, less water is produced in the stabilizer 140 and therefore there is no risk of water damaging the hydrogenation process catalyst or producing a separate aqueous phase.

[0096] With respect to isomerization, the product from a conventional renewable diesel plant typically contains a large amount of wax or normal paraffins and may, for example, have a cloud point of around 21° C. With the same initial feedstock, the product 142 of the treatment systems 10 and 70 hydrotreated in the stabilizer 140 is significantly different from the product hydrotreated in a conventional renewable diesel plant. Even after hydrotreatment in the stabilizer 140, there is less wax or normal paraffins in the stabilized product 142. Without any isomerization treatment, the stable product 142 will typically have a cloud point of 2.0°C, 1.5°C, 1.0°C, 0.5°C, 0°C, -0.5°C, -1.0°C, -1.5°C, -2.0°C, -2.5°C, -3.0°C, -3.5°C, -4.0°C, -4.5°C, -5.0°C, -5.5°C, -6.0°C, -6.5°C, -7.0°C, -7.5°C, -8.0°C, -8.5°C, -9.0°C, or -9.5°C or less. This is much lower than the hydroprocessed product from a conventional renewable diesel unit.

[0097] One of the advantages of the processing method and system 10, 70, 170, 220 is that it helps reduce GHG emissions. The method and system not only utilizes renewable feedstocks that have a lower environmental impact, but assuming that the feedstock received by the system 10, 70, 170, 220 has a CI score of zero, the stable product 142 produced from the system 10, 70 and the final product 206, 282 of the system 170, 220 meet the standards of renewable diesel, but will have a CI score of 10g / MJ or less (as established by the California LCFS standards of 2018). This is based on the natural gas fuel used for the reactor 16, 18, 20, and the power consumption of the various power equipment used to operate the system 10, 70, 170, 220. The power consumption used to calculate the CI value includes the power used to operate the pump device for the initial feedstock (e.g., pump 108), the pump device for the product (e.g., pump device 58, 126), and the forced convection heat exchanger (e.g., heat exchanger 40, 114). The thermal reaction products of the system help to heat the renewable raw materials, and the renewable raw materials help to cool the thermal reaction products. And using combustible waste gas as the fuel of system 10, 70 helps to further reduce CI. In certain embodiments, the stable product 142 will have a CI score of 10g / MJ, 9g / MJ, 8g / MJ, 7g / MJ, 6g / MJ, 5g / MJ, 4g / MJ, or 3g / MJ or less. This is in contrast to traditional renewable diesel products, which will generally still have a CI value of around 20g / MJ even if the initial CI score of the raw material is assumed to be zero.

[0098] The following examples are used to further illustrate various embodiments and applications.

[0099] Examples

[0100] Example 1

[0101] In a laboratory test plant, tank bottoms from distilled corn oil with high gum, resin, water and metal content were treated at 600 psig (413 g kPa) and 900°F (483°C) through a fired heater for a few seconds. The treated product was cooled to separate water and waste gas from the hydrocarbon phase. The final product contained trace amounts of water, 4 wt% waste gas and 96 vol% hydrocarbon liquid. The hydrocarbon liquid contained 19 vol% naphtha and 77 vol% diesel relative to the feed.

[0102] Although the present invention has been shown in only some forms, it should be apparent to those skilled in the art that it is not so limited but is susceptible to various changes and modifications without departing from the scope of the present invention. Therefore, it is appropriate that the present invention should be broadly understood.

Claims

1. A method of treating a non-petroleum or renewable feedstock containing oxygen and one or more of the following contaminants: metals, gums, and resins, the method comprising: Introducing a non-petroleum or renewable feedstock having an oxygen content of 8 wt % or more based on the total weight of the feedstock into a reactor at a flow rate of at least 6 m / sec, heating the feedstock in the reactor to a temperature of 370° C. to 595° C. to remove and / or reduce the content of one or more of gums and resins in fats and / or oils of the feedstock to form a reactor product; cooling the reactor product to a temperature of 125°C to 370°C to form a reduced temperature reactor product; introducing at least a portion of the letdown reactor product as a feed into a hydroprocessing reactor containing a hydroprocessing catalyst to form a hydroprocessed product; cooling the hydroprocessed product to a temperature of 125° C. or less to form a cooled hydroprocessed product; and Non-condensable gases, metals and water are separated and removed from the cooled hydrotreated product to form a final product having an oxygen content of 60% or less of the feed oxygen content and wherein the final product contains 25 wt % or less of any triglycerides, monoglycerides, diglycerides, free fatty acids, phospholipids, sterols, tocopherols, tocotrienols, and fatty alcohols, from 5 wt % to 30 wt % naphtha and 50 wt % or more diesel.

2. The method of claim 1, wherein: The final product meets the requirements of ASTM D975 for renewable diesel.

3. The method of claim 1, wherein: Without further treatment, the final product has a specific gravity ranging from 0.73 to 0.85, a specific gravity ranging from 0.5 cSt (5x10 -7 m 2 / s) to 5cSt(5x10 -6 m 2 / s) viscosity, and an oxygen content of 6wt% or less.

4. The method of claim 1, wherein: Without further treatment, the final product has a specific gravity ranging from 0.75 to 0.8, a specific gravity ranging from 0.5 cSt (5x10 -7 m 2 / s) to 2cSt(2x10 -6 m 2 / s) viscosity, and 0.2wt% or less oxygen content.

5. The method of claim 1, further comprising: At least a portion of the final product is fractionated into at least one of a naphtha fraction, a renewable jet fuel fraction, and a renewable diesel fraction.

6. The method of claim 1, wherein: Without further treatment, the final product has a pour point of 2°C or less.

7. The method of claim 1, wherein: Based on the 2018 California LCFS standard, when the feedstock has a CI selected as 0, the final product produced has a fuel carbon intensity score (CI) of 10gCO2e / MJ (grams of CO2 emissions / MJ fuel) or less.

8. The method of claim 1, further comprising: separating gas and liquid from the coolant reactor product, wherein the liquid separated from the coolant reactor product is recycled and introduced into the reactor together with the feedstock; And wherein: the gas separated from the coolant reactor product forms the feed introduced into the hydrogenation process reactor.

9. The method of claim 1, wherein: The final product has an oxygen content of 40% or less of the oxygen content of the feedstock.

10. The method of claim 1, wherein: The feedstock has at least one or more of triglycerides, monoglycerides, diglycerides, free fatty acids, phospholipids, sterols, tocopherols and tocotrienols, and fatty alcohols in an amount of 50 wt% or more based on the total weight of the feedstock.

11. The method of claim 1, wherein: The feedstock has 1 wt% or more of contaminants of one or more of metals, gums, and resins.

12. The method of claim 1, wherein: The final product comprises 20 wt% or less of any triglycerides, monoglycerides, diglycerides, free fatty acids, phospholipids, sterols, tocopherols, tocotrienols, and fatty alcohols; from 10 wt% to 30 wt% of naphtha; and 60 wt% or more of diesel; and wherein: the composition has a specific gravity of from 0.73 to 0.85, from 0.5 cSt (5 x 10 -7 m 2 / s) to 5cSt(5x10 -6 m 2 / s) and an oxygen content of 6wt% or less.

13. A method of processing a non-petroleum or renewable feedstock containing oxygen and one or more of the following contaminants: metals, gums, and resins, the method comprising: Introducing a non-petroleum or renewable feedstock into a reactor at a flow rate of from 6 m / sec to 35 m / sec, the feedstock having at least one or more of triglycerides, monoglycerides, diglycerides, free fatty acids, phospholipids, sterols, tocopherols and tocotrienols, and fatty alcohols in an amount of 50 wt% or more, based on the total weight of the feedstock, and having contaminants of one or more of metals, gums, and resins in an amount of 1 wt% or more, based on the total weight of the feedstock, and an oxygen content of 8 wt% or more, based on the total weight of the feedstock, heating the feedstock in the reactor to a temperature of 370° C. to 595° C. to remove and / or reduce the content of one or more of gums and resins in the fat and / or oil of the feedstock to form a reactor product; cooling the reactor product to a temperature of 125°C to 370°C to form a reduced temperature reactor product; introducing at least a portion of the letdown reactor product as a feed into a hydroprocessing reactor containing a hydroprocessing catalyst to form a hydroprocessed product; cooling the hydroprocessed product to a temperature of 125° C. or less to form a cooled hydroprocessed product; and Separating and removing non-condensable gases, metals and water from the cooled hydrotreated product to form a final product having an oxygen content of 60% or less of the oxygen content of the feedstock, and wherein the final product comprises 25 wt% or less of any triglycerides, monoglycerides, diglycerides, free fatty acids, phospholipids, sterols, tocopherols, tocotrienols and fatty alcohols, from 5 wt% to 30 wt% of naphtha and 50 wt% or more of diesel, and wherein without further treatment, the final product has a specific gravity of from 0.73 to 0.85, a viscosity of from 0.5 cSt (5 x 10 -7 m 2 / s) to 5cSt(5x10 -6 m 2 / s) and an oxygen content of 6wt% or less.

14. The method of claim 13, wherein: The final product meets the requirements of ASTM D975 for renewable diesel.

15. The method of claim 13, wherein: Without further treatment, the final product has a specific gravity ranging from 0.73 to 0.85, a specific gravity ranging from 0.5 cSt (5x10 -7 m 2 / s) to 5cSt(5x10 -6 m 2 / s) viscosity, and an oxygen content of 6wt% or less.

16. The method of claim 13, wherein: Without further treatment, the final product has a specific gravity ranging from 0.75 to 0.8, a specific gravity ranging from 0.5 cSt (5x10 -7 m 2 / s) to 2cSt(2x10 -6 m 2 / s) and an oxygen content of 0.2 wt% or less.

17. The method of claim 13, further comprising: At least a portion of the final product is fractionated into at least one of a naphtha fraction, a renewable jet fuel fraction, and a renewable diesel fraction.

18. The method of claim 13, wherein: Without further processing, the final product has a pour point of 35°F (1.67°C) or less.

19. The method of claim 13, wherein: Based on the 2018 California LCFS standard, when the feedstock has a CI selected as 0, the final product produced has a fuel carbon intensity score (CI) of 10gCO2e / MJ (grams of CO2 emissions / MJ fuel) or less.

20. The method of claim 13, further comprising: separating gas and liquid from the coolant reactor product, wherein the liquid separated from the coolant reactor product is recycled and introduced into the reactor together with the feedstock; And wherein: the gas separated from the coolant reactor product forms the feed introduced into the hydrogenation process reactor.

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