EP3280782B1 - Procédé de saturation pour fabriquer des huiles de base pour lubrifiant - Google Patents

Procédé de saturation pour fabriquer des huiles de base pour lubrifiant Download PDF

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EP3280782B1
EP3280782B1 EP15722814.9A EP15722814A EP3280782B1 EP 3280782 B1 EP3280782 B1 EP 3280782B1 EP 15722814 A EP15722814 A EP 15722814A EP 3280782 B1 EP3280782 B1 EP 3280782B1
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catalyst
aromatic saturation
temperature
effective
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EP3280782A1 (fr
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Gary P. Schleicher
Eric D. Joseck
Teck-mui HO
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Priority claimed from US14/681,331 external-priority patent/US9809762B2/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • This disclosure provides systems and methods for hydroprocessing of lubricant base oil boiling range feeds.
  • One of the goals in processing of petroleum fractions is to find a high value use for as much of a petroleum fraction as possible. Even if a process converts a large percentage of a feed into a desired product, if the residual portion of the feed cannot be used in a secondary product, the overall process may not be profitable.
  • hydrocracking of hydrocarbon feedstocks is often used to convert lower value hydrocarbon fractions into higher value products, such as conversion of vacuum gas oil (VGO) feedstocks to various fuels and lubricants.
  • VGO vacuum gas oil
  • a typical fuels hydrocracking process will also generate a portion of unconverted feed. For a typical fuels hydrocracking process to be profitable for a refinery, a beneficial use needs to be identified for this unconverted feed portion.
  • the present invention relates to a method for producing a lubricant base oil comprising aromatic saturation stage(s) according to claim 1.
  • Preferred optional features of the invention are set out in the dependent claims.
  • the aromatic content of a bottom fraction from a hydrocracking process is reduced using a aromatic saturation stage with multiple catalyst beds, or alternatively using a reactor (or reactors) with multiple aromatic saturation stages.
  • the catalysts in the various beds or stages are selected to provide different types of aromatic saturation activity.
  • An initial bed or stage can provide activity for saturation of 1-ring aromatics in the petroleum fraction.
  • One or more subsequent beds or stages, operating at successively lower temperature, can then be used to reduce the multiple-ring aromatic content of the petroleum fraction.
  • a fuels hydrocracking process typically has less stringent requirements for the sulfur and nitrogen content of a feed as compared to a lubricant base oil. Additionally, depending on the nature of the feed for the fuels hydrocracking process, the bottoms fraction may contain a relatively high level of aromatics compounds. Various regulations restrict the quantity and type of aromatic compounds that can be present in lubricant base oils. In order to use such a petroleum fraction as a lubricant base oil, the aromatic content needs to be reduced to levels that match the specifications and/or regulatory requirements for the desired type of lubricant base oil.
  • the method produces lubricant base stocks with reduced aromatic content. Based in part on changes in regulations in various countries, the desirable amount of aromatics in a lubricant base oil today can often be lower than in the past. As a result, methods that can allow an existing lubricant base oil production system to generate lower aromatic content base oils while reducing or minimizing the amount of additional equipment can be desirable. Additionally or alternately, methods that can allow an existing lubricant base oil production system to generate lower aromatic content base oils while reducing or minimizing any losses in total system throughput and/or losses in product yield can also be desirable.
  • the aromatic content of such a petroleum fraction can be reduced using an aromatic saturation stage with multiple catalyst beds, or alternatively using a reactor (or reactors) with multiple aromatic saturation stages.
  • the catalysts in the various beds or stages are selected to provide different types of aromatic saturation activity.
  • An initial bed or stage can provide activity for saturation of 1-ring aromatics in the petroleum fraction.
  • One or more subsequent beds or stages, operating at successively lower temperature, can then be used to reduce the multiple-ring aromatic content of the petroleum fraction.
  • the pressure can be selected to provide a desired type of lubricant base oil, with lower pressures being suitable for production of Group I type lubricant base oils and higher pressures being suitable for production of Group II type lubricant base oils.
  • the input feed is a bottoms cut from a fuels hydrocracking process.
  • an input feed can be a bottoms cut from a hydrocracking process for forming a lubricant base oil.
  • feeds with sulfur contents of less than 300 wppm can be used.
  • a typical bottoms fraction from a lubricant base oil production process will have a sulfur content of 10 wppm or less, along with a nitrogen content of 1 wppm or less.
  • a typical bottoms fraction from a fuels hydrocracking process will have a sulfur content of 100 wppm or less, along with a nitrogen content of 10 wppm or less.
  • a feed with up to 500 wppm of sulfur could be used. In such an alternative situation, the type of sulfur in the feed would need to be sulfur that could be removed during the aromatic saturation process to a level of 300 wppm or less.
  • Suitable input feeds for aromatic saturation will typically be feeds that contain various types of single ring and multi-ring aromatics.
  • the total aromatics content of a suitable feed can be at least 200 mmol/kg (equivalent to ⁇ mol/g), such as at least 600 mmol/kg, or at least 1000 mmol/kg.
  • the amount of multi-ring aromatics can be at least 50 mmol/kg, or at least 100 mmol/kg, or at least 200 mmol/kg.
  • the total aromatics content can be at least 75 mmol/kg, or at least 100 mmol/kg, or at least 150 mmol/kg, or at least 200 mmol/kg, or at least 400 mmol/kg, or at least 600 mmol/kg. Additionally or alternately, the total aromatics content can be 1000 mmol/kg or less, or 600 mmol/kg or less, or 400 mmol/kg or less, or 200 mmol/kg or less. It is noted that each of the above lower limits for total aromatics content is explicitly contemplated with each of the above upper limits for total aromatics content. In addition to and/or as an alternative to characterizing the total aromatics content, the amount of multi-ring aromatics is characterized.
  • the amount of multi-ring aromatics in the feed is 10 mmol/kg to 500 mmol/kg.
  • the content of multi-ring aromatics can be at least 25 mmol/kg, or at least 50 mmol/kg, or at least 100 mmol/kg, or at least 150 mmol/kg, or at least 200 mmol/kg.
  • the total aromatics content of a suitable feed is from 50 mmol/kg to 1200 mmol/kg, preferably 50 mmol/kg to 1000 mmol/kg, or 50 mmol/kg to 800 mmol/kg, or 50 mmol/kg to 600 mmol/kg, or 50 mmol/kg to 400 mmol/kg, or 50 mmol/kg to 200 mmol/kg, or 100 mmol/kg to 1200 mmol/kg, or 100 mmol/kg to 1000 mmol/kg, or 150 mmol/kg to 1200 mmol/kg, or 150 mmol/kg to 1000 mmol/kg, or 200 mmol/kg to 1200 mmol/kg, or 200 mmol/kg to 1000 mmol/kg.
  • the bottoms (or a portion of the bottoms) from a hydrocracking process as part of fuels and/or lubricant base oil production can be used.
  • the goal for processing this type of suitable feed can be to provide further improved aromatic saturation in the resulting product as compared to the aromatic saturation available from conventional methods.
  • the total aromatics content can be 50 mmol/kg to 600 mmol/kg, or 50 mmol/kg to 400 mmol/kg, or 50 mmol/kg to 200 mmol/kg, or 50 mmol/kg to 150 mmol/kg, or 75 mmol/kg to 600 mmol/kg, or 75 mmol/kg to 400 mmol/kg, or 75 mmol/kg to 200 mmol/kg, or 75 mmol/kg to 150 mmol/kg, or 100 mmol/kg to 600 mmol/kg, or 100 mmol/kg to 400 mmol/kg, or 100 mmol/kg to 200 mmol/kg.
  • the amount of multi-ring aromatics can also be characterized.
  • the amount of multi-ring aromatics in the feed can be 10 mmol/kg to 100 mmol/kg, or 10 mmol/kg to 75 mmol/kg, or 10 mmol/kg to 50 mmol/kg, or 10 mmol/kg to 30 mmol/kg, or 25 mmol/kg to 100 mmol/kg, or 25 mmol/kg to 75 mmol/kg, or 25 mmol/kg to 50 mmol/kg.
  • mutagenicity index is a value measured using an ASTM approved procedure called the modified Ames assay. In some situations, mutagenicity index can also be estimated or calculated based on correlations with compounds detected in a sample.
  • the mutagenicity index of an input feed can be at least 0.4, or at least 1.0.
  • a potential goal of the aromatic saturation processing can be to reduce the mutagenicity index of an input feed to 1.0 or less, or preferably to 0.4 or less.
  • a feed with a mutagenicity index of less than 0.4 can also be processed according to the disclosure to achieve still lower values of mutagenicity index. Lower values of mutagenicity index can be beneficial so that random processing variations during commercial scale production do not result in a sample with an undesirable mutagenicity index value.
  • the mutagenicity index for a sample can be estimated by measuring the absorptivity of the sample at 325 nm.
  • Table 1 shows an example of mutagenicity index values generated using a modified Ames assay versus measurements of the ultraviolet absorption for the same samples at 325 nm.
  • Table 1 Absorptivity at 325 nm Mutagenicity index 0.014 0.1 0.018 0.1 0.03 0.2 0.018 0.3 0.028 0.3 0.044 0.7 0.037 0.2 0.158 1.2 0.227 1.8
  • IP-346 is a standardized test that determines a weight percent of compounds that are extracted using a solvent, such as dimethyl sulfoxide (DMSO).
  • DMSO dimethyl sulfoxide
  • IP-346 is a test designed to measure a property of a sample that is somewhat similar to mutagenicity index, the results of an IP-346 measurement do not correspond to a mutagenicity index measurement in a straightforward manner.
  • substances with an IP-346 value of greater than 3 wt% may be required to have a label indicating that the substance is "toxic".
  • another potential goal of an aromatic saturation process is to process an input feed with an IP-346 value greater than 3.0 wt% to generate a product with an IP-346 value less than 3.0 wt%.
  • the IP-346 value of the product can be 1.5 wt% or less, or 1.0 wt% or less.
  • Lower IP-346 values can be beneficial so that random processing variations during commercial scale production do not result in a sample with an undesirable IP-346 value.
  • the input feed should also have suitable lubricant base oil properties.
  • an input feed intended for use as a Group I or Group II base oil can have a viscosity index (VI) of at least 80, preferably at least 90 or at least 95.
  • An input feed intended for use as a Group I+ base oil can have a VI of at least 100, while an input feed intended for use as a Group II+ base oil can have a VI of at least 110.
  • the viscosity of the input feed can be at least 2 cSt at 100°C, or at least 4 cSt at 100°C, or at least 6 cSt at 100°C.
  • a Group VIII noble metal refers to a metal selected from Pt, Pd, Rh, Ir, Ru, or Os, preferably Pt, Pd, or a combination thereof.
  • a base metal can refer to a base Group VIII metal or a base Group VIB metal.
  • a base Group VIII metal (alternatively referred to as a non-noble Group VIII metal) refers to Fe, Co, or Ni, preferably Co, Ni, or a combination thereof.
  • a Group VIB metal refers to Cr, Mo, or W, preferably Mo, W, or a combination thereof.
  • Group I basestocks or base oils are defined as base oils with less than 90 wt% saturated molecules and/or at least 0.03 wt% sulfur content. Group I basestocks also have a viscosity index (VI) of at least 80 but less than 120. Group II basestocks or base oils contain at least 90 wt% saturated molecules and less than 0.03 wt% sulfur. Group II basestocks also have a viscosity index of at least 80 but less than 120. Group III basestocks or base oils contain at least 90 wt% saturated molecules and less than 0.03 wt% sulfur, with a viscosity index of at least 120.
  • VI viscosity index
  • Group I basestocks may be referred to as a Group I+ basestock, which corresponds to a Group I basestock with a VI value of 103 to 108.
  • Some Group II basestocks may be referred to as a Group II+ basestock, which corresponds to a Group II basestock with a VI of at least 113.
  • Some Group III basestocks may be referred to as a Group III+ basestock, which corresponds to a Group III basestock with a VI value of at least 140.
  • reaction stage In a hydroprocessing reaction system, one way of characterizing a reaction stage is based on the stage being a "sweet" reaction stage or a "sour" reaction stage.
  • a reaction stage where the feedstock passed into to the stage contains at least 500 wppm of sulfur, or at least 1000 wppm of sulfur can be referred to as a "sour" reaction stage.
  • the reaction stage can be characterized based on the sulfur content of both the feedstock and any treat gas passed into the reaction stage.
  • a sour reaction stage can be in contrast to a "sweet" reaction stage, where the sulfur content in the feedstock passed into the stage is 500 wppm or less, or 300 wppm or less, or 100 wppm or less, or 50 wppm or less, or 15 wppm or less.
  • the severity of hydroprocessing performed on a feed can be characterized based on an amount of conversion of the feedstock.
  • the reaction conditions in the reaction system can be selected to generate a desired level of conversion of a feed.
  • Conversion of a feed is defined in terms of conversion of molecules that boil above a temperature threshold to molecules below that threshold.
  • the conversion temperature can be any convenient temperature.
  • a suitable conversion temperature can be from 650°F (343°C) to 750°F (399°C). Unless otherwise specified, the conversion temperature in this discussion is a conversion temperature of 700°F (371°C).
  • an input feed for an aromatic saturation process can be generated as a product or side-product from a previous type of hydroprocessing, such as hydrocracking for fuels or lubricant base stock production.
  • Suitable feedstocks include whole and reduced petroleum crudes, atmospheric and vacuum residua, propane deasphalted residua, e.g., brightstock, cycle oils, FCC tower bottoms, gas oils, including atmospheric and vacuum gas oils and coker gas oils, light to heavy distillates including raw virgin distillates, hydrocrackates, hydrotreated oils, dewaxed oils, slack waxes, Fischer-Tropsch waxes, raffinates, and mixtures of these materials.
  • One way of defining a feedstock is based on the boiling range of the feed.
  • One option for defining a boiling range is to use an initial boiling point for a feed and/or a final boiling point for a feed.
  • Another option, which in some instances may provide a more representative description of a feed is to characterize a feed based on the amount of the feed that boils at one or more temperatures. For example, a "T5" boiling point for a feed is defined as the temperature at which 5 wt% of the feed will boil off. Similarly, a "T95" boiling point is a temperature at 95 wt% of the feed will boil.
  • Typical feeds include, for example, feeds with an initial boiling point of at least 650°F (343°C), or at least 700°F (371°C), or at least 750°F (399°C).
  • a feed may be characterized using a T5 boiling point, such as a feed with a T5 boiling point of at least 300°C, or at least 350°C, or at least 400°C, or at least 450°C.
  • Typical feeds include feeds with a final boiling point of 1150°F (621°C) or less, or 1100°F (593°C) or less, or 1050°F (566°C) or less.
  • a feed may be characterized using a T95 boiling point, such as a feed with a T95 boiling point of 1150°F (621°C) or less, or 1100°F (593°C) or less, or 1050°F (566°C) or less.
  • a T95 boiling point such as a feed with a T95 boiling point of 1150°F (621°C) or less, or 1100°F (593°C) or less, or 1050°F (566°C) or less.
  • the sulfur content of a feed to a hydroprocessing reaction can be at least 100 ppm by weight of sulfur, or at least 1000 wppm, or at least 2000 wppm, or at least 4000 wppm, or at least 10,000 wppm, or at least 20,000 wppm. Additionally or alternately, the sulfur content can be 20,000 wppm or less, or 10,000 wppm or less, or 4000 wppm or less, or 2000 wppm or less, or 1000 wppm or less, or 500 wppm or less, or 100 wppm or less.
  • the amount of sulfur present before hydroprocessing can depend on the type and nature of the feed, as well as potentially other processing that the feed has been exposed to.
  • a biocomponent feedstock refers to a hydrocarbon feedstock derived from a biological raw material component, from biocomponent sources such as vegetable, animal, fish, and/or algae.
  • biocomponent sources such as vegetable, animal, fish, and/or algae.
  • vegetable fats/oils refer generally to any plant based material, and can include fat/oils derived from a source such as plants of the genus Jatropha.
  • the biocomponent sources can include vegetable fats/oils, animal fats/oils, fish oils, pyrolysis oils, and algae lipids/oils, as well as components of such materials, and in some embodiments can specifically include one or more type of lipid compounds.
  • Lipid compounds are typically biological compounds that are insoluble in water, but soluble in nonpolar (or fat) solvents. Non-limiting examples of such solvents include alcohols, ethers, chloroform, alkyl acetates, benzene, and combinations thereof.
  • lipids include, but are not necessarily limited to, fatty acids, glycerol-derived lipids (including fats, oils and phospholipids), sphingosine-derived lipids (including ceramides, cerebrosides, gangliosides, and sphingomyelins), steroids and their derivatives, terpenes and their derivatives, fat-soluble vitamins, certain aromatic compounds, and long-chain alcohols and waxes.
  • lipids In living organisms, lipids generally serve as the basis for cell membranes and as a form of fuel storage. Lipids can also be found conjugated with proteins or carbohydrates, such as in the form of lipoproteins and lipopolysaccharides.
  • vegetable oils examples include, but are not limited to rapeseed (canola) oil, soybean oil, coconut oil, sunflower oil, palm oil, palm kernel oil, peanut oil, linseed oil, tall oil, corn oil, castor oil, jatropha oil, jojoba oil, olive oil, flaxseed oil, camelina oil, safflower oil, babassu oil, tallow oil, and rice bran oil.
  • rapeseed canola
  • soybean oil coconut oil
  • sunflower oil palm oil
  • palm kernel oil peanut oil
  • linseed oil tall oil
  • corn oil castor oil
  • jatropha oil jatropha oil
  • jojoba oil olive oil
  • flaxseed oil camelina oil
  • safflower oil camelina oil
  • babassu oil babassu oil
  • tallow oil examples include, but are not limited to rice bran oil.
  • Vegetable oils as referred to herein can also include processed vegetable oil material.
  • processed vegetable oil material include fatty acids and fatty acid alkyl esters.
  • Alkyl esters typically include C 1 -C 5 alkyl esters. One or more of methyl, ethyl, and propyl esters are preferred.
  • animal fats examples include, but are not limited to, beef fat (tallow), hog fat (lard), turkey fat, fish fat/oil, and chicken fat.
  • the animal fats can be obtained from any suitable source including restaurants and meat production facilities.
  • Animal fats as referred to herein also include processed animal fat material.
  • processed animal fat material include fatty acids and fatty acid alkyl esters.
  • Alkyl esters typically include C 1 -C 5 alkyl esters. One or more of methyl, ethyl, and propyl esters are preferred.
  • Algae oils or lipids are typically contained in algae in the form of membrane components, storage products, and metabolites. Certain algal strains, particularly microalgae such as diatoms and cyanobacteria, contain proportionally high levels of lipids. Algal sources for the algae oils can contain varying amounts, e.g., from 2 wt% to 40 wt% of lipids, based on total weight of the biomass itself.
  • Algal sources for algae oils include, but are not limited to, unicellular and multicellular algae. Examples of such algae include a rhodophyte, chlorophyte, heteronochphyte, tribophyte, glaucophyte, chlorarachniophyte, euglenoid, haptophyte, cryptomonad, dinoflagellum, phytoplankton, and the like, and combinations thereof. In one embodiment, algae can be of the classes Chlorophyceae and/or Haptophyta.
  • Neochloris oleoabundans Scenedesmus dimorphus, Euglena gracilis, Phaeodactylum tricornutum, Pleurochrysis carterae, Prymnesium parvum, Tetraselmis chui, and Chlamydomonas reinhardtii.
  • the biocomponent feeds usable in the present disclosure can include any of those which comprise primarily triglycerides and free fatty acids (FFAs).
  • FFAs free fatty acids
  • the triglycerides and FFAs typically contain aliphatic hydrocarbon chains in their structure having from 8 to 36 carbons, preferably from 10 to 26 carbons, for example from 14 to 22 carbons.
  • Types of triglycerides can be determined according to their fatty acid constituents.
  • the fatty acid constituents can be readily determined using Gas Chromatography (GC) analysis.
  • This analysis involves extracting the fat or oil, saponifying (hydrolyzing) the fat or oil, preparing an alkyl (e.g., methyl) ester of the saponified fat or oil, and determining the type of (methyl) ester using GC analysis.
  • a majority (i.e., greater than 50%) of the triglyceride present in the lipid material can be comprised of C 10 to C 26 , for example C 12 to C 18 , fatty acid constituents, based on total triglyceride present in the lipid material.
  • a triglyceride is a molecule having a structure substantially identical to the reaction product of glycerol and three fatty acids.
  • a triglyceride is described herein as being comprised of fatty acids, it should be understood that the fatty acid component does not necessarily contain a carboxylic acid hydrogen.
  • Other types of feed that are derived from biological raw material components can include fatty acid esters, such as fatty acid alkyl esters (e.g., FAME and/or FAEE).
  • Biocomponent based feedstreams typically have relatively low nitrogen and sulfur contents.
  • a biocomponent based feedstream can contain up to 500 wppm nitrogen, for example up to 300 wppm nitrogen or up to 100 wppm nitrogen.
  • the primary heteroatom component in biocomponent feeds is oxygen.
  • Biocomponent diesel boiling range feedstreams e.g., can include up to 10 wt% oxygen, up to 12 wt% oxygen, or up to 14 wt% oxygen.
  • Suitable biocomponent diesel boiling range feedstreams, prior to hydrotreatment can include at least 5 wt% oxygen, for example at least 8 wt% oxygen.
  • a feed of biocomponent origin can be used that has been previously hydrotreated.
  • This can be a hydrotreated vegetable oil feed, a hydrotreated fatty acid alkyl ester feed, or another type of hydrotreated biocomponent feed.
  • a hydrotreated biocomponent feed can be a biocomponent feed that has been previously hydroprocessed to reduce the oxygen content of the feed to 500 wppm or less, for example to 200 wppm or less or to 100 wppm or less.
  • a biocomponent feed can be hydrotreated to reduce the oxygen content of the feed, prior to other optional hydroprocessing, to 500 wppm or less, for example to 200 wppm or less or to 100 wppm or less.
  • a biocomponent feed can be blended with a mineral feed, so that the blended feed can be tailored to have an oxygen content of 500 wppm or less, for example 200 wppm or less or 100 wppm or less.
  • that portion can be at least 2 wt%, for example at least 5 wt%, or at least 10 wt%, or at least 20 wt%, or at least 25 wt%, or at least 35 wt%, or at least 50 wt%, or at least 60 wt%, or at least 75 wt%.
  • the biocomponent portion can be 75 wt% or less, for example 60 wt% or less, or 50 wt% or less, or 35 wt% or less, or 25 wt% or less, or 20 wt% or less, or 10 wt% or less, or 5 wt% or less.
  • the content of sulfur, nitrogen, and oxygen in a feedstock created by blending two or more feedstocks can typically be determined using a weighted average based on the blended feeds.
  • a mineral feed and a biocomponent feed can be blended in a ratio of 80 wt% mineral feed and 20 wt% biocomponent feed.
  • the resulting blended feed could be expected to have a sulfur content of 802 wppm.
  • the aromatic saturation process can include multiple beds and/or stages of catalyst.
  • the input feed is exposed to the multiple beds or stages of catalyst under conditions effective for reducing the aromatics content of the input feed.
  • the effective conditions include lower processing temperatures as the input feed passes through the beds or stages.
  • the multiple beds or stages can be organized in a single reactor or in a plurality of reactors.
  • the following discussion will describe an embodiment where the aromatic saturation process is performed in a reactor containing multiple catalyst beds, with a different catalyst bed for each processing temperature.
  • other embodiments can include multiple beds at a given temperature, or multiple catalysts in a catalyst bed, or other convenient arrangements of catalyst.
  • aromatics such as some multi-ring aromatics having three or more rings, have a different saturation mechanism.
  • the reaction conditions during a typical aromatic saturation process lead to a situation where both non-aromatic and aromatic species are in equilibrium.
  • the aromatic species in the equilibrium are increasingly favored.
  • temperatures that lead to increased reduction of single ring aromatic species can also lead to increased formation of multi-ring aromatic species.
  • catalyst acidity An additional consideration during aromatic saturation is catalyst acidity. Many types of catalysts that perform aromatic saturation, such as hydrocracking catalysts, also have high acidity. At temperatures suitable for saturating single ring aromatics, an acidic catalyst will typically also facilitate cracking of molecules in a feed, resulting in conversion of lubricant base oil boiling range molecules to lower boiling molecules.
  • an aromatic saturation process includes multiple catalyst beds and processing temperatures. Earlier beds in the aromatic saturation process can be used to saturate single ring aromatic molecules while reducing or mitigating the number of multi-ring aromatics that are formed. Subsequent catalyst beds are used with lower processing temperatures to saturate the multi-ring aromatics. In addition to temperature, the partial pressure of hydrogen in the reaction beds or stages can impact the nature of the products.
  • the first catalyst bed is to use a dewaxing catalyst that includes a hydrogenation metal and a zeolite or molecular sieve that operates primarily by isomerization.
  • the hydrogenation metals include The amount of Pt relative to the weight of the catalyst can be from 0.1 wt% to 5.0 wt%, preferably from 0.3 wt% to 1.5 wt%, such as 0.6 wt% or 0.9 wt%.
  • the zeolites that operate primarily by isomerization include ZSM-48, ZSM-23. Catalysts with similar structures can also be used, such as EU-2, EU-11, ZBM-30, or SSZ-32.
  • Such a catalyst can include a low acidity binder, such as alumina, titania, or zirconia.
  • the weight of zeolite or molecular sieve relative to weight of binder can be from 80:20 to 20:80, such as 65% zeolite to 35% binder.
  • the ratio of zeolite or molecular sieve to binder can be 55:45 or less, or 50:50 or less, or 40:60 or less.
  • Another consideration during the reaction is the partial pressure of hydrogen.
  • the reaction conditions will be more likely to result in production of a Group I type lubricant base oil.
  • the reaction conditions will be more likely to result in production of a Group II type base oil. This is due to the requirement that a Group II base oil must have a sulfur content below 300 wppm and contain more than 90 wt% saturates.
  • the partial pressure of hydrogen during the reaction is increased, the likelihood of achieving at least 90 wt% of saturates also increases.
  • a process intended for making a Group I base oil could use a hydrogen partial pressure of 2.4 MPag (350 psig) to 3.4 MPag (500 psig), such as 2.8 MPag (400 psig).
  • a process intended for making a Group II base oil could use a hydrogen partial pressure of 5.2 MPag (750 psig) to 6.9 MPag (1000 psig), such as 5.5 MPag (800 psig).
  • Process conditions other than temperature and pressure for the reactor containing the first catalyst bed include a liquid hourly space velocity of from 0.2 hr -1 to 10 hr -1 , preferably 0.5 hr -1 to 3.0 hr -1 , and a hydrogen circulation rate of from 35.6 m 3 /m 3 to 1781 m 3 /m 3 (200 scf/B to 10,000 scf/B), preferably 178 m 3 /m 3 to 890.6 m 3 /m 3 (1000 scf/B to 5000 scf/B).
  • the hydrogen treat gas rates of from 213 m 3 /m 3 to 1068 m 3 /m 3 (1200 SCF/B to 6000 SCF/B).
  • one of the factors that can influence a treat gas rate is the amount of hydrogen used in a quench stream between catalyst beds or stages.
  • a quench stream can be used between the stages to reduce the temperature.
  • Any convenient gas quench stream can be used, such as a hydrogen stream, a nitrogen stream, another type of gas stream that is inert relative to the conditions in the reactor, or a combination thereof.
  • a liquid quench stream of an appropriate type could also be used.
  • the quench stream can be used to cool the output flow from the first catalyst bed prior to contacting the second catalyst bed.
  • the second catalyst bed can operate at a reduced temperature relative to the first catalyst bed, such as from 270°C to 330°C, or from 270°C to 300°C.
  • the temperature differential between the inlet or top of the first catalyst bed/stage and the inlet/top of the second catalyst bed/stage can be at least 20°C, or at least 25°C, or at least 30°C, or at least 35°C, or at least 40°C.
  • the temperature at the inlet/top of the second bed/stage can be at least 20°C lower than the temperature at the outlet of the first bed/stage, for example at least 25°C lower, at least 30°C lower, at least 35°C lower, at least 40°C lower, at least 45°C lower, or at least 50°C lower.
  • the hydrogen partial pressure, space velocity, and hydrogen treat gas rate values for the second catalyst bed can all be similar to the ranges for the first catalyst bed.
  • the catalyst in the second catalyst bed can be similar to the catalyst for the first catalyst bed, or a different type of catalyst can be selected.
  • MCM-41 a-catalyst based on the M41S family of catalyst supports, can be selected. Catalysts based on the M41S family of catalyst supports tend to have higher acidity values, and therefore are not as suitable for use in the first catalyst bed. However, at the lower reaction temperature used for the second catalyst bed, the potential for cracking of the feed is reduced, making this type of catalyst suitable for the second catalyst bed.
  • the M41S family of catalysts can be described as mesoporous materials having relatively high silica contents, e.g ., whose preparation is further described in J. Amer. Chem. Soc., 1992, 114, 10834 .
  • M41S materials can include, but are not limited to MCM-41, MCM-48, MCM-50, and combinations thereof.
  • Mesoporous is understood to refer to catalysts having pore sizes from 15 Angstroms to 100 Angstroms.
  • a preferred member of this class is MCM-41, whose preparation is described, e.g., in U.S. Patent No. 5,098,684 .
  • MCM-41 is an inorganic, porous, non-layered phase having a hexagonal arrangement of uniformly-sized pores.
  • MCM-41 The physical structure of MCM-41 is similar to a bundle of straws, in which the opening of the straws (the cell diameter of the pores) ranges from 15-100 Angstroms.
  • MCM-48 has a cubic symmetry and is described, for example, in U.S. Patent No. 5,198,203 .
  • MCM-50 has a lamellar structure.
  • MCM-41 can be made with different size pore openings in the mesoporous range.
  • an MCM-41 catalyst can have an average pore size of 40 angstroms or less, such as 25 angstroms or less.
  • the content of framework molecules in an MCM-41 catalyst can also vary.
  • the framework of the MCM-41 can include silica, in combination with alumina, titania, or zirconia. The ratio of silica to alumina, titania, or zirconia in the framework can vary from as high as 800:1 to as little as 25:1.
  • suitable binders for the M41S family, and specifically for MCM-41 can include alumina, silica, titania, silica-aluminas, or a combination thereof.
  • suitable binders for the M41S family, and specifically for MCM-41 can include alumina, silica, titania, silica-aluminas, or a combination thereof.
  • relatively high specific surface areas are possible with MCM-41 type catalysts, such as catalyst surface areas of at least 600 m 2 /g, or at least 750 m 2 /g, or at least 850 m 2 /g, or at least 950 m 2 /g.
  • binders providing a lower surface area can be selected, such as binders that provide a catalyst surface area of 650 m 2 /g or less, or 550 m 2 /g or less.
  • Low surface area alumina or titania binders are options for producing a MCM-41 type catalyst with a reduced surface area.
  • a suitable aromatic saturation catalyst is an alumina-bound mesoporous MCM-41 with Pt Pd or a mixture thereof.
  • Individual hydrogenation metal embodiments can include, but are not limited to, Pt only or Pd only, while mixed hydrogenation metal embodiments can include, but are not limited to, combinations of Pt and Pd.
  • the amount of Group VIII hydrogenation metal(s) can be at least 0.1 wt% based on the total weight of the catalyst, for example at least 0.5 wt% or at least 0.6 wt%.
  • the amount of Group VIII hydrogenation metal(s) can be 5.0 wt% or less based on the total weight of the catalyst, for example 3.5 wt% or less, or 2.5 wt% or less, or 1.5 wt% or less, or 1.0 wt% or less, or 0.9 wt% or less, or 0.75 wt% or less, or 0.6 wt% or less. Further additionally or alternately, the total amount of hydrogenation metal(s) can be at least 0.1 wt% based on the total weight of the catalyst, for example at least 0.25 wt%, or at least 0.5 wt%, or at least 0.6 wt%, or at least 0.75 wt%, or at least 1 wt%.
  • the total amount of hydrogenation metal(s) can be 35 wt% or less based on the total weight of the catalyst, for example 30 wt% or less, or 25 wt% or less, or 20 wt% or less, or 15 wt% or less, or 10 wt% or less, or 5 wt% or less.
  • MCM-41 has some acidity and/or hydrocracking activity.
  • an amorphous, low acidity support By selecting an amorphous, low acidity support, the amount of cracking or other feed conversion that occurs in the second catalyst bed can be reduced or minimized.
  • another quench stream can be used to cool the output flow from the second catalyst bed prior to contacting the third catalyst bed.
  • the catalyst used in the third catalyst bed comprises MCM-41 type catalyst as described above. If an MCM-41 type catalyst is used in the second catalyst bed, the MCM-41 catalyst in the third bed can be the same or different.
  • the catalyst in the second bed can be an MCM-41 catalyst with titania in the framework, a silica to titania ratio of from 25:1 to 80:1, and bound with a low surface area alumina or titania binder.
  • the catalyst in the third bed can be an MCM-41 catalyst with alumina in the framework, a silica to alumina ratio of from 25:1 to 80:1, and bound with a binder providing a surface area of at least 600 m 2 /g.
  • the catalysts in both the second bed and the third bed can include from 0.1 to 1.5 wt% of Pt, or alternatively from 0.1 to 0.5 wt% Pt in combination with 0.5 to 1.0 wt% Pd.
  • One source of input feed for an aromatic saturation process as described above is to use the bottoms from a fuels hydrocracking process as the input feed.
  • a fuels hydrocracking process a feed that has at least a portion boiling above the diesel range is hydrocracked to convert higher boiling molecules to molecules boiling in the diesel or naphtha boiling range.
  • a typical fuels hydrocracking process may also include a preliminary hydrotreating stage. When either hydrotreating or hydrocracking is used for substantial sulfur removal, a gas-liquid separator may be used to remove gas phase contaminants from the remaining liquid effluent.
  • a suitable process can be a lubricant base oil production process, which sometimes can be referred to as a lubricant base oil hydrocracking process.
  • a feed that has at least a portion boiling above the diesel range such as in the vacuum gas oil boiling range and/or in the 700°F+ (371°C) boiling range
  • Lubricant base oils can then be formed from the higher boiling portions, usually after performing additional processing steps such as dewaxing, hydrofinishing, aromatic saturation, and/or fractionation.
  • a typical lubricant base oil hydrocracking process may also include a preliminary hydrotreating stage. When either hydrotreating or hydrocracking is used for substantial sulfur removal, a gas-liquid separator may be used to remove gas phase contaminants from the remaining liquid effluent.
  • Hydrotreatment is typically used to reduce the sulfur, nitrogen, and aromatic content of a feed.
  • Hydrotreating conditions can include temperatures of 200°C to 450°C, or 315°C to 425°C; pressures of 250 psig (1.8 MPa) to 5000 psig (34.6 MPa) or 300 psig (2.1 MPa) to 3000 psig (20.8 MPa); Liquid Hourly Space Velocities (LHSV) of 0.2-10 h -1 ; and hydrogen treat rates of 200 scf/B (35.6 m 3 /m 3 ) to 10,000 scf/B (1781 m 3 /m 3 ), or 500 (89 m 3 /m 3 ) to 10,000 scf/B (1781 m 3 /m 3 ).
  • hydrotreatment is often performed for sulfur and/or nitrogen removal
  • hydrotreatment can be performed under what could be considered as “sweet” conditions, or alternatively “non-sour” conditions, where the sulfur content of the feed entering the hydrotreatment stage can be 500 wppm or less, or 200 wppm or less.
  • Hydrotreatment in a non-sour and/or sweet stage can still be effective for reducing the amount of sulfur, nitrogen, and/or aroamtics in a feed.
  • the hydrotreating conditions noted above can be effective for hydrotreatment under sweet conditions or non-sour conditions, although the conditions may tend to have lower severity than hydrotreatment conditions for a comparable boiling range feed with a higher sulfur content.
  • Hydrotreating catalysts are typically those containing Group VIB metals, such as molybdenum and/or tungsten, and non-noble Group VIII metals, such as, iron, cobalt and nickel and mixtures thereof. These metals or mixtures of metals are typically present as oxides or sulfides on refractory metal oxide supports. Suitable metal oxide supports include low acidic oxides such as silica, alumina or titania.
  • Preferred aluminas are porous aluminas such as gamma or eta having average pore sizes from 50 to 200 ⁇ , or 75 to 150 ⁇ ; a surface area from 100 to 300 m 2 /g, or 150 to 250 m 2 /g; and a pore volume of from 0.25 to 1.0 cm 3 /g, or 0.35 to 0.8 cm 3 /g.
  • the supports are preferably not promoted with a halogen such as fluorine as this generally increases the acidity of the support.
  • Preferred metal catalysts include cobalt/molybdenum (1-10% Co as oxide, 10-40% Mo as oxide), nickel/molybdenum (1-10% Ni as oxide, 10-40% Co as oxide), or nickel/tungsten (1-10% Ni as oxide, 10-40% W as oxide) on alumina.
  • the hydrotreating catalyst can be a bulk metal catalyst, or a combination of stacked beds of supported and bulk metal catalyst.
  • Hydrocracking catalysts typically contain sulfided base metals on acidic supports, such as amorphous silica alumina, cracking zeolites such as USY, or acidified alumina. Often these acidic supports are mixed or bound with other metal oxides such as alumina, titania or silica.
  • acidic supports such as amorphous silica alumina, cracking zeolites such as USY, or acidified alumina. Often these acidic supports are mixed or bound with other metal oxides such as alumina, titania or silica.
  • metals for hydrocracking catalysts include nickel, nickel-cobalt-molybdenum, cobalt-molybdenum, nickel-tungsten, nickel-molybdenum, and/or nickel-molybdenum-tungsten. Additionally or alternately, hydrocracking catalysts with noble metals can also be used.
  • noble metal catalysts include those based on platinum and/or palladium.
  • Support materials which may be used for both the noble and non-noble metal catalysts can comprise a refractory oxide material such as alumina, silica, alumina-silica, kieselguhr, diatomaceous earth, magnesia, zirconia, or combinations thereof, with alumina, silica, alumina-silica being the most common (and preferred, in one embodiment).
  • a refractory oxide material such as alumina, silica, alumina-silica, kieselguhr, diatomaceous earth, magnesia, zirconia, or combinations thereof, with alumina, silica, alumina-silica being the most common (and preferred, in one embodiment).
  • a hydrocracking catalyst includes Group VIII noble metals, such as for hydrocracking in a "sweet" hydrocracking stage
  • the one or more Group VIII metals can be present in an amount ranging from 0.1 wt% to 5.0 wt%, or 0.1 wt% to 2.0 wt%, or 0.3 wt% to 2.0 wt%, or 0.1 wt% to 1.5 wt%, or 0.3 wt% to 1.5 wt%.
  • the at least one Group VIII non-noble metal, in oxide form can typically be present in an amount ranging from 2 wt% to 40 wt%, preferably from 4 wt% to 15 wt%.
  • the at least one Group VIB metal, in oxide form can typically be present in an amount ranging from 2 wt% to 70 wt%, preferably for supported catalysts from 6 wt% to 40 wt% or from 10 wt% to 30 wt%. These weight percents are based on the total weight of the catalyst.
  • suitable hydrocracking catalysts can include nickel/molybdenum, nickel/tungsten, or nickel/molybdenum/tungsten as metals supported on the hydrocracking catalyst.
  • a hydrocracking catalyst can include a large pore molecular sieve that is selective for cracking of branched hydrocarbons and/or cyclic hydrocarbons.
  • Zeolite Y such as ultrastable zeolite Y (USY) is an example of a zeolite molecular sieve that is selective for cracking of branched hydrocarbons and cyclic hydrocarbons.
  • the silica to alumina ratio in a USY zeolite can be at least 10, such as at least 15, or at least 25, or at least 50, or at least 100.
  • the unit cell size for a USY zeolite can be 24.50 Angstroms or less, such as 24.45 Angstroms or less, or 24.40 Angstroms or less, or 24.35 Angstroms or less, such as 24.30 Angstroms.
  • a variety of other types of molecular sieves can be used in a hydrocracking catalyst, such as zeolite Beta and ZSM-5.
  • Still other types of suitable molecular sieves can include molecular sieves having 10-member ring pore channels or 12-member ring pore channels.
  • molecular sieves having 10-member ring pore channels or 12-member ring pore channels include molecular sieves having zeolite framework structures selected from MRE, MTT, EUO, AEL, AFO, SFF, STF, TON, OSI, ATO, GON, MTW, SFE, SSY, or VET.
  • the reaction conditions in the reaction system can be selected to generate a desired level of conversion of a feed.
  • Conversion of the feed can be defined in terms of conversion of molecules that boil above a temperature threshold to molecules below that threshold.
  • the conversion temperature can be any convenient temperature, such as 700°F (371°C).
  • the amount of conversion in the stage(s) of the reaction system can be selected to enhance diesel production while achieving a substantial overall yield of fuels.
  • the amount of conversion can correspond to the total conversion of molecules within any stage of a fuels hydrocracker, lubes hydrocracker, or other reaction system that is used to hydroprocess the lower boiling portion of the feed from the vacuum distillation unit.
  • Suitable amounts of conversion of molecules boiling above 700°F to molecules boiling below 700°F include converting at least 5 wt% of the 700°F+ portion of the feedstock to the stage(s) of the reaction system, or at least 15 wt%, or at least 25 wt%, or at least 35 wt%, or at least 45 wt%, or at least 55 wt%, or at least 65 wt%, or at least 75 wt%.
  • the conversion of the 700°F+ (371°C) portion can be at least 15 wt%, or at least 25 wt%, or at least 35 wt%, or at least 45 wt%, or at least 55 wt%, or at least 65 wt%, or at least 75 wt%.
  • the amount of conversion for the reaction system can be 85% or less, or 80% or less, or 75% or less, or 70% or less. Still larger amounts of conversion may also produce a suitable hydrocracker bottoms for forming lubricant base oils, but such higher conversion amounts will also result in a reduced yield of lubricant base oils.
  • Reducing the amount of conversion can increase the yield of lubricant base oils, but reducing the amount of conversion to below the ranges noted above may result in hydrocracker bottoms that are not suitable for formation of Group II, Group II+, or Group III lubricant base oils.
  • a fuels hydrocracking reaction system, lubricant base oil production reaction system, or other reaction system can include at least one hydrocracking catalyst.
  • Hydrocracking catalysts typically contain sulfided base metals on acidic supports, such as amorphous silica alumina, cracking zeolites such as USY, or acidified alumina. Often these acidic supports are mixed or bound with other metal oxides such as alumina, titania or silica. Examples of suitable acidic supports include acidic molecular sieves, such as zeolites or silicoaluminophophates.
  • zeolite is USY, such as a USY zeolite with cell size of 24.25 Angstroms or less. Additionally or alternately, the catalyst can be a low acidity molecular sieve, such as a USY zeolite with a Si to Al ratio of at least 20, and preferably at least 40 or 50. Zeolite Beta is another example of a potentially suitable hydrocracking catalyst.
  • metals for hydrocracking catalysts include metals or combinations of metals that include at least one Group VIII metal, such as nickel, nickel-cobalt-molybdenum, cobalt-molybdenum, nickel-tungsten, nickel-molybdenum, and/or nickel-molybdenum-tungsten.
  • hydrocracking catalysts with noble metals can also be used.
  • noble metal catalysts include those based on platinum and/or palladium.
  • Support materials which may be used for both the noble and non-noble metal catalysts can comprise a refractory oxide material such as alumina, silica, alumina-silica, kieselguhr, diatomaceous earth, magnesia, zirconia, or combinations thereof, with alumina, silica, alumina-silica being the most common (and preferred, in one embodiment).
  • the conditions selected for hydrocracking for lubricant base stock production can depend on the desired level of conversion, the level of contaminants in the input feed to the hydrocracking stage, and potentially other factors.
  • a hydrocracking process performed under sour conditions such as conditions where the sulfur content of the input feed to the hydrocracking stage is at least 500 wppm, can be carried out at temperatures of 550°F (288°C) to 840°F (449°C), hydrogen partial pressures of from 250 psig to 5000 psig (1.8 MPag to 34.6 MPag), liquid hourly space velocities of from 0.05 h -1 to 10 h -1 , and hydrogen treat gas rates of from 35.6 m 3 /m 3 to 1781 m 3 /m 3 (200 SCF/B to 10,000 SCF/B).
  • the conditions can include temperatures in the range of 600°F (343°C) to 815°F (435°C), hydrogen partial pressures of from 500 psig to 3000 psig (3.5 MPag-20.9 MPag), liquid hourly space velocities of from 0.2 h -1 to 2 h -1 and hydrogen treat gas rates of from 213 m 3 /m 3 to 1068 m 3 /m 3 (1200 SCF/B to 6000 SCF/B).
  • the conditions selected for hydrocracking for fuels hydrocracking and/or lubricant base stock production can depend on the desired level of conversion, the level of contaminants in the input feed to the hydrocracking stage, and potentially other factors.
  • hydrocracking conditions in the first stage and/or the second stage can be selected to achieve a desired level of conversion in the reaction system.
  • a hydrocracking process in the first stage can be carried out at temperatures of 550°F (288°C) to 840°F (449°C), hydrogen partial pressures of from 250 psig to 5000 psig (1.8 MPag to 34.6 MPag), liquid hourly space velocities of from 0.05 h -1 to 10 h -1 , and hydrogen treat gas rates of from 35.6 m 3 /m 3 to 1781 m 3 /m 3 (200 SCF/B to 10,000 SCF/B).
  • the conditions can include temperatures in the range of 600°F (343°C) to 815°F (435°C), hydrogen partial pressures of from 500 psig to 3000 psig (3.5 MPag-20.9 MPag), and hydrogen treat gas rates of from 213 m 3 /m 3 to 1068 m 3 /m 3 (1200 SCF/B to 6000 SCF/B).
  • the LHSV relative to only the hydrocracking catalyst can be from 0.25 h -1 to 50 h -1 , such as from 0.5 h -1 to 20 h , and preferably from 1.0 h -1 to 4.0 h -1
  • a portion of the hydrocracking catalyst and/or a dewaxing catalyst can be contained in a second reactor stage.
  • a first reaction stage of the hydroprocessing reaction system can include one or more hydrotreating and/or hydrocracking catalysts.
  • the conditions in the first reaction stage can be suitable for reducing the sulfur and/or nitrogen content of the feedstock.
  • a separator can then be used in between the first and second stages of the reaction system to remove gas phase sulfur and nitrogen contaminants.
  • One option for the separator is to simply perform a gas-liquid separation to remove contaminant.
  • Another option is to use a separator such as a flash separator that can perform a separation at a higher temperature.
  • Such a high temperature separator can be used, for example, to separate the feed into a portion boiling below a temperature cut point, such as 350°F (177°C) or 400°F (204°C), and a portion boiling above the temperature cut point.
  • a temperature cut point such as 350°F (177°C) or 400°F (204°C)
  • the naphtha boiling range portion of the effluent from the first reaction stage can also be removed, thus reducing the volume of effluent that is processed in the second or other subsequent stages.
  • any low boiling contaminants in the effluent from the first stage would also be separated into the portion boiling below the temperature cut point. If sufficient contaminant removal is performed in the first stage, the second stage can be operated as a "sweet" or low contaminant stage.
  • Still another option can be to use a separator between the first and second stages of the hydroprocessing reaction system that can also perform at least a partial fractionation of the effluent from the first stage.
  • the effluent from the first hydroprocessing stage can be separated into at least a portion boiling below the distillate (such as diesel) fuel range, a portion boiling in the distillate fuel range, and a portion boiling above the distillate fuel range.
  • the distillate fuel range can be defined based on a conventional diesel boiling range, such as having a lower end cut point temperature of at least 350°F (177°C) or at least 400°F (204°C) to having an upper end cut point temperature of 700°F (371°C) or less or 650°F (343°C) or less.
  • the distillate fuel range can be extended to include additional kerosene, such as by selecting a lower end cut point temperature of at least 300°F (149°C).
  • the portion boiling below the distillate fuel fraction includes, naphtha boiling range molecules, light ends, and contaminants such as H 2 S. These different products can be separated from each other in any convenient manner. Similarly, one or more distillate fuel fractions can be formed, if desired, from the distillate boiling range fraction.
  • the portion boiling above the distillate fuel range represents the potential lubricant base oils. In such aspects, the portion boiling above the distillate fuel range is subjected to further hydroprocessing in a second hydroprocessing stage.
  • a hydrocracking process performed under non-sour conditions can be performed under conditions similar to those used for sour conditions, or the conditions can be different.
  • a non-sour hydrocracking stage can have less severe conditions than a similar hydrocracking stage operating under sour conditions.
  • Suitable hydrocracking conditions can include temperatures of 450°F (232°C) to 840°F (449°C), or 450°F (232°C) to 800°F (427°C), or 450°F (249°C) to 750°F (399°C), or 500°F (260°C) to 840°F (449°C), or 500°F (260°C) to 800°F (427°C), or 500°F (260°C) to 750°F (399°C); hydrogen partial pressures of from 250 psig to 5000 psig (1.8 MPag to 34.6 MPag); liquid hourly space velocities of from 0.05 h -1 to 10 h -1 ; and hydrogen treat gas rates of from 35.6 m 3 /m 3 to 1781 m 3 /m 3 (200 SCF/B to 10,000 SCF/B).
  • the conditions can include temperatures in the range of 500°F (260°C) to 815°F (435°C), or 500°F (260°C) to 750°F (399°C), or 500°F (260°C) to 700°C (371°C); hydrogen partial pressures of from 500 psig to 3000 psig (3.5 MPag-20.9 MPag); liquid hourly space velocities of from 0.2 h -1 to 5 h -1 ; and hydrogen treat gas rates of from 213 m 3 /m 3 to 1068 m 3 /m 3 (1200 SCF/B to 6000 SCF/B).
  • multiple hydrocracking stages may be present, with a first hydrocracking stage operating under sour conditions, while a second hydrocracking stage operates under non-sour conditions and/or under conditions where the sulfur level is substantially reduced relative to the first hydrocracking stage.
  • the temperature in the second stage hydrocracking process can be 40°F (22°C) less than the temperature for a hydrocracking process in the first stage, or 80°F (44°C) less, or 120°F (66°C) less.
  • the pressure for the second stage hydrocracking process can be 100 psig (690 kPa) less than a hydrocracking process in the first stage, or 200 psig (1380 kPa) less, or 300 psig (2070 kPa) less.
  • the same conditions can be used for hydrotreating and hydrocracking beds or stages, such as using hydrotreating conditions for both or using hydrocracking conditions for both.
  • the pressure for the hydrotreating and hydrocracking beds or stages can be the same.
  • a dewaxing catalyst is also included as part of the process train that generates the input feed.
  • the dewaxing catalyst is located in a bed downstream from any hydrocracking catalyst stages and/or any hydrocracking catalyst present in a stage. This can allow the dewaxing to occur on molecules that have already been hydrotreated or hydrocracked to remove a significant fraction of organic sulfur- and nitrogen-containing species.
  • the dewaxing catalyst can be located in the same reactor as at least a portion of the hydrocracking catalyst in a stage.
  • the effluent from a reactor containing hydrocracking catalyst possibly after a gas-liquid separation, can be fed into a separate stage or reactor containing the dewaxing catalyst.
  • Suitable dewaxing catalysts can include molecular sieves such as crystalline aluminosilicates (zeolites).
  • the molecular sieve can comprise, consist essentially of, or be ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, zeolite Beta, or a combination thereof, for example ZSM-23 and/or ZSM-48, or ZSM-48 and/or zeolite Beta.
  • molecular sieves that are selective for dewaxing by isomerization as opposed to cracking can be used, such as ZSM-48, zeolite Beta, ZSM-23, or a combination thereof.
  • the molecular sieve can comprise, consist essentially of, or be a 10-member ring 1-D molecular sieve.
  • Examples include EU-1, ZSM-35 (or ferrierite), ZSM-11, ZSM-57, NU-87, SAPO-11, ZSM-48, ZSM-23, and ZSM-22.
  • Preferred materials are EU-2, EU-11, ZBM-30, ZSM-48, or ZSM-23.
  • ZSM-48 is most preferred.
  • a zeolite having the ZSM-23 structure with a silica to alumina ratio of from 20:1 to 40:1 can sometimes be referred to as SSZ-32.
  • the dewaxing catalyst can include a binder for the molecular sieve, such as alumina, titania, silica, silica-alumina, zirconia, or a combination thereof, for example alumina and/or titania or silica and/or zirconia and/or titania.
  • a binder for the molecular sieve such as alumina, titania, silica, silica-alumina, zirconia, or a combination thereof, for example alumina and/or titania or silica and/or zirconia and/or titania.
  • the dewaxing catalysts used in processes according to the disclosure are catalysts with a low ratio of silica to alumina.
  • the ratio of silica to alumina in the zeolite can be less than 200:1, or less than 110:1, or less than 100:1, or less than 90:1, or less than 80:1.
  • the ratio of silica to alumina can be from 30:1 to 200:1, or 60:1 to 110:1, or 70:1 to 100:1.
  • the catalysts according to the disclosure can further include a metal hydrogenation component.
  • the metal hydrogenation component is typically a Group VI and/or a Group VIII metal.
  • the metal hydrogenation component is a Group VIII noble metal.
  • the metal hydrogenation component is Pt, Pd, or a mixture thereof.
  • the metal hydrogenation component can be a combination of a non-noble Group VIII metal with a Group VI metal. Suitable combinations can include Ni, Co, or Fe with Mo or W, preferably Ni with Mo or W.
  • the metal hydrogenation component may be added to the catalyst in any convenient manner.
  • One technique for adding the metal hydrogenation component is by incipient wetness. For example, after combining a zeolite and a binder, the combined zeolite and binder can be extruded into catalyst particles. These catalyst particles can then be exposed to a solution containing a suitable metal precursor. Alternatively, metal can be added to the catalyst by ion exchange, where a metal precursor is added to a mixture of zeolite (or zeolite and binder) prior to extrusion.
  • the amount of metal in the catalyst can be at least 0.1 wt% based on catalyst, or at least 0.15 wt%, or at least 0.2 wt%, or at least 0.25 wt%, or at least 0.3 wt%, or at least 0.5 wt% based on catalyst.
  • the amount of metal in the catalyst can be 20 wt% or less based on catalyst, or 10 wt% or less, or 5 wt% or less, or 2.5 wt% or less, or 1 wt% or less.
  • the amount of metal can be from 0.1 to 5 wt%, preferably from 0.1 to 2 wt%, or 0.25 to 1.8 wt%, or 0.4 to 1.5 wt%.
  • the metal is a combination of a non-noble Group VIII metal with a Group VI metal
  • the combined amount of metal can be from 0.5 wt% to 20 wt%, or 1 wt% to 15 wt%, or 2.5 wt% to 10 wt%.
  • the dewaxing catalysts useful in processes according to the disclosure can also include a binder.
  • the dewaxing catalysts used in process according to the disclosure are formulated using a low surface area binder, a low surface area binder represents a binder with a surface area of 100 m 2 /g or less, or 80 m 2 /g or less, or 70 m 2 /g or less.
  • a zeolite can be combined with binder in any convenient manner.
  • a bound catalyst can be produced by starting with powders of both the zeolite and binder, combining and mulling the powders with added water to form a mixture, and then extruding the mixture to produce a bound catalyst of a desired size.
  • Extrusion aids can also be used to modify the extrusion flow properties of the zeolite and binder mixture.
  • the amount of framework alumina in the catalyst may range from 0.1 to 3.33 wt%, or 0.1 to 2.7 wt%, or 0.2 to 2 wt%, or 0.3 to 1 wt%.
  • Process conditions in a catalytic dewaxing zone can include a temperature of from 200 to 450°C, preferably 270 to 400°C, a hydrogen partial pressure of from 1.8 to 34.6 mPa (250 to 5000 psi), preferably 4.8 to 20.8 mPa, a liquid hourly space velocity of from 0.2 to 10 v/v/hr, preferably 0.5 to 3.0, and a hydrogen circulation rate of from 35.6 to 1781 m 3 /m 3 (200 to 10,000 scf/B), preferably 178 to 890.6 m 3 /m 3 (1000 to 5000 scf/B).
  • the conditions can include temperatures in the range of 600°F (343°C) to 815°F (435°C), hydrogen partial pressures of from 500 psig to 3000 psig (3.5 MPag-20.9 MPag), and hydrogen treat gas rates of from 213 m 3 /m 3 to 1068 m 3 /m 3 (1200 SCF/B to 6000 SCF/B).
  • the general conditions for a dewaxing stage include the conditions mentioned above for the first catalyst bed of an aromatic saturation process according to the disclosure.
  • some types of dewaxing catalysts correspond to catalysts suitable for use as a catalyst in a first bed of an aromatic saturation process.
  • the first catalyst bed of an aromatic saturation process can correspond to the final catalyst bed or stage of a prior process.
  • FIG. 1 shows an example of a reactor suitable for performing an aromatic saturation process according to the disclosure.
  • reactor 100 includes three catalyst beds 110, 120, and 130.
  • a catalyst bed 110, 120, or 130 shown in FIG. 1 can represent a plurality of beds if desired.
  • Catalyst bed 110 represents a bed for performing saturation of single ring aromatics.
  • a suitable dewaxing catalyst (such as one that operates primarily by isomerization) can be used at a reaction temperature of 320°C.
  • the hydrogen partial pressure in the reactor can be from 2.4 MPag to 6.9 MPag, such as at least 2.4 MPag or 6 MPag or less.
  • Catalyst bed 120 represents a second catalyst bed suitable for some additional saturation of single ring aromatics and some reduction of multi-ring aromatics.
  • suitable catalysts in the second catalyst bed include dewaxing catalysts that operate primarily by isomerization or MCM-41 type catalysts.
  • the temperature in the second bed can be, for example, 280°C.
  • the third catalyst bed 130 represents a catalyst bed suitable for reducing the amount of multi-ring aromatics.
  • MCM-41 type catalysts are suitable for use in catalyst bed 130.
  • the temperature in the third bed can be, for example, 240°C.
  • an input feed 105 can be introduced into reactor 100.
  • the input feed is successively exposed to the catalysts in catalyst beds 110, 120, and 130 in the presence of hydrogen.
  • Hydrogen can be introduced with the input feed 105 or as a separate hydrogen feed 107.
  • Hydrogen can optionally be introduced as a quench gas as part of quench gas streams 115 and 125. Quench gas streams 115 and 125 assist in controlling the temperature desired for processing in catalyst beds 120 and 130. Exposing the input feed 105 to the catalyst beds 110, 120, and 130 results in an effluent 133 with a reduced aromatic content.
  • FIG. 2 shows an example of an aromatic saturation reactor 200 as part of a larger reaction system, such as a fuels hydrocracking reaction system.
  • a feedstock 205 is introduced into a hydrotreatment reactor 240 to remove sulfur and nitrogen contaminants from the feedstock.
  • the effluent 243 from reactor 240 is separated in a gas-liquid separator 245.
  • the liquid effluent 253 is then passed into a hydrocracking reactor 250.
  • the effluent from hydrocracking reactor 250 is then fractionated in fractionator 260.
  • Fractionator 260 generates one or more fuels cuts, such as a naphtha cut 262 and a diesel cut 264.
  • a bottom cut 266 is also generated and fed into aromatic saturation reactor 200.
  • the effluent 233 from aromatic saturation reactor 200 is suitable for use as a Group I or Group II lubricant base oil, depending on the conditions in reactor 200.
  • FIG. 3 shows another possible configuration for performing an aromatic saturation process.
  • a hydroprocessing reactor 370 is shown that includes one or more types of catalyst beds and that receives an optionally previously hydroprocessed feedstock 371.
  • At least the bottom catalyst bed 372 of hydroprocessing reactor 370 corresponds to a bed of a dewaxing catalyst that operates primarily by isomerization.
  • catalyst bed 370 is operated under conditions corresponding to the first aromatic saturation stage according to the disclosure, including using a dewaxing catalyst suitable for a first bed for aromatic saturation.
  • the effluent 373 from reactor 370 is then fractionated 380 to generate various cuts or fractions, such as fraction 382 and fraction 386.
  • FIG. 3 shows another possible configuration for performing an aromatic saturation process.
  • fraction 386 is used as the input to reactor 300, where the remaining catalyst beds 320 and 330 for the aromatic saturation process are located.
  • the effluent 333 from aromatic saturation reactor 300 is suitable for use as a Group I or Group II lubricant base oil, depending on the conditions in reactor 300.
  • FIG. 6 shows another example of performing aromatic saturation as part of a larger reaction system, such as a reaction system for lubricant base oil production.
  • a feedstock 605 is introduced into a first hydroprocessing stage 640 to remove sulfur and nitrogen contaminants from the feedstock.
  • first hydroprocessing stage 640 can correspond to a plurality of reactors, if desired.
  • the first hydroprocessing stage can include hydrotreatment catalyst, hydrocracking catalyst, or a combination thereof.
  • the conditions in hydroprocessing stage 640 can be hydrotreating conditions, hydrocracking conditions, or a combination thereof.
  • the effluent 643 from hydroprocessing stage 640 is then passed into a separation stage 645. Separation stage 645 can perform several functions.
  • contaminant gases such as H 2 S and NH 3 that are generated in first hydroprocessing stage 640 can be removed.
  • An optional second function can be to separate out one or more streams 622 of naphtha and/or diesel boiling range compounds from effluent 643. This can allow these naphtha and/or diesel boiling range products to be removed from the reaction system, so that the products do not react further to form lower value compounds.
  • second (hydroprocessing) stage 650 can correspond to a plurality of reactors, if desired. If sufficient sulfur and/or nitrogen are removed from the feed in hydroprocessing stage 640, the effluent 648 passed into second stage reactor 650 can allow for operation of second stage reactor 650 as a "sweet" processing stage.
  • at least one catalyst bed 651 can correspond to a hydrocracking catalyst, for additional improvement of properties such as viscosity index.
  • second stage reactor 650 can also include one or more beds 659 of dewaxing catalyst, or catalyst bed(s) 659 can be located in a separate reactor. Regardless of the location, the reactor containing one or more beds 659 of dewaxing catalyst can correspond to an initial stage of aromatic saturation, as described herein.
  • the dewaxing catalyst can include a supported noble metal to assist with performing aromatic saturation.
  • At least a portion of the effluent 657 from second stage reactor 650 (or alternatively from another reactor containing bed(s) 659 of dewaxing catalyst) can then be passed into an intermediate aromatic saturation stage 670.
  • the effluent from second stage reactor 650 could be fractionated and/or separated prior to passing the at least a portion of the effluent to the intermediate aromatic saturation stage 670.
  • the temperature in intermediate aromatic saturation stage 670 can be lower than the exit temperature from second stage reactor 650 and/or the end of one or more dewaxing catalyst beds 659, depending on the location of the quench.
  • At least a portion of the effluent 667 from intermediate aromatic saturation stage 670 can then be passed into a hydrofinishing stage 680.
  • the effluent from intermediate aromatic saturation stage 670 could be fractionated and/or separated prior to passing the at least a portion of the effluent to the hydrofinishing stage 680.
  • the temperature in hydrofinishing stage 680 can be lower than the exit temperature from intermediate aromatic saturation stage 670 and/or the exit temperature from the final catalyst bed of the intermediate aromatic saturation stage, depending on the location of the quench.
  • the following example describes processing that corresponds to processing of a first bed or stage of an aromatic saturation process. Also described here is a comparative process not according to the disclosure.
  • a fuels hydrocracking process was used to process a feed boiling in the vacuum gas oil boiling range.
  • the final stage of the fuels hydrocracking process was a stage where the hydroprocessed feed was exposed to a dewaxing catalyst.
  • the dewaxing catalyst included 0.6 wt% Pt on an alumina bound ZSM-48 catalyst.
  • the silica to alumina ratio of the ZSM-48 was between 110:1 and 200:1.
  • ZSM-48 is a dewaxing catalyst that operates primarily by isomerization.
  • the feed was exposed to the dewaxing catalyst at a temperature of 320°C and a hydrogen partial pressure of 2.8 MPag (400 psig).
  • the dewaxing catalyst included 0.6 wt% Pt on alumina bound zeolite Beta.
  • Zeolite Beta is a dewaxing catalyst where a substantial portion of the dewaxing activity is due to cracking.
  • the feed was exposed to the zeolite Beta under conditions to generate a comparable yield of liquid product in a boiling range suitable for making lubricating oil basestock.
  • the hydroprocessing in the presence of a ZSM-48 dewaxing catalyst generated an effluent with a mutagenicity index of 0.5, a total aromatics content of 566 ⁇ mol/g, a viscosity index of 118, and a pour point of -22°C.
  • hydroprocessing in the presence of the zeolite Beta generated an effluent with a mutagenicity index of 2.4, a total aromatics content of 1154 ⁇ mol/g, a viscosity index of 96, and a pour point of -33°C.
  • the total aromatics content for the samples was estimated by correlation, according to method B3997/PGC.
  • the mutagenicity index was estimated based on the absorption of a sample at 325 nm. Based on the pour point, it would appear that the hydroprocessing conditions in the presence of the zeolite Beta were more severe than the processing conditions in the presence of the ZSM-48 catalyst.
  • the feed processed in the presence of the ZSM-48 catalyst corresponds to a more suitable initial stage for producing a lubricant base oil with reduced aromatic content.
  • the first aromatic saturation bed, or with a catalyst not according to the disclosure such as zeolite Beta the total aromatics concentration will be higher when the feed reaches the second and third aromatic saturation beds or stages.
  • a feed comparable to the effluent from processing with a ZSM-48 dewaxing catalyst as described in Example 1 was used as an input feed for aromatic saturation processes at various conditions.
  • the input feed had an initial aromatics content of 566 ⁇ mol/g.
  • the amount of aromatics with 2 or more rings was 204 ⁇ mol/g.
  • FIG. 4 shows the total aromatic content of samples after additional aromatic saturation. Once again, total aromatic content was estimated by correlation, according to method B3997/PGC.
  • FIG. 4 shows results from processing of a feed over an MCM-41 catalyst that supported 0.3 wt% Pt and 0.9 wt% Pd as hydrogenation metals. The results show processing at various temperatures at both 2.8 MPag (400 psig) and 5.5 MPag (800 psig). As shown in FIG. 4 , the processing at both 2.8 MPag and 5.5 MPag resulted in total aromatics content above 400 ⁇ mol/g for processing temperatures of 220°C or less. At 250°C and higher, the total aromatics content was reduced to a level near 300 ⁇ mol/g.
  • the total aromatics content was reduced to 100 ⁇ mol/g.
  • An aromatics content of 100 ⁇ mol/g will typically correspond to less than 3 wt% aromatics, which is required for a lubricant base oil to qualify as a Group II lubricant base oil.
  • FIG. 5 shows the UV absorption at 325 nm for the two aromatics saturation processes in FIG. 4 , as well as another process at 400 psig, but a lower space velocity. (For the two lines in the plot corresponding to the 400 psig processes, arrows are used to associate the symbols with the appropriate results.) Additionally, FIG.
  • FIG. 5 shows the UV absorption at 325 nm for a feed where a ZSM-48 dewaxing catalyst was used for the aromatic saturation, instead of the MCM-41 catalyst.
  • the ZSM-48 dewaxing catalyst included 0.6 wt% of Pt as a hydrogenation metal.
  • the absorption at 325 nm for the feed was 0.58.
  • a minimum in absorption at 325 nm is shown somewhere between 220°C and 250°C, depending on the processing pressure, for the MCM-41 type catalysts.
  • FIG. 5 also shows that increasing the temperature to 280°C leads to an increase in absorptivity for the MCM-41 type catalysts.
  • the ZSM-48 dewaxing catalyst shows a much higher absorptivity at all temperatures shown in FIG. 5 .
  • FIG. 4 and FIG. 5 illustrates the benefit of the processes in various aspects described herein.
  • An aromatic saturation process that involves processing at only one temperature will lead to one of two less desirable results.
  • a higher processing temperature such as 280°C
  • the total aromatics content is reduced to a lower level as shown in FIG. 4 , but the mutagenicity index will be higher, as shown in FIG 5 .
  • processing only at a lower temperature such as 240°C will result in a lower mutagenicity index, but a higher total aromatics content.
  • the total aromatics content can first be reduced to a desired level, followed by reducing the mutagenicity index.
  • FIG. 7 schematically shows an example of the reaction system used for processing a "feed" from an initial hydroprocessing stage.
  • the configuration shown in FIG. 7 corresponds to a hydrocracking stage plus three additional stages that can provide aromatic saturation activity.
  • the feed 705 is first passed into a reactor 750 for performing hydrocracking.
  • the feed was effectively exposed to three beds of a hydrocracking catalyst, as schematically shown in FIG. 7 .
  • the hydrocracking catalyst was an alumina bound USY catalyst with 0.6 wt% of Pt supported on the catalyst.
  • arrows with small arrowheads 727 are depicted between each of the catalyst beds in reactor 750. These arrows schematically represent the introduction of quench gas into the reactor 750 between the catalyst beds. The small arrowheads indicate that the quench streams were used so that the temperature at the top of each catalyst bed in reactor 750 was substantially the same.
  • the effluent from reactor 750 was then passed into a reactor 770.
  • the effluent Prior to passing the effluent into reactor 770, the effluent was quenched 729 to reduce the temperature of the effluent, so that the temperature of the effluent at the top of the first bed in reactor 770 was lower than the temperature of the catalyst beds in reactor 750.
  • This more substantial type of quench 729 is indicated by the larger arrowhead for the arrow 759 indicating the quench of the effluent from reactor 750.
  • Reactor 770 was configured to effectively have four catalyst beds. Three of the catalyst beds 772 corresponded to beds of a dewaxing catalyst.
  • the dewaxing catalyst was an alumina bound ZSM-48 catalyst with 0.6 wt% of Pt supported on the catatlyst.
  • the final catalyst bed 774 in reactor 770 was a bed of an aromatic saturation catalyst.
  • the aromatic saturation catalyst was an amorphous silica-alumina and zirconia support with both Pt and Pd on the support.
  • smaller quench streams 737 were used between the dewaxing catalyst beds 772 to maintain a substantially similar temperature between the dewaxing catalyst beds.
  • a larger quench stream 739 was used to reduce the temperature between the final dewaxing catalyst bed 772 and the aromatic saturation catalyst bed 774.
  • reactor 780 The effluent from reactor 770 was then passed into reactor 780. Prior to passing the effluent into reactor 780, the effluent was quenched 749 to reduce the temperature of the effluent, so that the temperature of the effluent at the top of the first bed in reactor 780 was lower than the temperature of catalyst bed 774 in reactor 770.
  • Reactor 780 was configured to effectively have three catalyst beds of a hydrofinishing catalyst.
  • the hydrofinishing catalyst was an alumina bound MCM-41 catalyst with 0.3 wt% of Pt and 0.9 wt% of Pd supported on the catalyst. It is noted that an additional larger quench stream 799 could be included between two of the catalyst beds in reactor 780 to potentially create yet another temperature stage, but this additional optional quench stream 799 was not used in this example.
  • FIG. 8 also shows results from processing a feed in a comparative two stage aromatic saturation process.
  • the comparative two stage process was similar to the three stage aromatic saturation process shown in FIG. 7 , with the exception that the catalyst bed 774 corresponding to the silica-alumina-zirconia supported Pt/Pd aromatic saturation catalyst was not included in the comparative run.
  • the partial pressure of hydrogen for exposure of the feed to the hydrocracking catalyst was somewhat different.
  • a process model was used to predict the impact of performing the comparative process at the same hydrogen partial pressure conditions in the hydrocracking stage. The adjustments based on the model are shown in parentheses in FIG. 8 .
  • the hydrocracking stage reduces the aromatics content of the feed from more than 600 mmol/kg to 100 mmol/kg or less.
  • the catalytic dewaxing stage corresponding to the first "aromatic saturation" stage, then reduced the aromatics content by about another 60%.
  • the effluent from the catalytic dewaxing was then exposed to the hydrofinishing catalyst.
  • the effluent from dewaxing was first exposed to the aromatic saturation catalyst, corresponding to Pt/Pd on a silica-alumina-zirconia support, followed by exposure to the hydrofinishing catalyst.
  • the hydrofinishing catalyst As in FIG.
  • FIG. 9 shows the results from modeling the configuration in FIG. 7 .
  • the modeled reaction conditions corresponded to the conditions shown in FIG. 8 , with the exception of the temperature for the intermediate aromatic saturation stage.
  • the temperature of the intermediate aromatic saturation stage was allowed to vary as shown in FIG. 9 .
  • FIG. 9 shows the results from modeling the configuration in FIG. 7 .
  • the modeled reaction conditions corresponded to the conditions shown in FIG. 8 , with the exception of the temperature for the intermediate aromatic saturation stage.
  • the temperature of the intermediate aromatic saturation stage was allowed to vary as shown in FIG. 9 .
  • Table 2 shows the impact of using an intermediate aromatic saturation stage to achieve a lower aromatics content target versus the impact of achieving the target in a conventional (two-stage) reaction system by altering the processing conditions.
  • the modeled results in Table 2 represent modifying a process to allow the final aromatics content in the product to be reduced from about 6 wt% to about 2 wt%. For the heavy feed described in this example, this can correspond to reduction of aromatics from about 120 mmol/kg to about 40 mmol/kg.
  • the first column of conditions corresponds to the "baseline” conditions for achieving the initial target of about 6 wt% aromatics content in a final lubricant base oil product generated by processing of a heavy hydrocrackate feed.
  • the second column shows the predicted change in process severity that would be required to lower the aromatics content to 2 wt%. This increase in severity is achieved by reducing the space velocity in the reaction system.
  • the aromatic saturation catalyst space velocity is shown as "N/A", as the intermediate aromatic saturation catalyst is not present.
  • the third column shows a modified reaction system that includes a bed of aromatic saturation catalyst to provide an intermediate aromatic saturation stage. As shown in Table 2, the space velocity over the dewaxing catalyst and the hydrofinishing catalyst is the same in the first and third columns.

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Claims (9)

  1. Procédé de production d'une huile de base lubrifiante comprenant une ou plusieurs étape(s) de saturation aromatique, lesdites une ou plusieurs étape(s) de saturation aromatique comprenant :
    la mise en contact de, en tant que charge d'entrée, une fraction de résidu d'un processus d'hydrocraquage ayant une teneur totale en aromatiques de 50 mmol/kg à 1200 mmol/kg, une teneur en aromatiques polycycliques de 10 à 500 mmol/kg, et un point d'ébullition T5 d'au moins 300 °C et un point d'ébullition T95 de 621 °C ou moins, avec un premier catalyseur fonctionnant principalement par isomérisation et comprenant ZSM-48, ZSM-23, ou une combinaison de ceux-ci, un liant, et de 0,1 à 1,5 % en poids de Pt soutenu sur le catalyseur dans des premières conditions de saturation aromatique efficaces pour produire un premier effluent ayant une teneur en aromatiques inférieure à 400 mmol/kg d'aromatiques, la teneur en aromatiques du premier effluent étant inférieure à la teneur en aromatiques de la charge d'entrée, les premières conditions de saturation aromatique efficaces comprenant une température de 320 °C à 370 °C, une pression partielle d'hydrogène de 1,8 à 6,9 Mpag, une vitesse spatiale liquide horaire de 0,2 à 10 h-1 et un taux de circulation d'hydrogène de 35,6 à 1 781 m3/m3 ;
    la mise en contact d'au moins une partie du premier effluent ayant un point d'ébullition au-dessus de la plage de distillat, c'est-à-dire de 204 °C à 343 °C, avec un deuxième catalyseur comprenant MCM-41, ZSM-48, ZSM-23, ou une combinaison de ZSM-48 et ZSM-23, un liant, et de 0,1 à 1,5 % en poids de Pt, Pd, ou une combinaison de Pt et Pd, dans des deuxièmes conditions de saturation aromatique efficaces pour produire un deuxième effluent, les deuxièmes conditions de saturation aromatique efficaces comprenant une température de 270 °C à 330 °C et une pression partielle d'hydrogène d'au moins 4,1 MPag (600 psig), la température des deuxièmes conditions de saturation aromatique efficaces étant au moins 10 °C au-dessous de la température des premières conditions de saturation aromatique efficaces ; et
    la mise en contact d'au moins une partie du deuxième effluent avec un troisième catalyseur comprenant MCM-41, un liant, et de 0,1 à 1,5 % en poids de Pt, Pd ou une combinaison de Pt et Pd dans des troisièmes conditions de saturation aromatique efficaces, les troisièmes conditions de saturation aromatique efficaces comprenant une température de 220 °C à 270 °C, la température des troisièmes conditions de saturation aromatique efficaces étant au moins 30 °C au-dessous de la température des deuxièmes conditions de saturation aromatique efficaces.
  2. Procédé selon la revendication 1, dans lequel
    a) la mise en contact d'au moins une partie du premier effluent avec un deuxième catalyseur comprend l'exposition d'une partie du premier effluent à un premier catalyseur intermédiaire dans des premières conditions d'hydrotraitement intermédiaire efficaces pour produire un premier effluent intermédiaire, et la mise en contact d'au moins une partie de du premier effluent intermédiaire avec le deuxième catalyseur ; et/ou
    b) la mise en contact d'au moins une partie du deuxième effluent avec un troisième catalyseur comprend l'exposition d'une partie du deuxième effluent à un deuxième catalyseur intermédiaire dans des deuxièmes conditions d'hydrotraitement intermédiaire efficaces pour produire un deuxième effluent intermédiaire, et la mise en contact d'au moins une partie du deuxième effluent intermédiaire avec le troisième catalyseur.
  3. Procédé selon la revendication 2, dans lequel les premières conditions d'hydrotraitement intermédiaire efficaces comprennent des conditions de saturation aromatique comprenant une température de 280 °C à 330 °C, la température des premières conditions d'hydrotraitement intermédiaire efficaces étant au moins 10 °C au-dessous des premières conditions de saturation aromatique efficaces, facultativement au moins 20 °C au-dessous, ou au moins 30 °C au-dessous, ou au moins 40 °C au-dessous ; dans lequel les deuxièmes conditions de saturation aromatique efficaces comprennent une température de 270 °C à 300 °C ; et dans lequel la température des deuxièmes conditions de saturation aromatique efficaces est au moins 10 °C au-dessous de la température des premières conditions d'hydrotraitement intermédiaire efficaces, facultativement au moins 20 °C au-dessous, ou au moins 30 °C au-dessous, ou au moins 40 °C au-dessous.
  4. Procédé selon la revendication 2, dans lequel les deuxièmes conditions de saturation aromatique efficaces comprennent une température de 280 °C à 330 °C ; dans lequel les deuxièmes conditions d'hydrotraitement intermédiaire efficaces comprennent des conditions de saturation aromatique comprenant une température de 270 °C à 300 °C, la température des deuxièmes conditions d'hydrotraitement intermédiaire efficaces étant au moins 10 °C au-dessous des deuxièmes conditions de saturation aromatique efficaces, facultativement au moins 20 °C au-dessous, ou au moins 30 °C au-dessous, ou au moins 40 °C au-dessous ; et dans lequel la température des troisièmes conditions de saturation aromatique efficaces est au moins 10 °C au-dessous de la température des deuxièmes conditions d'hydrotraitement intermédiaire efficaces, facultativement au moins 20 °C au-dessous, ou au moins 30 °C au-dessous, ou au moins 40 °C au-dessous.
  5. Procédé selon l'une quelconque des revendications ci-dessus, dans lequel la température des deuxièmes conditions de saturation aromatique efficaces est au moins 20 °C au-dessous de la température des premières conditions de saturation aromatique efficaces, ou au moins 30 °C au-dessous, ou au moins 40 °C au-dessous.
  6. Procédé selon l'une quelconque des revendications ci-dessus, dans lequel la température des troisièmes conditions de saturation aromatique efficaces est au moins 40 °C au-dessous de la température des deuxièmes conditions de saturation aromatique efficaces.
  7. Procédé selon l'une quelconque des revendications ci-dessus, le procédé comprenant en outre :
    l'hydrocraquage d'une matière première ayant un point d'ébullition T5 d'au moins 300 °C dans des conditions d'hydrocraquaqe efficaces pour former une matière première hydrocraquée ayant une teneur en aromatiques de 200 mmol/kg ou moins,
    dans lequel la mise en contact d'une charge d'entrée ayant une teneur en aromatiques de 50 mmol/kg à 1200 mmol/kg qui comprend la mise en contact d'au moins une partie de la matière première hydrocraquée.
  8. Procédé selon l'une quelconque des revendications ci-dessus, le procédé comprenant en outre :
    l'hydrocraquage d'une matière première ayant un point d'ébullition T5 d'au moins 300 °C dans des conditions d'hydrocraquage efficaces pour former une première matière première hydrocraquée ;
    le fractionnement de la première matière première hydrocraquée pour former au moins une fraction diesel et une fraction ayant une plage d'ébullition supérieure à la fraction diesel ; et
    l'hydrocraquage d'au moins une partie de la fraction ayant une plage d'ébullition plus élevée que la fraction diesel dans des conditions d'hydrocraquage non acides pour former une deuxième matière première hydrocraquée ayant une teneur en aromatiques de 200 mmol/kg ou moins,
    dans lequel la mise en contact d'une charge d'entrée ayant une teneur en aromatiques de 50 mmol/kg à 1200 mmol/kg comprend la mise en contact d'au moins une partie de la deuxième matière première hydrocraquée.
  9. Procédé selon l'une quelconque des revendications ci-dessus, dans lequel les deuxièmes conditions de saturation aromatique efficaces comprennent une pression partielle d'hydrogène d'au moins 5,2 MPag (750 psig), ou le procédé comprenant en outre le refroidissement du premier effluent en utilisant un flux de refroidissement en phase gazeuse contenant de l'hydrogène, ou une combinaison de ceux-ci.
EP15722814.9A 2015-04-08 2015-04-23 Procédé de saturation pour fabriquer des huiles de base pour lubrifiant Active EP3280782B1 (fr)

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US14/681,331 US9809762B2 (en) 2011-12-15 2015-04-08 Saturation process for making lubricant base oils
PCT/US2015/027204 WO2016164053A1 (fr) 2015-04-08 2015-04-23 Procédé de saturation pour fabriquer des huiles de base pour lubrifiant

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US20240076564A1 (en) * 2021-01-19 2024-03-07 Chevron U.S.A. Inc. Method for producing high quality base oils using two stage hydrofinishing

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US5198203A (en) 1990-01-25 1993-03-30 Mobil Oil Corp. Synthetic mesoporous crystalline material
US5102643A (en) 1990-01-25 1992-04-07 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis
US5976353A (en) * 1996-06-28 1999-11-02 Exxon Research And Engineering Co Raffinate hydroconversion process (JHT-9601)
US5911874A (en) * 1996-06-28 1999-06-15 Exxon Research And Engineering Co. Raffinate hydroconversion process
US7482300B2 (en) * 2005-12-13 2009-01-27 Exxonmobil Research And Engineering Company High activity ZSM-48 and methods for dewaxing
US8524069B2 (en) * 2008-02-29 2013-09-03 Exxonmobil Research And Engineering Company Production of high viscosity index lube base oils
US8617383B2 (en) * 2010-06-29 2013-12-31 Exxonmobil Research And Engineering Company Integrated hydrocracking and dewaxing of hydrocarbons
US20120000818A1 (en) * 2010-06-30 2012-01-05 Exxonmobil Research And Engineering Company Process for the preparation of group ii and group iii lube base oils
US9029301B2 (en) * 2011-12-15 2015-05-12 Exxonmobil Research And Engineering Company Saturation process for making lubricant base oils

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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SG11201705834TA (en) 2017-10-30
EP3280782A1 (fr) 2018-02-14

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