KR20230131487A - Production of lube base oil using unconverted oil - Google Patents

Abstract

A method of producing a lube base oil product by hydrotreating the unconverted oil from a hydrocracker in an unconverted oil upgrading reactor to produce upgraded unconverted oil and dewaxing the upgraded unconverted oil to produce a lube base oil product.

Description

Production of lube base oil using unconverted oil

Cross-reference to related applications

This application claims the benefit of priority to U.S. Provisional Application Serial Nos. 63/138,940, filed January 19, 2021, and 63/138,779, filed January 18, 2021, the disclosures of which are incorporated in their entirety. It is integrated into the main hospital.

technology field

The present disclosure relates to methods and systems for producing base oil products, methods for modifying base oil product manufacturing processes and systems, base oil products, lubricants, and associated uses.

Lube base oil supplies applications as a base stock for the manufacture of lubricants. The American Petroleum Institute (API) classifies lube base oils into five grades I-V. API grades I-III relate to base oils refined from crude petroleum and are distinguished by sulfur content, saturation level and viscosity index (VI), while grades IV and V refer to base oils from synthetic base oils or other sources, e.g. For example, it relates to a lubricating base oil obtained from silicon). While Class I and Class II base oils require a VI of 80 to 120, base oils refined from petroleum must achieve a VI of greater than 120 to qualify as Class III base oils.

Grade I to III lube base oils are produced by refining crude petroleum. Grade I base oils are the least refined type and can be produced by solvent-refined or hydrotreated crude oil spills. Grade II base oils are typically produced from hydrocracking effluents and are therefore more refined than Grade I base oils. The most refined Class III lube base oils have typically undergone significant hydrocracking, hydroisomerization and/or hydrotreating processes. Dewaxing by either physical or chemical processes is typically necessary to reduce the wax content for all grades I-III.

Due to the high values of VI required, high-quality feedstocks (e.g. straight-run vacuum gas oils obtained from light or medium crude oils) are typically used in the production of Group III lube base oils. do. The production of Group III lube base oils from lower-quality, heavier feedstocks (including, for example, those obtained from upgraded bottoms fractions (such as heavy coker gas oil) or heavier crude oils) is desirable. . However, it can be difficult to achieve the VI required for qualification as a Class III lube base oil when starting with these lower-quality, heavier feedstocks. In general, improved methods and systems for increasing the VI of lube base oils produced from any type of feedstock would be desirable.

According to a first aspect, a method of producing a lube base oil product is provided. The method includes: hydrotreating unconverted milk from a hydrocracker to produce upgraded unconverted oil; and dewaxing the upgraded unconverted oil to produce a lubricant base oil product.

It will be appreciated that hydrocracking generally involves contacting a hydrocarbonaceous feedstock with a hydrocracking catalyst in the presence of hydrogen, resulting in cracking and hydrogenation of longer hydrocarbon molecules and production of smaller hydrocarbon molecules. Hydrocarbon feedstocks, such as gas oil (e.g. vacuum gas oil (VGO), atmospheric gas oil, coker gas oil, e.g. heavy coker gas oil (HCGO), visbreaker gas oil), demetallized oil, vacuum residue, atmospheric residue , hydrocracking of deasphalted oils, Fischer-Tropsch streams and/or FCC streams, for example, to remove impurity products (e.g. hydrogen sulfide (H ₂ S) and ammonia (NH ₃ )). ), light oils (e.g., refinery gas, propane, butane, and naphtha), middle distillate products (e.g., jet, kerosene, and diesel), and unconverted oil (UCO). . Therefore, unconverted oil is the portion of hydrocracker effluent that remains when impure products, light oils and middle distillates have been removed. Unconverted milk typically has a boiling point ranging from about 662°F to about 1112°F (i.e., about 350°C to 600°C). Unconverted oil can be separated from other components of the hydrocracker effluent by fractional distillation.

The method includes hydroprocessing unconverted oil from a hydrocracker to produce upgraded unconverted oil. Therefore, the input to this process may be unconverted oil from the hydrocracker. In other words, the method of the first aspect includes: providing or obtaining unconverted milk from a hydrocracker; and hydrotreating the unconverted oil from the hydrocracker to produce upgraded unconverted oil. Therefore, the method can be performed independently of hydrocracking, for example at a location different from where the hydrocracker is located (e.g. in a different plant).

Alternatively, the method of the first aspect may include a hydrocracking step. For example, prior to hydroprocessing unconverted oil from a hydrocracker, the method includes: hydrocracking a hydrocarbon-based feedstock in the hydrocracker to produce hydrocracked wastewater containing unconverted oil; and separating the unconverted oil from the hydrocracked wastewater (e.g., by fractional distillation). Therefore, hydrocracking and hydroprocessing can occur at the same location (e.g. in the same plant). The hydrocarbon feedstock may have a boiling point in the range of about 572°F to about 1112°F (i.e., about 300°C to 600°C). Hydrocarbon feedstocks include gas oil (e.g. vacuum gas oil (VGO), atmospheric gas oil, coker gas oil, e.g. heavy coker gas oil (HCGO), visbreaker gas oil), demetallized oil, vacuum residue, atmospheric residue, and deasphalted oil. It may include oil, Fischer-Tropsch stream and/or FCC stream. In some examples, the hydrocarbon feedstock includes gas oil, such as vacuum gas oil (VGO) or heavy coker gas oil (HCGO).

Hydroprocessing the unconverted milk from the hydrocracker to produce upgraded unconverted milk may include increasing the viscosity index (VI) of the unconverted milk. It will be appreciated that the viscosity index of a fluid is a measure of the tendency of the viscosity of a fluid to change as a function of temperature. The viscosity index of a fluid can be measured by the methods set forth in standard ASTM D-2270, which is hereby incorporated by reference in its entirety. According to ASTM D-2270, the viscosity index is calculated based on the kinematic viscosity of the fluid as measured at 40°C (i.e., 104°F) and at 100°C (i.e., 212°F). The viscosity index obtained by this method is a unitless value. A higher viscosity index indicates a smaller decrease in kinematic viscosity with increasing temperature. Accordingly, the step of hydroprocessing unconverted oil from a hydrocracker to produce upgraded unconverted oil typically reduces the tendency of the kinematic viscosity of the upgraded oil to decrease as a function of increasing temperature. The present inventors have discovered that by increasing the VI of the unconverted oil prior to dewaxing, the process can produce base oil products that meet the requirements for classification as Class II or Class III base oils, including low-quality, heavier feedstocks. It has been discovered that this makes it possible to produce, for example, from upgraded bottoms fractions (e.g. HCGO) or those obtained from heavy crude oil.

Hydroprocessing the unconverted oil from the hydrocracker to produce upgraded unconverted oil may include contacting the unconverted oil with a hydroprocessing catalyst under hydroprocessing conditions and in the presence of hydrogen. The hydroprocessing catalyst and/or hydroprocessing conditions may be selected such that VI-increasing molecular modifications dominate the hydroprocessing. It will be appreciated that a VI-increasing molecular modification is a molecular modification that tends to increase the viscosity index of the unconverted milk. Examples of VI-increasing molecular modifications include hydroisomerization and hydrogenation. Hydroisomerization modifications can increase hydrocarbon branching, for example, conversion of normal paraffins (i.e., normal alkanes) to iso-paraffins (i.e., branched alkanes). Additionally, or alternatively, hydroisomerization transformations may include ring-opening molecular transformations, such as converting naphthenes (i.e., cycloalkanes) to paraffins (i.e., linear alkanes). Hydrogenation modifications may include saturated aromatic and/or olefinic (i.e., alkene) hydrocarbons.

Hydroprocessing catalysts typically include: (a) one or more metals and/or one or more compounds thereof (e.g., one or more oxides or sulfides) selected from groups VI and VIII to X of the Periodic Table of the Elements; and (b) a catalyst support (e.g., a porous refractory support such as alumina, silica, amorphous silica-alumina material, or combinations thereof). The hydroprocessing catalyst may optionally further comprise: (c) one or more molecular sieves (e.g., one or more zeolites).

For the avoidance of doubt, Group VI of the Periodic Table of Elements includes chromium (Cr), molybdenum (Mo), tungsten (W) and sibo (Sg). Group VII of the periodic table of elements includes manganese (Mn), technetium (Tc), rhenium (Re), and borium (Bh). Group VIII of the periodic table of elements includes iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs). Group IX of the periodic table of elements includes cobalt (Co), rhodium (Rh), iridium (Ir), and meitnerium (Mt). Group

Hydroprocessing catalysts may be provided in the form of catalyst extrudates and/or formed particles. The catalyst extrudate and/or formed particles may have a diameter of about 0.5 mm to about 5 mm, such as about 1 mm to about 3 mm, or about 1 mm to about 2 mm. The catalyst extrudate and/or formed particles may have a length/diameter ratio of about 1 to about 5, such as about 1 to about 4, or about 2 to about 5, or about 2 to about 4, or about 2 to about 3. You can have The catalyst extrudate and/or formed particles may be combined with an interstitial packing material, such as glass beads.

The hydroprocessing catalyst may be a hydrotreating catalyst, hydrocracking catalyst, and/or hydroisomerization catalyst.

For example, the hydroprocessing catalyst may be a hydroprocessing catalyst comprising: (a) one or more metals selected from Groups VI and Groups VIII to oxide or sulfide); and (b) a catalyst support (e.g., a porous refractory support such as alumina, silica, amorphous silica-alumina material, or combinations thereof). Examples of hydrotreating catalysts include alumina supported cobalt-molybdenum, nickel sulfide, nickel-tungsten, cobalt-tungsten and nickel-molybdenum. Hydrotreating catalysts may be presulfurized.

Alternatively, the hydroprocessing catalyst may be a hydrocracking catalyst comprising: (a) one or more metals selected from Groups VI and Groups VIII to oxide or sulfide); (b) catalyst support (e.g., a porous refractory support such as alumina, silica, amorphous silica-alumina material, or combinations thereof); and (c) one or more molecular sieves (e.g., one or more zeolites). Hydrocracking catalysts are typically bifunctional catalysts. One or more metals selected from groups VI and VIII to You can. The one or more molecular sieves may be one or more zeolites selected from Y-type (e.g., SY, USY and VUSY), REX, REY, beta and/or ZSM-5 zeolites. The hydrocracking catalyst may include one or more promoters selected from, for example, phosphorus, boron, fluorine, silicon, aluminum, zinc, manganese, and mixtures thereof. The balance between the cracking and hydrogenation functions of a hydrocracking catalyst can be adjusted to optimize activity and selectivity.

Further alternatively, the hydroprocessing catalyst may be a hydroisomerization catalyst comprising: (a) one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof (e.g. , one or more oxides or sulfides); (b) catalyst support (e.g., a porous refractory support such as alumina, silica, amorphous silica-alumina material, or combinations thereof); and (c) one or more molecular sieves (e.g., one or more zeolites). Hydroisomerization catalysts are typically bifunctional catalysts. One or more metals selected from groups VI and VIII to You can. One or more molecular sieves are MFI, MEL, TON, MTT, ^* MRE, FER, AEL, EUO-type, SSZ-32, small crystalline SSZ-32, ZSM-23, ZSM-48, MCM-22, ZSM-5, It may be one or more zeolites selected from ZSM-12, ZSM-22, ZSM-35 and MCM-68-type zeolites and/or ^* may be a zeolite with MRE and/or MTT framework topology. The hydroisomerization catalyst may include one or more cocatalysts selected from, for example, magnesium, calcium, strontium, barium, potassium, lanthanum, praseodymium, neodymium, chromium, and mixtures thereof.

Hydroprocessing the unconverted oil from the hydrocracker to produce upgraded unconverted oil may include contacting the unconverted oil with two or more (i.e., different) hydroprocessing catalysts under hydroprocessing conditions and in the presence of hydrogen. The two or more hydroprocessing catalysts may be of the same general type (e.g., two or more hydrotreating catalysts, two or more hydrocracking catalysts, or two or more hydroisomerization catalysts). Alternatively, the two or more hydroprocessing catalysts may be of different general types (e.g., (i) at least one hydrotreating catalyst and at least one hydrocracking catalyst, (ii) at least one hydrocracking catalyst and at least one hydroisomerization catalyst, (iii) one or more hydroisomerization catalysts and one or more hydroprocessing catalysts, or (iv) a combination of one or more hydroprocessing catalysts, one or more hydrocracking catalysts and one or more hydroisomerization catalysts.

As discussed above herein, the hydroprocessing catalyst(s) may be selected such that VI-increasing molecular modifications (such as hydroisomerization and hydrogenation) dominate the hydroprocessing. For example, the method may include selecting one or more hydrotreating and/or hydroisomerization catalysts such that hydrogenation and/or hydroisomerization molecular modifications dominate during hydrocracking. Additionally, or alternatively, the method may include selecting one or more mild hydrocracking catalysts. Mild hydrocracking catalysts include less active molecular sieves (e.g., zeolites) and/or lower amounts (e.g., zero amount) of molecular sieves compared to hydrocracking catalysts commonly used in hydrocrackers. It will be appreciated that hydrocracking catalysts contain (e.g. zeolites). Accordingly, hydrocarbonaceous feedstocks exposed to mild hydrocracking catalysts typically undergo less hydrocracking (and typically more hydroisomerization) than when exposed to stronger hydrocracking enzymes under the same reaction conditions.

In some examples, the hydroprocessing catalyst is: (a) a sulfide of one or more metals selected from Groups VI and Groups VIII to X; (b) a catalyst support comprising alumina and/or amorphous silica-alumina material; and (c) one or more zeolites. For example, the hydroprocessing catalyst may comprise: (a) a sulfide of one or more metals selected from Groups VI and Groups VIII to X; (b) a catalyst support comprising alumina and/or amorphous silica-alumina material; and (c) one or more Y-type zeolites. In some examples, the hydrotreating catalyst is a mild hydrocracking catalyst comprising: (a) a sulfide of one or more metals selected from Groups VI and Groups VIII to X; (b) a catalyst support comprising alumina and/or amorphous silica-alumina material; and (c) one or more low-activity Y-type zeolites.

The hydrotreatment conditions are about 400°F or higher, for example, about 450°F or higher, about 500°F or higher, about 550°F or higher, about 600°F or higher, about 650°F or higher, about 700°F or higher, or about 750°F or higher, or It may include a reaction temperature of about 800°F or higher. Hydroprocessing conditions may include a reaction temperature of less than or equal to about 950°F, such as less than or equal to about 900°F, or less than or equal to about 850°F, or less than or equal to about 800°F, or less than or equal to about 750°F, or less than or equal to about 700°F. Hydroprocessing conditions may range from about 400°F to about 950°F, for example, from about 400°F to about 900°F, or from about 400°F to about 850°F, or from about 400°F to about 800°F, or from about 400°F to about 750°F. , or about 400°F to about 700°F, or about 450°F to about 950°F, or about 450°F to about 900°F, or about 450°F to about 850°F, or about 450°F to about 800°F, or about 450°F to about 750°F, or from about 450°F to about 700°F, or from about 500°F to about 950°F, or from about 500°F to about 900°F, or from about 500°F to about 850°F, or from about 500°F to about 800°F, or About 500°F to about 750°F, or about 500°F to about 700°F, or about 550°F to about 950°F, or about 550°F to about 900°F, or about 550°F to about 850°F, or about 550°F to about 800°F, or about 550°F to about 750°F, or about 550°F to about 700°F, or about 600°F to about 950°F, or about 600°F to about 900°F, or about 600°F to about 850°F, or about 600°F to about 800°F, or about 600°F to about 750°F, or about 600°F to about 700°F, or about 650°F to about 950°F, or about 650°F to about 900°F, or about 650°F to about 850°F °F, or about 650°F to about 800°F, or about 650°F to about 750°F, or about 650°F to about 700°F, or about 700°F to about 950°F, or about 700°F to about 900°F, or about 700°F ℉ to about 850 ℉, or about 700 ℉ to about 800 ℉, or about 700 ℉ to about 750 ℉, or about 750 ℉ to about 950 ℉, or about 750 ℉ to about 900 ℉, or about 750 ℉ to about 850 ℉ , or about 750°F to about 800°F, or about 800°F to about 950°F, or about 800°F to about 900°F, or about 800°F to about 850°F.

Hydroprocessing conditions may include a reaction gauge pressure of at least about 500 psi, for example at least about 750 psi, or at least about 1000 psi, or at least about 1200 psi, or at least about 1500 psi, or at least about 2000 psi. Hydroprocessing conditions may include a reaction gauge pressure of less than or equal to about 5000 psi, such as less than or equal to about 4000 psi, or less than or equal to about 3000 psi, or less than or equal to about 2500 psi, or less than or equal to about 2000 psi. Hydrotreating conditions may be from about 500 psi to about 5000 psi, for example from about 500 psi to about 4000 psi, or from about 500 psi to about 3000 psi, or from about 500 psi to about 2500 psi, or from about 500 psi to about 2000 psi. , or about 750 psi to about 5000 psi, or about 750 psi to about 4000 psi, or about 750 psi to about 3000 psi, or about 750 psi to about 2500 psi, or about 750 psi to about 2000 psi, or about 1000 psi. to about 5000 psi, or about 1000 psi to about 4000 psi, or about 1000 psi to about 3000 psi, or about 1000 psi to about 2500 psi, or about 1000 psi to about 2000 psi, or about 1200 psi to about 5000 psi, or about 1200 psi to about 4000 psi, or about 1200 psi to about 3000 psi, or about 1200 psi to about 2500 psi, or about 1200 psi to about 2000 psi, or about 1500 psi to about 5000 psi, or about 1500 psi about 4000 psi, or about 1500 psi to about 3000 psi, or about 1500 psi to about 2500 psi, or about 1500 psi to about 2000 psi, or about 2000 psi to about 5000 psi, or about 2000 psi to about 4000 psi, or A reaction gauge pressure may be from about 2000 psi to about 3000 psi, or from about 2000 psi to about 2500 psi.

Hydrotreating conditions may include a liquid space velocity (LHSV) of at least about 0.1 hr ^-1 , for example at least about 0.2 hr ^-1 , or at least about 0.5 hr ^-1 , or at least about 1 hr ^-1 . Hydrotreating conditions may include an LHSV of less than about 15 hr ^-1 , for example, less than or equal to about 10 hr ^-1 , or less than or equal to about 5 hr ^-1 , or less than or equal to about 2.5 hr ^-1 . Hydrogenation conditions are about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.1 hr ^-1 to about 10 hr ^-1 , or about 0.1 hr ^-1 to about 5 hr ^-1 , or about 0.1 hr ^{-1 1} to about 2.5 hr ^-1 , or about 0.2 hr ^-1 to about 15 hr ^-1 , or about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 5 hr ^-1 , or about 0.2 hr -1 hr ^-1 to about 2.5 hr ^-1 , or about 0.5 hr ^-1 to about 15 hr ^-1 , or about 0.5 hr ^-1 to about 10 hr ^-1 , or about 0.5 hr ^-1 to about 5 hr ^-1 , or From about 0.5 hr ^-1 to about 2.5 hr ^-1 , or from about 1 hr ^-1 to about 15 hr ^-1 , or from about 1 hr ^-1 to about 10 hr ^-1 , or from about 1 hr ^-1 to about 5 hr ^-1 , or about 1 hr ^-1 to about 2.5 hr ^-1 of LHSV.

Hydroprocessing conditions may be at least about 100 scf per barrel of liquid hydrocarbon feed, for example, at least about 200 scf per barrel of liquid hydrocarbon feed, or at least about 300 scf per barrel of liquid hydrocarbon feed, or at least about 300 scf per barrel of liquid hydrocarbon feed. It may include a hydrogen consumption of at least about 400 scf per barrel, or at least about 500 scf per barrel of liquid hydrocarbon feed. Hydroprocessing conditions may be less than or equal to about 2500 scf per barrel of liquid hydrocarbon feed, for example, less than or equal to about 2000 scf per barrel of liquid hydrocarbon feed, or less than or equal to about 1500 scf per barrel of liquid hydrocarbon feed, or less than or equal to about 1500 scf per barrel of liquid hydrocarbon feed. May include hydrogen consumption of less than 1000 scf. Hydroprocessing conditions may range from about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed, for example, from about 100 scf to about 2000 scf per barrel of liquid hydrocarbon feed, or from about 100 scf to about 1500 scf per barrel of liquid hydrocarbon feed. , or about 100 scf to about 1000 scf per barrel of liquid hydrocarbon feed, or about 200 scf to about 2500 scf per barrel of liquid hydrocarbon feed, or about 200 scf to about 2000 scf per barrel of liquid hydrocarbon feed, or about 200 scf to about 2000 scf per barrel of liquid hydrocarbon feed. About 200 scf to about 1500 scf per barrel of water, or about 200 scf to about 1000 scf per barrel of liquid hydrocarbon feed, or about 300 scf to about 2500 scf per barrel of liquid hydrocarbon feed, or about 300 scf per barrel of liquid hydrocarbon feed. scf to about 2000 scf, or about 300 scf to about 1500 scf per barrel of liquid hydrocarbon feed, or about 300 scf to about 1000 scf per barrel of liquid hydrocarbon feed, or about 400 scf to about 2500 scf per barrel of liquid hydrocarbon feed. , or about 400 scf to about 2000 scf per barrel of liquid hydrocarbon feed, or about 400 scf to about 1500 scf per barrel of liquid hydrocarbon feed, or about 400 scf to about 1000 scf per barrel of liquid hydrocarbon feed, or about 400 scf to about 1000 scf per barrel of liquid hydrocarbon feed. About 500 scf to about 2500 scf per barrel of water, or about 500 scf to about 2000 scf per barrel of liquid hydrocarbon feed, or about 500 scf to about 1500 scf per barrel of liquid hydrocarbon feed, or about 500 scf per barrel of liquid hydrocarbon feed. It may include a hydrogen consumption of from scf to about 1000 scf.

Accordingly, hydroprocessing conditions may be: (a) about 400°F to about 950°F, such as about 400°F to about 900°F, or about 400°F to about 850°F, or about 400°F to about 800°F, or about 400°F to about 750°F, or about 400°F to about 700°F, or about 450°F to about 950°F, or about 450°F to about 900°F, or about 450°F to about 850°F, or about 450°F to about 800°F °F, or about 450°F to about 750°F, or about 450°F to about 700°F, or about 500°F to about 950°F, or about 500°F to about 900°F, or about 500°F to about 850°F, or about 500°F From about 500°F to about 800°F, or from about 500°F to about 750°F, or from about 500°F to about 700°F, or from about 550°F to about 950°F, or from about 550°F to about 900°F, or from about 550°F to about 850°F. , or about 550°F to about 800°F, or about 550°F to about 750°F, or about 550°F to about 700°F, or about 600°F to about 950°F, or about 600°F to about 900°F, or about 600°F to about 850°F, or from about 600°F to about 800°F, or from about 600°F to about 750°F, or from about 600°F to about 700°F, or from about 650°F to about 950°F, or from about 650°F to about 900°F, or about 650°F to about 850°F, or about 650°F to about 800°F, or about 650°F to about 750°F, or about 650°F to about 700°F, or about 700°F to about 950°F, or about 700°F to About 900°F, or about 700°F to about 850°F, or about 700°F to about 800°F, or about 700°F to about 750°F, or about 750°F to about 950°F, or about 750°F to about 900°F, or a reaction temperature of from about 750°F to about 850°F, or from about 750°F to about 800°F, or from about 800°F to about 950°F, or from about 800°F to about 900°F, or from about 800°F to about 850°F; (b) about 500 psi to about 5000 psi, for example, about 500 psi to about 4000 psi, or about 500 psi to about 3000 psi, or about 500 psi to about 2500 psi, or about 500 psi to about 2000 psi, or from about 750 psi to about 5000 psi, or from about 750 psi to about 4000 psi, or from about 750 psi to about 3000 psi, or from about 750 psi to about 2500 psi, or from about 750 psi to about 2000 psi, or from about 1000 psi about 5000 psi, or about 1000 psi to about 4000 psi, or about 1000 psi to about 3000 psi, or about 1000 psi to about 2500 psi, or about 1000 psi to about 2000 psi, or about 1200 psi to about 5000 psi, or About 1200 psi to about 4000 psi, or about 1200 psi to about 3000 psi, or about 1200 psi to about 2500 psi, or about 1200 psi to about 2000 psi, or about 1500 psi to about 5000 psi, or about 1500 psi to about 4000 psi, or about 1500 psi to about 3000 psi, or about 1500 psi to about 2500 psi, or about 1500 psi to about 2000 psi, or about 2000 psi to about 5000 psi, or about 2000 psi to about 4000 psi, or about a reaction gauge pressure from 2000 psi to about 3000 psi, or from about 2000 psi to about 2500 psi; (c) from about 0.1 hr ^-1 to about 15 hr ^-1 , for example from about 0.1 hr ^-1 to about 10 hr ^-1 , or from about 0.1 hr ^-1 to about 5 hr ^-1 , or from about 0.1 hr ^-1 to About 2.5 hr ^-1 , or about 0.2 hr ^-1 to about 15 hr ^-1 , or about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 5 hr ^-1 , or about 0.2 hr ^{-1 1} to about 2.5 hr ^-1 , or about 0.5 hr ^-1 to about 15 hr ^-1 , or about 0.5 hr ^-1 to about 10 hr ^-1 , or about 0.5 hr ^-1 to about 5 hr ^-1 , or about 0.5 hr -1 hr ^-1 to about 2.5 hr ^-1 , or about 1 hr ^-1 to about 15 hr ^-1 , or about 1 hr ^-1 to about 10 hr ^-1 , or about 1 hr ^-1 to about 5 hr ^-1 , or LHSV from about 1 hr ^-1 to about 2.5 hr ^-1 ; and/or (d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed, such as about 100 scf to about 2000 scf per barrel of liquid hydrocarbon feed, or about 100 scf per barrel of liquid hydrocarbon feed. 1500 scf, or about 100 scf to about 1000 scf per barrel of liquid hydrocarbon feed, or about 200 scf to about 2500 scf per barrel of liquid hydrocarbon feed, or about 200 scf to about 2000 scf per barrel of liquid hydrocarbon feed, or liquid About 200 scf to about 1500 scf per barrel of hydrocarbon feed, or about 200 scf to about 1000 scf per barrel of liquid hydrocarbon feed, or about 300 scf to about 2500 scf per barrel of liquid hydrocarbon feed, or about 300 scf to about 2500 scf per barrel of liquid hydrocarbon feed. About 300 scf to about 2000 scf, or about 300 scf to about 1500 scf per barrel of liquid hydrocarbon feed, or about 300 scf to about 1000 scf per barrel of liquid hydrocarbon feed, or about 400 scf per barrel of liquid hydrocarbon feed. 2500 scf, or about 400 scf to about 2000 scf per barrel of liquid hydrocarbon feed, or about 400 scf to about 1500 scf per barrel of liquid hydrocarbon feed, or about 400 scf to about 1000 scf per barrel of liquid hydrocarbon feed, or liquid About 500 scf to about 2500 scf per barrel of hydrocarbon feed, or about 500 scf to about 2000 scf per barrel of liquid hydrocarbon feed, or about 500 scf to about 1500 scf per barrel of liquid hydrocarbon feed, or about 500 scf to about 1500 scf per barrel of liquid hydrocarbon feed. It may include a hydrogen consumption of about 500 scf to about 1000 scf.

In some examples, hydroprocessing conditions include: (a) a reaction temperature of about 400°F to about 950°F, such as about 650°F to about 850°F; (b) a reaction gauge pressure of about 500 psi to about 5000 psi, for example, about 1500 psi to about 2500 psi, or about 1200 psi to about 2500 psi; (c) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or (d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed, such as about 200 scf to about 2500 scf per barrel of liquid hydrocarbon feed, or about 100 scf per barrel of liquid hydrocarbon feed. Includes hydrogen consumption of 1500 scf.

As discussed above herein, hydroprocessing conditions may be selected such that VI-increasing molecular modifications (such as hydroisomerization and hydrogenation) dominate the hydroprocessing. Therefore, hydroprocessing conditions can be selected depending on the hydroprocessing catalyst(s) selected.

For example, the method may include contacting unconverted oil with one or more hydroprocessing catalysts in the presence of hydrogen and hydroprocessing conditions comprising: (a) about 400°F to about 950°F, e.g. For example, a reaction temperature of about 650°F to about 850°F; (b) a reaction gauge pressure of about 500 psi to about 5000 psi, such as about 1200 psi to about 2500 psi; (c) LHSV from about 0.1 hr ^-1 to about 15 hr ^-1 , for example, from about 0.2 hr ^-1 to about 2.5 hr ^-1 ; and/or (d) hydrogen consumption of about 200 scf to about 2500 scf per barrel of liquid hydrocarbon feed. Alternatively, the method may include contacting the unconverted oil with one or more hydrocracking catalysts in the presence of hydrogen and hydrocracking conditions comprising: (a) from about 400°F to about 950°F, e.g. For example, a reaction temperature of about 650°F to about 850°F; (b) a reaction gauge pressure of about 500 psi to about 5000 psi, such as about 1500 psi to about 2500 psi; (c) LHSV from about 0.5 hr ^-1 to about 15 hr ^-1 , eg, from about 1 hr ^-1 to about 10 hr ^-1 ; and/or (d) hydrogen consumption of about 100 scf to about 1500 scf per barrel of liquid hydrocarbon feed. Still further alternatively, the method may include contacting the unconverted oil with one or more hydroisomerization catalysts in the presence of hydrogen and hydroisomerization conditions comprising: (a) about 400° F. to about 950° F. °F, for example, a reaction temperature of about 650°F to about 850°F; (b) a reaction gauge pressure of about 500 psi to about 5000 psi, such as about 1500 psi to about 2500 psi; (c) LHSV from about 0.5 hr ^-1 to about 15 hr ^-1 , eg, from about 1 hr ^-1 to about 10 hr ^-1 ; and/or (d) hydrogen consumption of about 100 scf to about 1500 scf per barrel of liquid hydrocarbon feed.

It will be appreciated that the catalytic activity of a hydroprocessing catalyst can be affected by hydroprocessing conditions. For example, the selectivity of a hydroprocessing catalyst may depend on the hydroprocessing conditions. Accordingly, in some instances, the method involves hydrotreating unconverted milk to cause VI-increasing molecular modifications (e.g., hydrogenation and/or hydroisomerization modifications) to predominate (e.g., over hydrocracking modifications). and contacting the hydrocracking catalyst under conditions and presence of hydrogen. For example, the method includes contacting unconverted oil with a hydrocracking catalyst under mild hydrocracking conditions (e.g., at relatively low temperatures) and in the presence of hydrogen such that the hydroisomerization reaction dominates the hydrocracking reaction. can do.

Accordingly, hydroprocessing the unconverted oil from the hydrocracker to produce upgraded unconverted oil may include hydrotreating, hydroisomerizing, and/or hydrocracking the unconverted oil from the hydrocracker. However, the hydrotreating and/or hydroisomerization reactions are typically more significant than the hydrocracking reactions in hydroprocessing. For example, the step of hydrotreating unconverted oil from a hydrocracker may include hydrocracking the unconverted oil from the hydrocracker, but the level of hydrocracking conversion during hydrocracking of the unconverted oil from the hydrocracker ( Apparent conversion, which is, for example, the mass of the resulting hydrocracked products (e.g., light and middle fractions) expressed as a proportion (e.g., as a percentage) of the mass of hydrotreated unconverted oil. is less than the level of hydrocracking conversion (e.g., apparent conversion) during hydrocracking of hydrocarbon feedstock in a hydrocracker. In some examples, hydrocracking the unconverted oil from the hydrocracker may be performed at a rate of about 5% to about 30% (e.g., about 5% to about 20%, or about 10% to about 30%, or about 10% to about 30%). 20%) of the hydrocracking conversion (i.e., apparent conversion), whereas hydrocracking of the hydrocarbon feedstock in the hydrocracker occurs from about 30% to about 70% (e.g., about 40% to about 70%). , or about 50% to about 70%, or about 30% to about 60%, or about 40% to about 60%, or about 50% to about 60%, or about 30% to about 50%, or about 40% to about 50%) of the hydrolysis conversion (i.e., apparent conversion).

The method may include hydrotreating unconverted milk under clean conditions. For example, prior to hydroprocessing the unconverted oil, the sulfur, nitrogen and/or metal content of the unconverted oil may be low. In some instances, prior to hydroprocessing, the unconverted oil is substantially sulfur-, nitrogen- and/or metal-free. For example, prior to hydroprocessing the unconverted oil from a hydrocracker, the unconverted oil may have: (a) less than or equal to about 100 ppm, such as less than or equal to about 75 ppm, or less than or equal to about 50 ppm of sulfur; (b) 20 ppm, for example, about 15 ppm or less, or about 10 ppm or less of nitrogen; and/or (c) less than or equal to about 1 ppm, for example, less than or equal to about 0.5 ppm of nickel, vanadium and/or copper.

Additionally or alternatively, prior to hydroprocessing the unconverted oil from the hydrocracker, the unconverted oil may be: (a) from about 25 to about 45, for example from about 30 to about 45, or from about 25 to about 40, or an API specific gravity of about 30 to about 40, or about 25 to about 35, or about 30 to about 35; (b) at the true boiling point (TBP) 95% point ( i.e., the temperature at which 95% of the unconverted milk evaporates); and/or (c) from about 100 to about 150, for example from about 110 to about 150, or from about 120 to about 150, or from about 100 to about 140, or from about 110 to about 150, as measured according to ASTM D-2270. 140, or about 120 to about 140, or about 100 to about 130, or about 110 to about 130, or about 120 to about 130, or about 100 to about 120, or about 110 to about 120, at 100° C. (i.e. It may have a viscosity index (VI) at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 212°F.

Hydroprocessing the unconverted oil to produce a lube base oil product may include increasing the VI of the unconverted oil by at least about 5, such as at least about 10, or at least about 15. Hydroprocessing the unconverted oil to produce a base oil product may include increasing the VI of the unconverted oil by less than or equal to about 30, such as less than or equal to about 25, or less than or equal to about 20. Hydrotreating the unconverted oil to produce a lubricant base oil product can be accomplished by about 5 to about 30 percent, for example, about 10 to about 30 percent, or about 15 to about 30 percent, or about 5 to about 25 percent, or about It may include increasing the VI of the unconverted milk by 10 to about 25, or by about 15 to about 25, or by about 5 to about 20, or by about 10 to about 20, or by about 15 to about 20.

It will be appreciated that dewaxing the upgraded unconverted milk reduces the wax content of the upgraded unconverted milk. Dewaxing the upgraded unconverted milk includes removing wax from the upgraded unconverted milk by one or more physical processes, for example, by cooling the upgraded unconverted milk to coagulate the wax component and filtering to remove the coagulated wax component. may include For example, dewaxing the upgraded unconverted milk may include solvent dewaxing the upgraded unconverted milk, wherein solvent dewaxing comprises: diluting the upgraded unconverted milk with a solvent; cooling the diluted upgraded unconverted milk to coagulate the wax component; Filtering to separate the coagulated wax component and the filtrate; and recovering solvent from the coagulated wax component and/or filtrate. Additionally, or alternatively, dewaxing the upgraded unconverted oil includes reducing the wax content of the upgraded unconverted oil by one or more chemical processes, for example, by catalytic decomposition and/or isomerization of wax molecules. may include. For example, dewaxing upgraded unconverted oil may include catalytically dewaxing the upgraded unconverted oil by hydrocracking the wax component and/or isomerizing-dewaxing the upgraded unconverted oil by hydroisomerizing the wax component. You can. The step of hydrocracking and/or hydroisomerizing the wax component may utilize a hydrocracking and/or hydroisomerization catalyst, such as an isomerization-dewaxing catalyst.

The base oil product produced by the method has a 4 cSt( It can have a VI at a kinematic viscosity of 4 mm ² s ^-1 ). The base oil product produced by the method has a 4 cSt at 100°C (i.e., 212°F), as measured in accordance with ASTM D-2270, of less than or equal to about 200, e.g., less than or equal to about 175, or less than or equal to about 150. It can have a VI at a kinematic viscosity of (4 mm ² s ^-1 ). The base oil product produced by the method may have a lube base oil product of about 120 to about 200, as measured according to ASTM D-2270, for example, about 120 to about 175, or about 120 to about 150, as measured according to ASTM D-2270. , or from about 130 to about 200, or from about 130 to about 175, or from about 130 to about 150, or from about 140 to about 200, or from about 140 to about 175, or from about 140 to about 150.

The base oil product produced by the method may be a Group III base oil product as defined by the American Petroleum Institute (API).

The base oil product may be a base oil for use in the manufacture of lubricating oils, motor oils, and/or metal processing fluids (e.g., cutting fluids). The base oil product may be a blend of two or more (i.e. different) base oils.

The method can be carried out in a lube base oil production plant. Hydroprocessing the unconverted oil from the hydrocracker to produce upgraded unconverted oil may occur, for example, in an unconverted oil upgrading reactor according to the third aspect described herein below.

The method may include any other steps known in the art for producing a base oil product, including filtration, distillation, stripping and/or hydrofinishing steps, as desired. .

In a second aspect, a method is provided for modifying an existing base oil product manufacturing process to increase the viscosity index (VI) of the produced base oil. Existing lube base oil product manufacturing processes include: hydrocracking hydrocarbon feedstock in a hydrocracker to produce hydrocracked wastewater containing unconverted oil; Separating unconverted milk from hydrocracked wastewater; and dewaxing the unconverted oil separated from the hydrocracked wastewater to produce a lubricant base oil product. A method of modifying an existing base oil product manufacturing process includes: hydrotreating unconverted oil separated from hydrocracked wastewater prior to dewaxing the unconverted oil to produce a base oil product.

The hydrocarbonaceous feedstock may be any hydrocarbonaceous feedstock as described above herein in relation to the first aspect.

The steps of the process (including hydrocracking, separation, hydrotreating and dewaxing steps) may, mutatis mutandis, have any characteristics (input feeds, output, molecules) of the corresponding steps of the process according to the first aspect, mutatis mutandis. including modifications, catalysts, and reaction conditions).

In a third aspect, a system for producing a lube base oil product is provided. The system includes: a hydrocracker for hydrocracking hydrocarbon feedstock to produce hydrocracked wastewater containing unconverted oil; and an unconverted oil upgrading reactor for producing upgraded unconverted oil by hydrotreating unconverted oil separated from hydrocracked wastewater.

The unconverted oil upgrading reactor may be configured to hydrotreat unconverted oil separated from hydrocracked wastewater by the method according to the first aspect described above herein. Accordingly, the input feed to the unconverted oil upgrading reactor, the output therefrom, and the catalyst and reaction conditions thereof may be as described above herein with respect to the first aspect.

The unconverted oil upgrading reactor may have a hydroprocessing zone comprising one or more beds containing one or more hydroprocessing catalysts as described above herein with respect to the first aspect. The one or more beds may be a fixed bed, a slurry bed, and/or a fluid (e.g., blister-like) bed. In instances where one or more beds contain more than one (i.e., different) hydroprocessing catalyst, the one or more hydroprocessing catalysts may be layered. One or more beds may further contain interstitial packing material, such as glass beads. The hydroprocessing zone may be maintained at hydroprocessing conditions as described above herein with respect to the first aspect.

The system may further include: a dewaxing unit for dewaxing the unconverted oil produced by the unconverted oil upgrading reactor to produce a lube base oil product. The dewaxing unit may be configured to dewax the unconverted oil by any of the dewaxing methods described in connection with the first aspect (e.g., solvent dewaxing, catalytic dewaxing, and/or isomerization-dewaxing).

The system may be a lube base oil production plant.

In a fourth aspect, a method is provided for modifying an existing system for producing a base oil product to increase the viscosity index (VI) of the base oil product. Existing systems for producing base oil products include: a hydrocracker to hydrocrack hydrocarbon-like feedstock to produce hydrocracked wastewater containing unconverted oil; and a dewaxing unit for dewaxing unconverted oil separated from hydrocracked wastewater to produce a lube base oil product. Methods for modifying the existing system include: installing an unconverted oil upgrading reactor in the existing system to hydroprocess the unconverted oil separated from the hydrocracked wastewater prior to dewaxing the unconverted oil to produce lubricant base oil products; Includes.

The hydrocarbonaceous feedstock may be any hydrocarbonaceous feedstock as described above herein in relation to the first aspect.

The unconverted oil upgrading reactor may, mutatis mutandis, have any of the characteristics of the unconverted oil upgrading reactor (input feed, output, structure, function, molecular modification, catalyst and including reaction conditions). Moreover, modifying an existing system by installing a non-converted oil upgrading reactor into the existing system may result in a system having any of the characteristics of the system as described in connection with the third aspect.

In a fifth aspect, an unconverted oil upgrading reactor is provided for hydrotreating unconverted oil separated from hydrocracked wastewater of a hydrocracker prior to dewaxing the unconverted oil to produce a lubricant base oil product. The unconverted oil upgrading reactor may, mutatis mutandis, have any of the characteristics of the unconverted oil upgrading reactor (input feed, output, structure, function, molecular modification, catalyst and including reaction conditions).

In a sixth aspect, (a) by a method according to the first aspect, (b) by a method modified by the method of the second aspect, (c) using a system according to the third aspect, or (d) A lube base oil product produced using a system modified by the method according to the fourth aspect is provided. The base oil product may be a Group II base oil product or a Group III base oil product, preferably a Group III base oil product.

The base oil product may be a base oil for use in the manufacture of lubricating oils, motor oils, and/or metalworking fluids (e.g., cutting fluids). The base oil product may be a blend of two or more (i.e. different) base oils.

In a seventh aspect, a lubricant comprising the lube base oil product according to the sixth aspect is provided. A lubricant may include two or more (i.e., different) base oil products (e.g., base oils). The lubricant may further include one or more additives, such as anti-wear additives, corrosion inhibitors, surfactants, dispersants, friction modifiers, pour point depressants and/or viscosity index improvers. The lubricant may be a lubricating oil (eg, motor oil), a metalworking oil (eg, cutting oil), or a lubricating grease (eg, soap emulsified with a base oil product).

In an eighth aspect, there is provided the use of the upgraded unconverted oil in the manufacture of the base oil product to increase the viscosity index (VI) of the manufactured base oil product.

Upgraded unconverted milk can be produced by upgrading (e.g., hydrotreating) unconverted milk obtained from a hydrocracker by a method according to the first aspect or by using a system according to the third aspect. For example, the upgraded unconverted oil has a boiling point in the range of about 572°F to about 1112°F (i.e., about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or heavy coker gas oil (HCGO). ) can be obtained by hydrotreating unconverted oil obtained from hydrocracking hydrocarbon feedstock containing. Manufacturing the base oil product may include dewaxing the upgraded unconverted oil in a dewaxing unit.

In a ninth aspect, there is provided the use of dewaxed, upgraded unconverted oil as a base oil product in a lubricant to increase the viscosity index (VI) of the lubricant.

The dewaxed, upgraded unconverted oil is upgraded by the method according to the first aspect or by using the system according to the third aspect or by using the unconverted oil upgrading reactor of the fifth aspect (e.g. , hydrogenation); It can be obtained by dewaxing the upgraded oil. For example, a dewaxed, upgraded unconverted oil may: (a) have a boiling point in the range of about 572°F to about 1112°F (i.e., about 300°C to about 600°C) and/or be converted to gas oil, such as vacuum gas oil (VGO); ) or by hydrotreating unconverted oil obtained from hydrocracking of hydrocarbon feedstock including heavy coker gas oil (HCGO); and (b) dewaxing hydrotreated unconverted milk.

Those skilled in the art will recognize that, except where mutually exclusive, features described in connection with any one of the above embodiments may be applied mutatis mutandis to any other embodiment. Moreover, except where mutually exclusive, any feature described herein may apply to any aspect described herein and/or be combined with any other feature.

Embodiments will now be described by way of example only, with reference to the drawings, where:
1 is a schematic process flow diagram illustrating a process for producing lubricant base oil;
Figure 2 shows the viscosity index (VI) as a function of the percentage hydrocracking conversion ( ) is a plot.
Figure 3 is a plot of VI as a function of viscosity at 100°C for (a) direct vacuum gas oil and (b) unconverted oil obtained directly from hydrocracking a blend of direct vacuum gas oil and heavy coker gas oil.
Figure 4 shows the VI as a function of It's a plot.
Figure 5 shows the viscosity at 100°C for dewaxed oils obtained by dewaxing (a) direct vacuum gas oil and (b) unconverted oil obtained directly from hydrocracking a blend of direct current vacuum gas oil and heavy coker gas oil. This is a plot of VI as a function.
Figure 6 shows the plots for unconverted oil obtained directly from hydrocracking a blend of (a) direct vacuum gas oil and (b) direct current vacuum gas oil and heavy coker gas oil, each at three different hydrocracking conversion percentages (X). Plot of VI as a function of viscosity at 100°C.
Figure 7 shows the dewaxing obtained by dewaxing unconverted oil obtained directly from the hydrocracking of (a) direct vacuum gas oil and (b) a blend of direct current vacuum gas oil and heavy coker gas oil, each at three different values of This is a plot of VI as a function of viscosity at 100°C for the oils prepared.
Figure 8 shows (a) unconverted oil obtained directly from hydrocracking a blend of direct-current vacuum gas oil and heavy coker gas oil at a 63.5% hydrocracking conversion, (b) direct-current vacuum gas oil at a 74% hydrocracking conversion. and (c) unconverted oil obtained directly from the hydrocracking of a blend of heavy coker gasoil, and (c) directly from the hydrocracking of a blend of direct vacuum gasoil and heavy coker gasoil at a hydrocracking conversion of 63.5%. Plot of VI as a function of viscosity at 100°C for dewaxed oil obtained by dewaxing upgraded unconverted oil obtained by upgrading the unconverted oil to a total hydrocracking conversion percentage of 74%.
Figure 9 shows (a) unconverted oil obtained directly from hydrocracking direct vacuum gas oil at a 77% hydrocracking conversion and (b) a blend of direct current vacuum gas oil and heavy coker gas oil at a 63.5% hydrocracking conversion. VI as a function of viscosity at 100°C for dewaxed oil obtained by dewaxing upgraded unconverted oil obtained by upgrading unconverted oil obtained directly from hydrocracking to a total hydrocracking conversion percentage of 74%. It's a plot.

For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers, percentages or ratios, and other numerical values used in the specification and claims are in all cases modified by the term "about". It should be understood as Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties to be achieved. It should be noted that as used in this specification and the appended claims, the singular forms "a", "an" and "the" include plural references unless clearly and unambiguously limited to one referent. do. As used herein, the term “comprise” and grammatical variations thereof are intended to be non-limiting so that citation of an item in a list does not exclude other similar items that may be substituted for or added to the listed item. As used herein, the term "comprising" means including the elements or steps identified following the term, but is not exhaustive of any such elements or steps and embodiments include other elements or steps. can do.

Unless otherwise specified, references to classes of elements, materials or other components from which individual components or mixtures of components may be selected are intended to include all possible sub-generic combinations of the listed components and mixtures thereof. Moreover, all numerical ranges presented herein include their upper and lower values.

When reference is made to a standard test herein, unless otherwise specified, the version of the test to which it is referred is the most recent version at the time of filing this patent application.

The patentable scope is defined by the claims and may include other examples that occur to those skilled in the art. Other such examples are within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they contain equivalent structural elements with minor differences from the literal language of the claims. It is intended to be. To the extent not inconsistent with this application, all citations referred to herein are hereby incorporated by reference.

process flow

1 illustrates an example process flow for producing lube base oil for use in the manufacture of lubricants. The initial hydrocarbon feedstock (1) is fed into a hydrocracker (2) where the hydrocarbon feedstock (1) undergoes hydrocracking, thereby producing unconverted oil (3) and other products (not shown in Figure 1). . Unconverted oil (3) is fed from the hydrocracker (2) to a dewaxing block (10) comprising an upgrading reactor (4), a dewaxing reactor (6) and a hydrofinishing reactor (8). The unconverted oil is upgraded inside the dewaxing block 10 to increase the viscosity index (VI) of the unconverted oil 3, thereby producing an upgraded reactor 4 to produce the upgraded unconverted oil 5. is supplied first. The upgraded unconverted oil (5) is supplied from the upgrading reactor (4) to the dewaxing reactor (6), which dewaxes the upgraded unconverted oil (5) to produce dewaxed oil (DWO) (7). The dewaxed oil (7) is fed from the upgrading reactor (6) into a hydrofinishing reactor (8) where the dewaxed oil (7) is hydrofinished to produce a lubricating base oil (9) suitable for use as a base oil in the manufacture of lubricants. do.

The example process flow diagram illustrated in FIG. 1 can be used to process many different types of hydrocarbon feedstocks (e.g., gas oil (e.g., vacuum gas oil (VGO), atmospheric gas oil, coker gas oil, such as heavy oil), as known in the art. It is suitable for processing (including coker gas oil (HCGO), visbreaker gas oil), demetallized oil, vacuum resid, atmospheric resid, deasphalted oil, Fischer-Tropsch stream and/or FCC stream. In some embodiments, a typical input feed comprises hydrocarbons having boiling points in the range of about 572°F to about 1112°F (i.e., about 300°C to about 600°C) and therefore obtained directly from the fractional distillation of crude petroleum (i.e., i.e., “direct”) gasoil (e.g., VGO), as well as gasoil (e.g., coker gasoil) obtained from bottom fraction upgrading processes (e.g., coking of vacuum resid). there is. The process flow diagram illustrated in FIG. 1 is for hydrocarbon feeds that are typically considered lower quality or generally more difficult to process, such as heavy or heavy crude oil (i.e., relatively low API gravity, e.g., less than about 31.1°, or crude oil products having less than about 22.3°) or heavy coker gas oil (e.g., HCGO) or light oil (VGO).

The VI of hydrocarbon feedstock 1 depends on its composition and origin. A typical light oil feed can have a VI value of about 60 to about 100. The VI values of direct current gasoil are generally higher than those of diesel obtained by upgrading the bottom fraction. For example, direct current VGO typically has a VI value of about 70 to about 100, while coker diesel typically has a VI value of less than about 60.

Hydrocracker 2 may take any form known in the art for hydrocracking hydrocarbon feeds, such as VGO and/or coker gas oil (e.g., HCGO). Hydrocracker 2 typically includes one or more beds (e.g., fixed bed, slurry bed, fluid (e.g., blister-like) bed) containing one or more hydrocracking catalysts.

Hydrocracking catalysts are well-known in the art and include one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof, a hydrocracking catalyst support (e.g. an amorphous silica-alumina material) , and, optionally, one or more molecular sieves (e.g., zeolites). Hydrocracking catalysts are typically bifunctional catalysts: the hydrogenation/dehydrogenation reactions are promoted by the metals present, while the cracking reactions are promoted by solid acids (e.g. zeolites and/or amorphous silica-alumina materials). do. Typical metals used include iron, chromium, molybdenum, tungsten, cobalt or nickel, or their sulfides or oxides, and/or platinum or palladium. Typically used zeolites include Y types (e.g. SY, USY and VUSY), REX, REY, BETA and ZSM-5. The hydrocracking catalyst may also include one or more cocatalysts such as phosphorus, boron, fluorine, silicon, aluminum, zinc, manganese, or mixtures thereof.

During hydrocracking, the hydrocarbonaceous feed passes through one or more beds of hydrocracker 2, bringing the hydrocarbonaceous feed into contact with a hydrocracking catalyst and hydrogen. The hydrocracking process operates at a liquid space velocity (LHSV) from about 0.1 hr ^-1 to about 15 hr ^-1 and from about 500 scf to about 2500 scf per barrel of liquid hydrocarbon feed (i.e., from about 89 to about 445 m ³ H ₂ / m ³ ) at a temperature of from about 400°F to about 950°F (i.e., from about 204°C to about 510°C) and from about 500 psi to about 5000 psi (i.e., from about 3447 kPa to about 34474 kPa). Typically performed at gauge pressure.

Hydrocracking results in the cleavage of carbon-carbon bonds in longer hydrocarbon chains, thereby undergoing isomerization and dehydrogenation to form carbocation to form olefin intermediate products. The olefins are then hydrogenated to form lower boiling point middle distillate products such as light and heavy naphtha, jet, kerosene and diesel. In this way, heavier hydrocarbons are converted to lighter hydrocarbons, while aromatics and naphthenes are converted to non-cyclic paraffins.

Hydrotreating can also occur in hydrocracking (2). Hydrotreating is a process in which impurities such as nitrogen, sulfur, oxygen and metals are removed from a hydrocarbon feed. Hydrocracker 2 may therefore also include one or more beds (e.g., fixed beds, slurry beds, flowing (e.g., blister-like) beds) containing one or more hydrotreating catalysts. Hydrotreating catalysts are well-known in the art and include one or more metals selected from Groups VI and Groups VIII to alumina). Examples of hydrotreating catalysts are alumina supported cobalt-molybdenum, nickel sulfide, nickel-tungsten, cobalt-tungsten and nickel-molybdenum. Hydrotreating catalysts are typically pre-sulfurized.

In some embodiments, hydrocracker 2 includes two or more different catalysts. For example, hydrocracker 2 may include both a hydrocracking catalyst and a hydrotreating catalyst. Different catalysts may be layered within the hydrocracker 2, for example within the same bed.

Outputs from hydrocracker 2 include impurity products (e.g. H ₂ S and NH ₃ ), light oils (e.g. refinery gas, propane, butane and naphtha), middle distillate products (e.g. jet, kerosene and diesel). ) and unconverted milk (UCO). Therefore, UCO is the portion of wastewater from hydrocracker 2 that remains when impurities, light oils and middle distillates have been removed, and typically has a boiling point ranging from about 662°F to about 1112°F (i.e., from about 350°C to about 600°C). has UCO can be separated from other components of wastewater by fractional distillation.

The VI of the UCO leaving hydrocracker 2 depends on the characteristics of the input hydrocarbon feed 1, the catalyst(s) used within hydrocracker 2, the reaction conditions within hydrocracker 2, and, therefore, the hydrocracking conversion. depends on the level of However, UCO leaving hydrocracker 2 typically has a VI of about 110 to about 160. The VI of UCO produced by hydrocracking direct current light oil is generally higher than that of UCO produced by hydrocracking light oil obtained by upgrading the bottom fraction. For example, direct current VGO can be applied to an apparent conversion level of about 50% to about 80% (i.e., of light and middle cuts produced by a hydrocracker, expressed as a percentage of the total mass of the hydrocarbon feedstock input to the hydrocracker). mass) typically produces UCO with a VI of about 120 to about 160, while blends of direct VGO and HCGO (e.g., about 85 vol.% direct VGO and about 15 vol.% Hydrocracking (containing HCGO) at a conversion level of about 50% to about 80% typically produces UCO with a VI of about 100 to about 140.

The upgrade reactor (4) receives UCO (3) from the hydrocracker (2). Upgrading reactor 4 includes one or more beds (e.g., fixed bed, slurry bed, fluidized (e.g., blister) bed) containing one or more hydroprocessing catalysts for hydroprocessing UCO. During an upgrade, the low-VI component of the UCO is typically converted to a higher-VI component. Accordingly, the upgrade reactor 4 is generally configured such that hydrotreating the UCO results in an increase in the VI of the UCO. In other words, the one or more hydroprocessing catalysts and/or reaction conditions in the upgrading reactor 4 are selected such that VI-increasing molecular modifications dominate. VI-increasing molecular modifications typically include hydrotreating, hydrogenation, and/or isomerization (e.g., hydroisomerization) modifications. For example, during upgrading of UCO, aromatic and olefinic hydrocarbons become saturated and cyclic hydrocarbons (such as naphthenes) may undergo ring-opening transformation, thereby increasing the paraffin content of UCO. Therefore, one or more hydroprocessing catalysts and/or reaction conditions may be selected such that hydrotreating, hydrogenation and/or isomerization (e.g., hydroisomerization) modifications dominate (e.g., over hydrocracking modifications).

The one or more hydroprocessing catalysts may be a hydroprocessing catalyst, a hydroisomerization catalyst, and/or a hydrocracking catalyst. Hydrotreating and hydrocracking catalysts are described above herein. Hydroisomerization catalysts are well-known in the art and include one or more metals selected from Groups VI and Groups VIII to materials), and, optionally, one or more molecular sieves (e.g., zeolites). Hydroisomerization catalysts are typically bifunctional: the hydrogenation/dehydrogenation reaction is catalyzed by the metal present, while the isomerization reaction is catalyzed by solid acids (e.g. zeolites and/or amorphous silica-alumina materials). promoted by Typical metals used include iron, chromium, molybdenum, tungsten, cobalt or nickel, or their sulfides or oxides, and/or platinum or palladium. Typical molecular sieves used are MFI, MEL, TON, MTT, ^* MRE, FER, AEL and EUO-type, SSZ-32, small crystalline SSZ-32, ZSM-23, ZSM-48, MCM-22, ZSM-5. , ZSM-12, ZSM-22, ZSM-35 and MCM-68-type, as well as molecular sieves with ^* MRE and/or MTT framework topology. The hydroisomerization catalyst may also include one or more cocatalysts such as magnesium, calcium, strontium, barium, potassium, lanthanum, praseodymium, neodymium, chromium, or mixtures thereof.

For example, in some implementations, upgrading reactor 4 includes a hydrotreating catalyst as described hereinabove. In another example, upgrading reactor 4 includes a hydrocracking catalyst as described hereinabove. In a further example, upgrading reactor 4 includes a hydroisomerization catalyst as described hereinabove. In still further examples, upgrading reactor 4 contains both hydrotreating and hydrocracking catalysts, both hydrocracking and hydroisomerization catalysts, or both hydrotreating and hydroisomerization catalysts. In some examples, the upgrading reactor includes a hydroprocessing catalyst, a hydrocracking catalyst, and a hydroisomerization catalyst.

As discussed above herein, the one or more hydroprocessing catalysts and/or reaction conditions within upgrading reactor 4 are selected such that VI-increasing molecular modifications (e.g., hydroisomerization modifications) dominate.

In some implementations, one or more hydroprocessing catalysts are selected such that VI-increasing molecular modifications (such as hydroisomerization modifications) dominate. For example, one or more hydrotreating and/or hydroisomerization catalysts may be selected such that VI-increasing molecular modifications (e.g., hydroisomerization modifications) dominate hydrocracking modifications. Additionally or alternatively, one or more mild hydrocracking catalysts may be selected, wherein the mild hydrocracking catalysts include molecular sieves (e.g., zeolites) that are less active compared to hydrocracking catalysts commonly used in hydrocracking. /or is understood to be a hydrocracking catalyst containing a smaller amount of molecular sieves (e.g. zeolites). In some examples, the mild hydrocracking catalyst contains substantially no molecular sieve material (e.g., zeolite).

In other implementations, the reaction conditions within the upgrading reactor 4 are selected such that VI-increasing molecular modifications (such as hydroisomerization modifications) dominate. For example, one or more hydrocracking catalysts may be selected while reaction conditions are selected such that only low levels of hydrocracking occur. For example, one or more hydrocracking catalysts can be operated at low temperatures (relative to temperatures typically used in hydrocracking) such that hydroisomerization dominates over hydrocracking.

In still further implementations, both the one or more hydroprocessing catalysts and the reaction conditions are selected such that VI-increasing molecular modifications (such as hydroisomerization modifications) dominate.

During upgrading, UCO 3 passes through one or more beds of the upgrading reactor, bringing the oil into contact with hydroprocessing catalyst and hydrogen. The upgrading process is performed at a temperature of about 400° ^F to about 800° ^F (i.e., about It is typically performed at a temperature of between 204° C. and about 427° C. and a gauge pressure of between about 500 psi and about 5000 psi. Because hydroisomerization reactions dominate in upgrade reactor 4 and any hydrocracking that occurs is typically selective and mild, the upgrading process can be performed at higher liquid space velocities (compared to operation of hydrocracker 2) and with reduced This can be done with hydrogen consumption.

Upgrade reactor 4 also generally operates under clean conditions. This means that the UCO (3) received by the upgrading reactor (4) typically contains only low levels of nitrogen or sulfur. In particular, the majority of the nitrogen and sulfur originally present in the hydrocarbon feedstock are removed in the form of ammonia and hydrogen sulfide when the wastewater from the hydrocracker (2) is fractionated before the UCO (3) reaches the upgrading reactor (4). . For example, UCO (3) received by upgrading reactor (4) may contain less than about 20 ppm nitrogen and less than about 100 ppm sulfur. Moreover, the upgrade reactor (4) can share the dewaxing block hydrogen supply with the dewaxer (6) and hydrofinisher (8). The dewaxing block hydrogen supply produces higher purity hydrogen than the hydrocracking block's hydrogen supply system because lower levels of contaminants are produced during upgrading, dewaxing and hydrofinishing, and because the hydrogen is recycled within the dewaxing block 10. Typically provided.

Because the upgrading reactor 4 operates under clean conditions and therefore the hydrotreating catalyst used in the upgrading reactor 4 is exposed to lower levels of contaminants (such as nitrogen) known to inhibit hydrocracking, the upgrading reactor ( The reaction conditions in 4) are typically selected so that they are less harsh (e.g. reaction temperatures and pressures may be lower) than in hydrocracker 2 so that excess hydrocracking is carried out in upgrade reactor 4. does not occur, again allowing VI-increasing molecular modifications to dominate.

Therefore, the upgraded UCO (5) produced by the upgrade reactor (4) generally exhibits a higher VI compared to the UCO before the upgrade. For example, upgrading a UCO can increase the value of VI by about 5 to about 30.

The dewaxing reactor (6) receives upgraded UCO (5) from the upgrading reactor (4) and produces dewaxed oil (DWO) (7). The dewaxing reactor 6 may take any form known in the art for dewaxing oil. For example, dewaxing reactor 6 may be configured to dewax oil by solvent dewaxing, catalytic dewaxing and/or isomerization dewaxing processes as are well-known in the art.

Solvent dewaxing is a physical wax removal process in which UCO is diluted with a solvent, cooled to solidify the wax component, and filtered to remove the solidified wax. The solvent is then recovered from the wax and filtered for recycling. Catalytic dewaxing is a chemical wax removal process in which hydrocracking catalysts and conditions are used to crack and isomerize the waxy normal paraffins in UCO to produce shorter chain isoparaffins. Isomerization dewaxing is the removal of chemical waxes where the catalyst and conditions are selected such that the isomerization reaction is superior to decomposition, thereby enabling the conversion of waxy normal paraffins into isoparaffins and cyclic species while preserving their paraffinicity. It's fair. Isomerization dewaxing may be preferred over alternative solvent dewaxing or catalytic dewaxing techniques because it typically leads to higher dewaxed oil yields and higher viscosity indices.

Dewaxing is performed to reduce the pour point and cloud point of the oil. The dewaxing process also tends to increase the viscosity and reduce the VI of the oil. For example, dewaxing UCO can increase the viscosity by about 1% to about 10% and decrease the viscosity index by about 5% to about 25%.

The hydrofinishing reactor (8) receives the dewaxed oil (7) from the dewaxing reactor (6) and produces lubricating base oil (9). The hydrofinishing reactor 8 can take any form known in the art for hydrofinishing lube base oils. As is well-known in the art, hydrofinishing involves dewaxing oil by performing hydrotreating at relatively low temperatures and pressures to remove aromatic and heterocyclic compounds and/or exposing the oil to materials such as clay or bauxite. This entails improving its color, as well as its oxidation and thermal stability. The hydrofinishing reactor 8 therefore typically employs a hydrotreating catalyst as described hereinabove.

In the example process flow diagram illustrated in Figure 1, upgrading reactor (4), dewaxing reactor (6) and hydrofinishing reactor (8) all form part of the same dewaxing block (10). This means that the upgrading, dewaxing and hydrofinishing processes all occur under the clean conditions discussed hereinabove.

The following examples serve to illustrate, but not limit, the invention.

Example

Lube base oil was produced starting from two different hydrocarbon feeds A and B. Supply A was DC Middle East VGO. Feed B was a blend of 85 vol.% direct current VGO from Feed A and 15 vol.% HCGO. A detailed description of feeds A and B is provided in Table 1.

[Table 1]

Both feeds A and B were cracked separately in a hydrocracker operated in Single Stage Once-Through mode using a layered catalyst system comprising a hydrotreating catalyst and a hydrocracking catalyst. The hydrotreating catalyst consisted of NiMo sulfide on an alumina support. The hydrocracking catalyst consisted of non-metal sulfide, Y-type zeolite, and alumina support. The two catalysts were layered from top to bottom in the reactor with volume percentage “hydrotreating catalyst: hydrocracking catalyst: hydrotreating catalyst” = 45:50:5. The catalyst extrudates had a diameter of approximately 1.5 mm and were shortened to a length/diameter ratio of 2 to 3 before use. Glass beads of 60/80 mesh size were used as interstitial packing within the catalyst bed of the reactor.

Prior to introducing feed A or B, the catalyst system was sulphurized according to standard procedures. Process conditions during hydrocracking were as follows: LHSV was 0.8 h ^-1 ; The hydrogen/oil ratio was 5000 scf/bbl; Total gauge pressure was 2300 psi. Unconverted hydrogen was recycled to the reactor inlet. Three liquid product streams were separated and collected in separate sections: naphtha, diesel and UCO.

The reactor temperature was adjusted during hydrocracking to achieve three different conversion levels at mid 50s, mid 60s and mid 70s for both feeds A and B. Typically, the catalyst system responded with about a 1% conversion change per degree F of temperature change. The process for blend feed B required temperatures about 10 degrees Fahrenheit higher to achieve similar conversion levels compared to feed A. Feed A was hydroprocessed at a temperature ranging from 748°F to 768°F, and feed B was hydroprocessed at a temperature ranging from 758°F to 775°F. UCO product samples from all six yield periods were prepared and analyzed, and equal volumes of three cuts were also isolated from each yield period.

Table 2 shows the different conversion levels and four 12-hour yield periods obtained with feed A.

[Table 2]

Table 3 shows the different conversion levels and four 12-hour yield periods obtained with feed B.

[Table 3]

Table 4 shows the conversion levels at 60s and 70s obtained with blend feed B and two extended yield periods.

[Table 4]

Table 5 shows the characteristics of UCO product samples from six extended yield periods (each at three conversion levels, both feeds A and B at X).

[Table 5]

Figure 2 shows the VI as a function of the hydrocracking conversion percentage Shows the plot. Although VI increases continuously as a function of conversion level for both feeds, the VI of UCO obtained from blend feed B is consistently lower than that of UCO obtained from feed A for the same conversion level.

Figure 3 shows the temperature at 100°C (i.e., 212°F) for UCO obtained directly from hydrocracking feed A (represented using filled circles) and feed B (represented using filled squares). Shows a plot of VI as a function of viscosity. VI decreased continuously as a function of viscosity for UCO obtained from both feed A and feed B. The VI of the UCO obtained from blend feed B is lower than that of the UCO obtained from direct current feed A at lower viscosity.

Samples of the six UCOs shown in Table 5 were dewaxed by cooling the samples to 5°F (i.e., -15°C) and filtering to coagulate the wax to produce six dewaxed oil (DWO) samples. The properties of six dewaxed oil samples are presented in Table 6.

[Table 6]

This data is also plotted in Figures 4 and 5. In particular, Figure 4 shows VI as a function of hydrocracking conversion percentage for dewaxed oils obtained by dewaxing UCO obtained directly from hydrocracking of feed A (filled circles) and feed B (filled squares). Shows the plot. Figure 5 shows the temperature at 100°C (i.e., 212°F) for dewaxed oil obtained by dewaxing UCO obtained directly from hydrocracking Feed A (filled circles) and Feed B (filled squares). Shows a plot of VI as a function of viscosity.

As can be seen in Table 6 and Figures 4 and 5, UCO made from both feeds A and B are suitable for making API Group II lube base oils requiring VI values of 80 to 120. It is also possible to make API Group III lube base oils requiring VI values greater than 120 from UCO obtained from direct current feed A. However, it is more difficult to produce API Group III lube base oils from UCO obtained directly from hydrocracking blend feed B, especially when targeting a viscosity of 4 cSt at 100°C (i.e., 212°F). . In particular, when processing feed B, a conversion level of about 70% or higher is required to ensure that the dewaxed oil achieves a VI greater than 120; However, the viscosity at 100° C. (i.e., 212° F.) for this dewaxed oil will be close to 5 cSt.

The six UCO samples identified in Table 6 were cut by distillation into three portions of equal volume with different viscosities. The properties of the three cuts, with Cut 1 being the lightest and Cut 3 being the heaviest, are presented in Tables 7 and 8.

[Table 7]

[Table 8]

Figure 6 shows a plot of VI as a function of viscosity at 100°C (i.e., 212°F) for different cuts 1, 2, and 3 obtained from feeds A and B at three different hydrocracking conversion percentages X. VI increases as a function of viscosity for both feeds A and B processed under all conditions.

Distillation cuts of UCO samples were cooled to 5°F (i.e., -15°C) and dewaxed again by filtering off the coagulated wax. The properties of the resulting dewaxed oil are presented in Table 9.

[Table 9]

Figure 7 shows a plot of VI as a function of viscosity at 100°C (i.e., 212°F) for different cuts of dewaxed oil given in Table 9. As can be seen in Table 9 and Figure 7, the lighter fractions of UCO made from feed A at high hydrocracking conversion levels have properties suitable for use in the manufacture of API Group III lube base oils (i.e., at 100°C VI greater than 120 at a viscosity of about 4 cSt). In contrast, when starting with feed blend B, the higher hydrocracking conversion levels cannot produce UCO suitable for the manufacture of Group III lube base oils.

Samples of three distillation cuts of UCO obtained from hydrocracking feed B at 63.5% conversion were then subjected to upgrading in the upgrading reactor. In the upgrading reactor, the samples were contacted with hydrogen in the presence of a mild hydrocracking catalyst consisting of base metal sulfide, small amounts of low activity Y-zeolite, amorphous silica-alumina and alumina. The catalyst extrudates had a diameter of approximately 1.5 mm and were shortened to a length/diameter ratio of approximately 2 to 3 prior to use. Glass beads of 60/80 mesh size were used as interstitial packing within the catalyst bed of the reactor. The upgrade process operates at a temperature of 680°F to 710°F (i.e., 360°C to 377°C) and 2300 psi, with a liquid space velocity of 2.5 hr ^-1 to 5 hr ^-1 at a hydrogen to oil ratio of 4000 scf/bbl. It was performed at a gauge pressure of . Hydrogen consumption ranged from 20 scf to 600 scf per barrel of liquid hydrocarbon feed, depending on conditions. The level of conversion achieved in the upgrade reactor was in the range of 20% to 50%. When combining the initial conversion level of feed B in the hydrocracker with the additional conversion of UCO in the upgrade reactor, the overall conversion level compared to the original feed B was 72-81%. The upgraded oil samples obtained from the upgrading process were cooled to 5°F (i.e., -15°C) and dewaxed again by filtering off the coagulated wax.

Figure 8 shows 100 for dewaxed, upgraded UCO obtained from three distillation cuts compared to non-upgraded dewaxed oil obtained from hydrocracking feed B at 63.5 and 74% conversion levels. A plot of VI as a function of viscosity in °C (i.e., 212°F) is shown. As can be seen in Figure 8, the upgrading process either compares the dewaxed oil obtained from hydrocracked feed B to the same initial level (63.5%) or dewaxed oil obtained from hydrocracked feed B. Significantly increases the VI of the dewaxed oil at all viscosities, whether compared to the same final level (74%). The VI of the dewaxed, upgraded oil is above 120, especially at a viscosity of 4 cSt at 100°C and is therefore suitable for producing API class III lube base oils.

Figure 9 shows a plot comparing VI as a function of viscosity at 100°C (i.e., 212°F) for the dewaxed, upgraded UCO shown in Figure 8 with dewaxed oil obtained by hydrocracking direct current feed A. . From Figure 9, it can be seen that the upgrading process allows equal or better properties to be obtained from blended feed B compared to feed A processed without upgrading.

For the avoidance of doubt, this application relates to the subject matter set forth in the following numbered paragraphs.

One. A method of producing a lube base oil product, the method comprising:

Hydrotreating unconverted milk from a hydrocracker to produce upgraded unconverted milk; and

A method comprising dewaxing upgraded unconverted oil to produce a lube base oil product.

2. The method of claim 1, prior to hydrotreating the unconverted oil from the hydrocracker,

Hydrocracking hydrocarbon feedstock in a hydrocracker to produce hydrocracked wastewater containing unconverted oil; and

A method further comprising the step of separating unconverted milk from hydrocracked wastewater.

3. 3. The method of claim 2, wherein the hydrocarbon feedstock has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or heavy coker gas oil ( How to include HCGO)

4. 4. The process of any one of claims 1 to 3, wherein hydroprocessing the unconverted oil from the hydrocracker to produce upgraded unconverted oil comprises increasing the viscosity index (VI) of the unconverted oil.

5. The method of any one of claims 1 to 4, wherein the step of hydrotreating the unconverted oil from the hydrocracker to produce upgraded unconverted oil includes contacting the unconverted oil with a hydroprocessing catalyst under hydroprocessing conditions and in the presence of hydrogen. A method that includes being told to do so.

6. 6. The process of claim 5, wherein the hydroprocessing catalyst and/or hydroprocessing conditions are selected such that VI-increasing molecular modifications predominate in the hydroprocessing.

7. 7. The method of claim 5 or 6, wherein the hydrotreating catalyst is:

(a) one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof; and

(b) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,

(c) a method comprising one or more molecular sieves, such as zeolites.

8. The method according to any one of claims 5 to 7, wherein the hydrotreatment conditions are:

(a) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);

(b) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of 8274 kPa to about 17237 kPa);

(c) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or

(d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to about 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed).

9. 9. The method of any one of claims 1 to 8, wherein the step of hydrotreating the unconverted oil from the hydrocracker to produce upgraded unconverted oil comprises hydrotreating, hydroisomerizing and/or A method comprising hydrocracking.

10. 10. The method of claim 9, wherein, when relying on claim 2, the step of hydrotreating the unconverted oil from the hydrocracker comprises hydrocracking the unconverted oil from the hydrocracker and hydrocracking the unconverted oil from the hydrocracker. A method in which the level of hydrocracking conversion during hydrocracking is less than the level of hydrocracking conversion during hydrocracking of hydrocarbon feedstock in a hydrocracker.

11. 11. The method of claim 10, wherein hydrocracking the unconverted oil from the hydrocracker occurs at a hydrocracking conversion of about 5% to about 30%, and hydrocracking the hydrocarbon feedstock in the hydrocracker occurs in about 30%. % to about 70% hydrocracking conversion.

12. 12. The process according to any one of claims 1 to 11, wherein prior to hydrotreating the unconverted oil from the hydrocracker, the unconverted oil is:

(a) less than or equal to about 100 ppm sulfur;

(b) less than or equal to about 20 ppm nitrogen; and/or

(c) comprising less than or equal to about 1 ppm of nickel, vanadium and/or copper.

13. 13. The process according to any one of claims 1 to 12, wherein prior to hydrotreating the unconverted oil from the hydrocracker, the unconverted oil is:

(a) API specific gravity of about 25 to about 45;

(b) at the 95% TBP point between about 800°F and about 1100°F (about 427°C and about 593°C); and/or

(c) a viscosity index (VI) of about 100 to about 150 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270.

14. 14. The method of any one of claims 1 to 13, wherein hydrotreating the unconverted oil to produce a base oil product comprises increasing the viscosity index (VI) of the unconverted oil by about 5 to about 30. .

15. The method of any one of paragraphs 1 to 14, wherein the base oil product has a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270. A method having a viscosity index (VI) of 120 or more.

16. 16. The method of any one of claims 1 to 15, wherein the base oil product is a Group III base oil product.

17. 17. The method of any one of claims 1 to 16, wherein hydroprocessing the unconverted oil from the hydrocracker to produce upgraded unconverted oil occurs in an unconverted oil upgrading reactor.

18. As a method of modifying the existing lube base oil product manufacturing process to increase the viscosity index (VI) of the produced lube base oil, the existing lube base oil product manufacturing process includes:

Hydrocracking hydrocarbon feedstock in a hydrocracker to produce hydrocracked wastewater containing unconverted oil;

Separating unconverted milk from hydrocracked wastewater; and

Dewaxing the unconverted oil separated from the hydrocracked wastewater to produce a lubricant base oil product;

Methods for modifying the existing lubricant base oil product manufacturing process include:

A method comprising hydrotreating unconverted oil separated from hydrocracked wastewater prior to dewaxing the unconverted oil to produce a lube base oil product.

19. 19. The method of claim 18, wherein the hydrocarbon feedstock has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or heavy coker gas oil ( How to include HCGO)

20. 20. The method of claim 18 or 19, wherein hydrotreating the unconverted oil comprises increasing the viscosity index (VI) of the unconverted oil.

21. 21. The method of any one of claims 18 to 20, wherein hydroprocessing the unconverted oil comprises contacting the unconverted oil with a hydroprocessing catalyst under hydroprocessing conditions and in the presence of hydrogen.

22. 22. The process of claim 21, wherein the hydroprocessing catalyst and/or hydroprocessing conditions are selected such that VI-increasing molecular modifications predominate in the hydroprocessing.

23. 23. The method of claim 21 or 22, wherein the hydroprocessing catalyst:

(a) one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof; and

(b) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,

(c) a method comprising one or more molecular sieves, such as zeolites.

24. The method according to any one of claims 21 to 23, wherein the hydrotreatment conditions are:

(a) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);

(b) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of 8274 kPa to about 17237 kPa);

(c) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or

(d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to about 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed).

25. 25. The method of any one of claims 18 to 24, wherein hydroprocessing the unconverted milk comprises hydrotreating, hydroisomerizing and/or hydrocracking the unconverted milk.

26. 26. The method of claim 25, wherein the step of hydrotreating the unconverted oil comprises hydrocracking the unconverted oil and the level of hydrocracking conversion during hydrocracking the unconverted oil is determined by hydrocracking the hydrocarbon feedstock in the hydrocracker. Method less than the level of hydrocracking conversion during.

27. 27. The method of claim 26, wherein hydrocracking the unconverted oil occurs at a hydrocracking conversion of about 5% to about 30%, and hydrocracking the hydrocarbon feedstock in the hydrocracker occurs at a hydrocracking conversion of about 5% to about 70%. What happens in the hydrocracking conversion of %.

28. 28. The process according to any one of claims 18 to 27, wherein prior to hydrotreating the unconverted oil, the unconverted milk is:

(a) less than or equal to about 100 ppm sulfur;

(b) less than or equal to about 20 ppm nitrogen; and/or

(c) comprising less than or equal to about 1 ppm of nickel, vanadium and/or copper.

29. 29. The process according to any one of claims 18 to 28, wherein prior to hydrotreating the unconverted oil, the unconverted milk is:

(a) API specific gravity of about 25 to about 45;

(b) at the 95% TBP point between about 800°F and about 1100°F (about 427°C and about 593°C); and/or

(c) a viscosity index (VI) of about 100 to about 150 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270.

30. 30. The method of any one of claims 18 to 29, wherein hydrotreating the unconverted milk comprises increasing the viscosity index (VI) of the unconverted milk by about 5 to about 30.

31. The method of any one of paragraphs 18 to 30, wherein the base oil product has a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270. A method having a viscosity index (VI) of 120 or more.

32. 32. The method of any one of claims 18 to 31, wherein the base oil product is a Group III base oil product.

33. 33. The method of any one of claims 18 to 32, wherein hydroprocessing the unconverted oil from the hydrocracker to produce upgraded unconverted oil occurs in an unconverted oil upgrading reactor.

34. A system for producing a lube base oil product, the system comprising:

A hydrocracker for hydrocracking hydrocarbon feedstock to produce hydrocracked wastewater containing unconverted oil; and

A system comprising an unconverted oil upgrading reactor for producing upgraded unconverted oil by hydrotreating unconverted oil separated from hydrocracked wastewater.

35. According to clause 34,

A system further comprising a dewaxing unit for dewaxing unconverted oil produced by an unconverted oil upgrading reactor to produce a lube base oil product.

36. 36. The method of claim 34 or 35, wherein the hydrocarbonaceous feedstock has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or Systems containing heavy coker gas oil (HCGO).

37. 37. The system of any one of claims 34 to 36, wherein the unconverted oil upgrading reactor is configured to increase the viscosity index (VI) of the unconverted oil.

38. 38. The system of any one of claims 34 to 37, wherein the unconverted oil upgrading reactor has a hydroprocessing zone comprising one or more beds containing a hydroprocessing catalyst, and the hydroprocessing zone is maintained at hydroprocessing conditions. .

39. 39. The system of claim 38, wherein the hydroprocessing catalyst and/or hydroprocessing conditions are selected such that VI-increasing molecular modifications dominate the hydroprocessing.

40. 40. The method of claim 38 or 39, wherein the hydrotreating catalyst:

(a) one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof; and

(b) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,

(c) a system comprising one or more molecular sieves, such as zeolites.

41. The method according to any one of claims 38 to 40, wherein the hydrotreatment conditions are:

(a) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);

(b) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of 8274 kPa to about 17237 kPa);

(c) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or

(d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to about 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or a hydrogen consumption of about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed).

42. 42. The system of any one of claims 38 to 41, wherein hydroprocessing the unconverted milk comprises hydrotreating, hydroisomerizing and/or hydrocracking the unconverted milk.

43. 43. The method of claim 42, wherein the step of hydroprocessing the unconverted oil comprises hydrocracking the unconverted oil and the hydroprocessing zone and the hydrocracker are at a level of hydrocracking conversion during hydrocracking of the unconverted oil in the hydroprocessing zone. A system configured to achieve less than the level of hydrocracking conversion during hydrocracking of hydrocarbon feedstock in the hydrocracker.

44. 44. The method of claim 43, wherein the hydroprocessing zone and the hydrocracker are such that hydrocracking the unconverted oil occurs at a hydrocracking conversion of about 5% to about 30% and hydrocracking the hydrocarbonaceous feedstock within the hydrocracker. A system configured to occur at a hydrocracking conversion of about 30% to about 70%.

45. 45. The system of any one of claims 34 to 44, wherein the system is configured to feed unconverted oil from a hydrocracker to an unconverted oil upgrading reactor comprising:

(a) less than or equal to about 100 ppm sulfur;

(b) less than or equal to about 20 ppm nitrogen; and/or

(c) about 1 ppm or less of nickel, vanadium and/or copper.

46. 46. The system of any one of claims 34 to 45, wherein the system is configured to feed unconverted oil from a hydrocracker to an unconverted oil upgrading reactor having:

(a) API specific gravity of about 25 to about 45;

(b) at the 95% TBP point between about 800°F and about 1100°F (about 427°C and about 593°C); and/or

(c) a viscosity index (VI) of about 100 to about 150 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270.

47. 47. The system of any one of claims 34 to 46, wherein the unconverted oil upgrading reactor is configured to increase the viscosity index (VI) of the unconverted oil by about 5 to about 30.

48. The method of any one of items 34 to 47, wherein the viscosity index is greater than or equal to 120 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270. A system configured to produce a lube base oil product having (VI).

49. 49. The system of any one of claims 34-48, wherein the system is configured to produce a Group III base oil product.

50. 49. The system according to any one of claims 34 to 49, wherein the system is a base oil production plant.

51. A method of modifying an existing system for producing a base oil product to increase the viscosity index (VI) of the base oil product, the existing system for producing a base oil product comprising:

A hydrocracker for hydrocracking hydrocarbon feedstock to produce hydrocracked wastewater containing unconverted oil; and

It includes a dewaxing unit for producing a lubricant base oil product by dewaxing unconverted oil separated from hydrocracked wastewater;

Here's how to modify an existing system:

A method comprising installing an unconverted oil upgrading reactor in an existing system to hydroprocess unconverted oil separated from hydrocracked wastewater prior to dewaxing the unconverted oil to produce a lube base oil product.

52. 52. The method of claim 51, wherein the hydrocarbon feedstock has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or heavy coker gas oil ( HCGO).

53. 53. The method of claim 51 or 52, wherein the unconverted oil upgrading reactor is configured to increase the viscosity index (VI) of the unconverted oil.

54. 54. The method of any one of claims 51 to 53, wherein the unconverted oil upgrading reactor has a hydroprocessing zone comprising one or more beds containing a hydroprocessing catalyst, and the hydroprocessing zone is maintained at hydroprocessing conditions. .

55. 55. The process of claim 54, wherein the hydroprocessing catalyst and/or hydroprocessing conditions are selected such that VI-increasing molecular modifications predominate in the hydroprocessing.

56. 56. The method of claim 54 or 55, wherein the hydrotreating catalyst:

(a) one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof; and

(b) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,

(c) a method comprising one or more molecular sieves, such as zeolites.

57. The method according to any one of claims 54 to 56, wherein the hydrotreatment conditions are:

(a) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);

(b) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of 8274 kPa to about 17237 kPa);

(c) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or

(d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to about 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed).

58. 58. The method of any one of claims 51-57, wherein hydroprocessing the unconverted milk comprises hydrotreating, hydroisomerizing and/or hydrocracking the unconverted milk.

59. 59. The method of claim 58, wherein said step of hydroprocessing the unconverted oil comprises hydrocracking the unconverted oil and said hydroprocessing zone and hydrocracker have a level of hydrocracking conversion during hydrocracking of the unconverted oil in the hydroprocessing zone. A method comprising reducing the level of hydrocracking conversion during hydrocracking of hydrocarbon feedstock in a hydrocracker.

60. 60. The method of claim 59, wherein the hydroprocessing zone and the hydrocracker are such that hydrocracking the unconverted oil occurs at a hydrocracking conversion of about 5% to about 30% and hydrocracking the hydrocarbonaceous feedstock within the hydrocracker. A process configured to occur at a hydrocracking conversion of about 30% to about 70%.

61. 61. The method of any one of claims 51 to 60, comprising configuring an existing system to feed unconverted oil from a hydrocracker to an unconverted oil upgrading reactor comprising:

(a) less than or equal to about 100 ppm sulfur;

(b) less than or equal to about 20 ppm nitrogen; and/or

(c) about 1 ppm or less of nickel, vanadium and/or copper.

62. 62. The method of any one of claims 51 to 61, comprising configuring an existing system to feed unconverted oil from a hydrocracker to an unconverted oil upgrading reactor comprising:

(a) API specific gravity of about 25 to about 45;

(b) at the 95% TBP point between about 800°F and about 1100°F (about 427°C and about 593°C); and/or

(c) a viscosity index (VI) of about 100 to about 150 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270.

63. 63. The method of any one of claims 51 to 62, wherein the unconverted oil upgrading reactor is configured to increase the viscosity index (VI) of the unconverted oil by about 5 to about 30.

64. The method of any one of paragraphs 51 to 63, wherein after modifying the existing system, the lube base oil product produced has a reduction of 4 cSt (at 100° C. (212° F.)), as measured in accordance with ASTM D-2270. A method having a viscosity index (VI) of more than 120 at a kinematic viscosity of 4 mm ² s ^-1 ).

65. 65. The method of any one of claims 51 to 64, wherein, after modifying an existing system, the base oil product produced is a Group III base oil product.

66. 66. The method of any one of claims 51 to 65, wherein the existing system is a base oil production plant.

67. An unconverted oil upgrading reactor for hydrotreating unconverted oil separated from the hydrocracked wastewater of a hydrocracker prior to dewaxing the unconverted oil to produce a lubricant base oil product. The unconverted oil upgrading reactor is:

(a) having a hydroprocessing zone comprising one or more beds containing a hydroprocessing catalyst, wherein the hydroprocessing zone is maintained at hydroprocessing conditions;

(b) An unconverted oil upgrading reactor configured to increase the viscosity index (VI) of the unconverted oil.

68. 67. The method of claim 67, wherein:

(a) The hydrotreating catalyst is:

(i) one or more metals and/or one or more compounds thereof selected from groups VI and VIII to X; and

(ii) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,

(iii) comprises one or more molecular sieves, such as zeolites;

(b) Hydrotreatment conditions are:

(i) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);

(ii) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of from 8274 kPa to about 17237 kPa);

(iii) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or

(iv) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed).

69. (a) by a method according to any one of claims 1 to 17, (b) using a system according to any of claims 34 to 50, or (c) by a method according to any of claims 51 to 50. Lube base oil products produced using a system modified by the method according to any one of paragraph 66.

70. Lubricants containing the lubricant base oil product of claim 69.

71. Use of upgraded unconverted oil in the manufacture of base oil products to increase the viscosity index (VI) of the manufactured base oil product.

72. 72. The use of claim 71, wherein the production of the base oil product comprises dewaxing the upgraded unconverted oil in a dewaxing unit.

73. 73. The method of claim 71 or 72, wherein the upgraded unconverted oil has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or Use obtained by hydrotreating unconverted oil obtained from hydrocracking of hydrocarbon feedstock containing heavy coker gas oil (HCGO).

74. Use of dewaxed, upgraded unconverted oil as base oil product in lubricants to increase the viscosity index (VI) of the lubricant.

75. 75. The method of claim 74, wherein the dewaxed, upgraded unconverted oil (a) has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO). ) or (b) by hydrotreating unconverted oil obtained from hydrocracking of hydrocarbon feedstocks comprising heavy coker gas oil (HCGO), and (b) by dewaxing the hydrotreated unconverted oil.

It will be understood that the present invention is not limited to the embodiments described above and that various modifications and improvements may be made without departing from the concepts described herein. Except where mutually exclusive, any feature may be used individually or in combination with any other feature and this disclosure extends to and includes any combination or sub-combination of one or more features described herein.

Claims (73)

A method of producing a base oil product comprising:
Hydrotreating the unconverted oil from the hydrocracker in a separate unconverted oil upgrading reactor to produce upgraded unconverted oil; and
A method comprising dewaxing upgraded unconverted oil to produce a lube base oil product. The method of claim 1, prior to hydrotreating the unconverted oil from the hydrocracker,
Hydrocracking hydrocarbon feedstock in a hydrocracker to produce hydrocracked wastewater containing unconverted oil; and
A method further comprising the step of separating unconverted milk from hydrocracked wastewater. 3. The method of claim 2, wherein the hydrocarbon feedstock has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or heavy coker gas oil ( HCGO). 4. The process of any one of claims 1 to 3, wherein hydroprocessing the unconverted oil from the hydrocracker to produce upgraded unconverted oil comprises increasing the viscosity index (VI) of the unconverted oil. The method of any one of claims 1 to 4, wherein the step of hydrotreating the unconverted oil from the hydrocracker to produce upgraded unconverted oil includes contacting the unconverted oil with a hydroprocessing catalyst under hydroprocessing conditions and in the presence of hydrogen. A method that includes being told to do so. 6. The process of claim 5, wherein the hydroprocessing catalyst and/or hydroprocessing conditions are selected such that VI-increasing molecular modifications predominate in the hydroprocessing. 7. The method of claim 5 or 6, wherein the hydrotreating catalyst is:
(a) one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof; and
(b) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,
(c) a method comprising one or more molecular sieves, such as zeolites. The method according to any one of claims 5 to 7, wherein the hydrotreatment conditions are:
(a) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);
(b) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of 8274 kPa to about 17237 kPa);
(c) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or
(d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to about 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed). 9. The method of any one of claims 1 to 8, wherein the step of hydrotreating the unconverted oil from the hydrocracker to produce upgraded unconverted oil comprises hydrotreating, hydroisomerizing and/or A method comprising hydrocracking. 10. The method of claim 9, wherein, when relying on claim 2, the step of hydrotreating the unconverted oil from the hydrocracker comprises hydrocracking the unconverted oil from the hydrocracker and hydrocracking the unconverted oil from the hydrocracker. A method in which the level of hydrocracking conversion during hydrocracking is less than the level of hydrocracking conversion during hydrocracking of hydrocarbon feedstock in a hydrocracker. 11. The method of claim 10, wherein hydrocracking the unconverted oil from the hydrocracker occurs at a hydrocracking conversion of about 5% to about 30% and hydrocracking the hydrocarbon feedstock in the hydrocracker occurs at a hydrocracking conversion of about 5% to about 30%. A method that occurs at a hydrocracking conversion of from about 70%. 12. The process according to any one of claims 1 to 11, wherein prior to hydrotreating the unconverted oil from the hydrocracker, the unconverted oil is:
(a) less than or equal to about 100 ppm sulfur;
(b) less than or equal to about 20 ppm nitrogen; and/or
(c) comprising less than or equal to about 1 ppm of nickel, vanadium and/or copper. 13. The process according to any one of claims 1 to 12, wherein prior to hydrotreating the unconverted oil from the hydrocracker, the unconverted oil is:
(a) API specific gravity of about 25 to about 45;
(b) at the 95% TBP point between about 800°F and about 1100°F (about 427°C and about 593°C); and/or
(c) a viscosity index (VI) of about 100 to about 150 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270. 14. The method of any one of claims 1 to 13, wherein hydrotreating the unconverted oil to produce a base oil product comprises increasing the viscosity index (VI) of the unconverted oil by about 5 to about 30. . 15. The method of any one of claims 1 to 14, wherein the base oil product has a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), measured according to ASTM D-2270. A method having a viscosity index (VI) of or higher. 16. The method of any one of claims 1 to 15, wherein the base oil product is a Group III base oil product. As a method of modifying the existing lube base oil product manufacturing process to increase the viscosity index (VI) of the produced lube base oil, the existing lube base oil product manufacturing process includes:
Hydrocracking hydrocarbon feedstock in a hydrocracker to produce hydrocracked wastewater containing unconverted oil;
Separating unconverted milk from hydrocracked wastewater; and
Dewaxing the unconverted oil separated from the hydrocracked wastewater to produce a lubricant base oil product;
Methods for modifying the existing lubricant base oil product manufacturing process include:
A method comprising hydrotreating unconverted oil separated from hydrocracked wastewater in a separate unconverted oil upgrading reactor prior to dewaxing the unconverted oil to produce a base oil product. 18. The method of claim 17, wherein the hydrocarbon feedstock has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or heavy coker gas oil ( HCGO). 19. The method of claim 17 or 18, wherein hydrotreating the unconverted oil comprises increasing the viscosity index (VI) of the unconverted oil. 20. The method of any one of claims 17 to 19, wherein hydroprocessing the unconverted oil comprises contacting the unconverted oil with a hydroprocessing catalyst under hydroprocessing conditions and in the presence of hydrogen. 21. The process of claim 20, wherein the hydroprocessing catalyst and/or hydroprocessing conditions are selected such that VI-increasing molecular modifications predominate in the hydroprocessing. 22. The method of claim 20 or 21, wherein the hydrotreating catalyst:
(a) one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof; and
(b) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,
(c) a method comprising one or more molecular sieves, such as zeolites. The method according to any one of claims 20 to 22, wherein the hydrotreatment conditions are:
(a) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);
(b) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of 8274 kPa to about 17237 kPa);
(c) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or
(d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to about 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed). 24. The method of any one of claims 17 to 23, wherein hydroprocessing the unconverted milk comprises hydrotreating, hydroisomerizing and/or hydrocracking the unconverted milk. 25. The method of claim 24, wherein the step of hydrotreating the unconverted oil includes hydrocracking the unconverted oil and the level of hydrocracking conversion during hydrocracking the unconverted oil is determined by hydrocracking the hydrocarbon feedstock in the hydrocracker. Method less than the level of hydrocracking conversion during. 26. The method of claim 25, wherein hydrocracking the unconverted oil occurs at a hydrocracking conversion of about 5% to about 30%, and hydrocracking the hydrocarbon feedstock in the hydrocracker occurs at a hydrocracking conversion of about 5% to about 70%. What happens in the hydrocracking conversion of %. 27. The process according to any one of claims 17 to 26, wherein prior to hydrotreating the unconverted oil, the unconverted oil is:
(a) less than or equal to about 100 ppm sulfur;
(b) less than or equal to about 20 ppm nitrogen; and/or
(c) comprising less than or equal to about 1 ppm of nickel, vanadium and/or copper. 28. The process according to any one of claims 17 to 27, wherein prior to hydrotreating the unconverted milk, the unconverted milk is:
(a) API specific gravity of about 25 to about 45;
(b) at the 95% TBP point between about 800°F and about 1100°F (about 427°C and about 593°C); and/or
(c) a viscosity index (VI) of about 100 to about 150 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270. 29. The method of any one of claims 17-28, wherein hydrotreating the unconverted milk comprises increasing the viscosity index (VI) of the unconverted milk by about 5 to about 30. 29. The method of any one of claims 17 to 29, wherein the base oil product has a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), measured according to ASTM D-2270. A method having a viscosity index (VI) of or higher. 31. The method of any one of claims 17 to 30, wherein the base oil product is a Group III base oil product. A system for producing a lube base oil product, the system comprising:
A hydrocracker for hydrocracking hydrocarbon feedstock to produce hydrocracked wastewater containing unconverted oil; and
A system comprising a separate unconverted oil upgrading reactor for hydroprocessing unconverted oil separated from hydrocracked wastewater to produce upgraded unconverted oil. According to clause 32,
A system further comprising a dewaxing unit for dewaxing unconverted oil produced by an unconverted oil upgrading reactor to produce a lube base oil product. 34. The method of claim 32 or 33, wherein the hydrocarbonaceous feedstock has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or Systems containing heavy coker gas oil (HCGO). 35. The system of any one of claims 32 to 34, wherein the unconverted oil upgrading reactor is configured to increase the viscosity index (VI) of the unconverted oil. 36. The system of any one of claims 32 to 35, wherein the unconverted oil upgrading reactor has a hydroprocessing zone comprising one or more beds containing a hydroprocessing catalyst, and the hydroprocessing zone is maintained at hydroprocessing conditions. . 37. The system of claim 36, wherein the hydroprocessing catalyst and/or hydroprocessing conditions are selected such that VI-increasing molecular modifications dominate the hydroprocessing. 38. The method of claim 36 or 37, wherein the hydrotreating catalyst:
(a) one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof; and
(b) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,
(c) a system comprising one or more molecular sieves, such as zeolites. The method according to any one of claims 36 to 38, wherein the hydrotreatment conditions are:
(a) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);
(b) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of 8274 kPa to about 17237 kPa);
(c) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or
(d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to about 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or a hydrogen consumption of about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed). 40. The system of any one of claims 36 to 39, wherein hydroprocessing the unconverted milk comprises hydrotreating, hydroisomerizing and/or hydrocracking the unconverted milk. 41. The method of claim 40, wherein said step of hydroprocessing the unconverted oil comprises hydrocracking the unconverted oil and said hydroprocessing zone and hydrocracker have a level of hydrocracking conversion during hydrocracking of the unconverted oil in the hydroprocessing zone. A system configured to achieve less than the level of hydrocracking conversion during hydrocracking of hydrocarbon feedstock in a hydrocracker. 42. The method of claim 41, wherein the hydroprocessing zone and the hydrocracker are such that hydrocracking the unconverted oil occurs at a hydrocracking conversion of about 5% to about 30% and hydrocracking the hydrocarbonaceous feedstock within the hydrocracker. A system configured to occur at a hydrocracking conversion of about 30% to about 70%. 43. The system of any one of claims 32 to 42, wherein the system is configured to feed unconverted oil from a hydrocracker to an unconverted oil upgrading reactor comprising:
(a) less than or equal to about 100 ppm sulfur;
(b) less than or equal to about 20 ppm nitrogen; and/or
(c) about 1 ppm or less of nickel, vanadium and/or copper. 44. The system of any one of claims 32 to 43, wherein the system is configured to feed unconverted oil from a hydrocracker to an unconverted oil upgrading reactor having:
(a) API specific gravity of about 25 to about 45;
(b) at the 95% TBP point between about 800°F and about 1100°F (about 427°C and about 593°C); and/or
(c) a viscosity index (VI) of about 100 to about 150 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270. 45. The system of any one of claims 32 to 44, wherein the unconverted oil upgrading reactor is configured to increase the viscosity index (VI) of the unconverted oil by about 5 to about 30. 46. The method of any one of claims 32 to 45, wherein the viscosity index (VI) is greater than or equal to 120 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270. A system configured to produce a lubricant base oil product having ). 47. The system of any one of claims 32 to 46, wherein the system is configured to produce a Group III base oil product. 48. The system of any one of claims 32 to 47, wherein the system is a base oil production plant. A method of modifying an existing system for producing a base oil product to increase the viscosity index (VI) of the base oil product, the existing system for producing a base oil product comprising:
A hydrocracker for hydrocracking hydrocarbon feedstock to produce hydrocracked wastewater containing unconverted oil; and
It includes a dewaxing unit for producing a lubricant base oil product by dewaxing unconverted oil separated from hydrocracked wastewater;
Here's how to modify an existing system:
A method comprising installing a separate unconverted oil upgrading reactor in an existing system to hydroprocess unconverted oil separated from hydrocracked wastewater prior to dewaxing the unconverted oil to produce a lube base oil product. 50. The method of claim 49, wherein the hydrocarbon feedstock has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or heavy coker gas oil ( HCGO). 51. The method of claim 49 or 50, wherein the unconverted oil upgrading reactor is configured to increase the viscosity index (VI) of the unconverted oil. 52. The method of any one of claims 49 to 51, wherein the unconverted oil upgrading reactor has a hydroprocessing zone comprising one or more beds containing a hydroprocessing catalyst, and the hydroprocessing zone is maintained at hydroprocessing conditions. . 53. The process of claim 52, wherein the hydroprocessing catalyst and/or hydroprocessing conditions are selected such that VI-increasing molecular modifications predominate in the hydroprocessing. 54. The method of claim 52 or 53, wherein the hydrotreating catalyst:
(a) one or more metals selected from groups VI and VIII to X and/or one or more compounds thereof; and
(b) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,
(c) a method comprising one or more molecular sieves, such as zeolites. 55. The process according to any one of claims 52 to 54, wherein the hydrotreatment conditions are:
(a) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);
(b) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of 8274 kPa to about 17237 kPa);
(c) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or
(d) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to about 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed). 56. The method of any one of claims 49-55, wherein hydroprocessing the unconverted milk comprises hydrotreating, hydroisomerizing and/or hydrocracking the unconverted milk. 57. The method of claim 56, wherein hydroprocessing the unconverted oil comprises hydrocracking the unconverted oil and the hydroprocessing zone and hydrocracker have a level of hydrocracking conversion during hydrocracking of the unconverted oil in the hydroprocessing zone. A method comprising reducing the level of hydrocracking conversion during hydrocracking of hydrocarbon feedstock in a hydrocracker. 58. The method of claim 57, wherein the hydroprocessing zone and hydrocracker are such that hydrocracking the unconverted oil occurs at a hydrocracking conversion of about 5% to about 30% and hydrocracking the hydrocarbonaceous feedstock within the hydrocracker. A process configured to occur at a hydrocracking conversion of about 30% to about 70%. 59. The method of any one of claims 49-58, comprising configuring an existing system to feed unconverted oil from a hydrocracker to an unconverted oil upgrading reactor comprising:
(a) less than or equal to about 100 ppm sulfur;
(b) less than or equal to about 20 ppm nitrogen; and/or
(c) about 1 ppm or less of nickel, vanadium and/or copper. 60. The method of any one of claims 49 to 59, comprising configuring an existing system to feed unconverted oil from a hydrocracker to an unconverted oil upgrading reactor comprising:
(a) API specific gravity of about 25 to about 45;
(b) at the 95% TBP point between about 800°F and about 1100°F (about 427°C and about 593°C); and/or
(c) a viscosity index (VI) of about 100 to about 150 at a kinematic viscosity of 4 cSt (4 mm ² s ^-1 ) at 100° C. (212° F.), as measured according to ASTM D-2270. 61. The method of any one of claims 49-60, wherein the unconverted oil upgrading reactor is configured to increase the viscosity index (VI) of the unconverted oil by about 5 to about 30. 62. The method of any one of claims 49 to 61, wherein after modifying an existing system, the lube base oil product produced has a 4 cSt (4 mm A method having a viscosity index (VI) of more than 120 at a kinematic viscosity of ² s ^-1 ). 63. The method of any one of claims 49 to 62, wherein, after modifying an existing system, the base oil product produced is a Group III base oil product. 64. A method according to any one of claims 49 to 63, wherein the existing system is a base oil production plant. An unconverted oil upgrading reactor for hydrotreating unconverted oil separated from the hydrocracked wastewater of a hydrocracker prior to dewaxing the unconverted oil to produce a lubricant base oil product. The unconverted oil upgrading reactor is:
(a) having a hydroprocessing zone comprising one or more beds containing a hydroprocessing catalyst, wherein the hydroprocessing zone is maintained at hydroprocessing conditions;
(b) An unconverted oil upgrading reactor configured to increase the viscosity index (VI) of the unconverted oil. 65. The method of claim 65, wherein:
(a) The hydrotreating catalyst is:
(i) one or more metals and/or one or more compounds thereof selected from groups VI and VIII to X; and
(ii) a catalyst support, such as a porous refractory support, such as alumina, silica, amorphous silica-alumina material, or combinations thereof; and, optionally,
(iii) comprises one or more molecular sieves, such as zeolites;
(b) Hydrotreatment conditions are:
(i) a reaction temperature of about 400°F to about 950°F (about 204°C to about 510°C), such as about 650°F to about 850°F (about 343°C to about 454°C);
(ii) about 500 psi to about 5000 psi (about 3447 kPa to about 34474 kPa), such as about 1500 psi to about 2500 psi (about 10342 kPa to about 17237 kPa), or about 1200 psi to about 2500 psi. a reaction gauge pressure of 8274 kPa to about 17237 kPa);
(iii) about 0.1 hr ^-1 to about 15 hr ^-1 , for example, about 0.2 hr ^-1 to about 10 hr ^-1 , or about 0.2 hr ^-1 to about 2.5 hr ^-1 , or about 0.1 hr ^-1 LHSV from about 10 hr ^-1 ; and/or
(iv) about 100 scf to about 2500 scf per barrel of liquid hydrocarbon feed (about 17.8 to 445 m ³ H ₂ /m ³ feed), for example, about 200 scf to about 2500 scf per barrel (about 35.6 to about 35.6 scf). 445 m ³ H ₂ /m ³ feed), or about 100 scf to about 1500 scf per barrel (about 17.8 to about 267 m ³ H ₂ /m ³ feed). (a) by a method according to any one of claims 1 to 16, (b) using a system according to any of claims 32 to 48, or (c) by a method according to any of claims 49 to 48. Lube base oil products produced using a system modified by the method according to any one of paragraph 64. Lubricants containing the lube base oil product of claim 67. Use of upgraded unconverted oil in the manufacture of base oil products to increase the viscosity index (VI) of the manufactured base oil product. 70. Use according to claim 69, wherein the production of the base oil product comprises dewaxing the upgraded unconverted oil in a dewaxing unit. 71. The method of claim 69 or 70, wherein the upgraded unconverted oil has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO) or Use obtained by hydrotreating unconverted oil obtained from hydrocracking of hydrocarbon feedstock containing heavy coker gas oil (HCGO). Use of dewaxed, upgraded unconverted oil as base oil product in lubricants to increase the viscosity index (VI) of the lubricant. 73. The method of claim 72, wherein the dewaxed, upgraded unconverted oil (a) has a boiling point in the range of about 572°F to about 1112°F (about 300°C to about 600°C) and/or is a gas oil, such as vacuum gas oil (VGO). ) or (b) by hydrotreating unconverted oil obtained from hydrocracking of hydrocarbon feedstocks comprising heavy coker gas oil (HCGO), and (b) by dewaxing the hydrotreated unconverted oil.

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