WO2021030003A1 - Procédé d'évaluation de charges d'hydrocarbures pour craquage catalytique - Google Patents

Procédé d'évaluation de charges d'hydrocarbures pour craquage catalytique Download PDF

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Publication number
WO2021030003A1
WO2021030003A1 PCT/US2020/042348 US2020042348W WO2021030003A1 WO 2021030003 A1 WO2021030003 A1 WO 2021030003A1 US 2020042348 W US2020042348 W US 2020042348W WO 2021030003 A1 WO2021030003 A1 WO 2021030003A1
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Prior art keywords
catalytic cracking
cracking feedstock
potential
potential catalytic
feedstock
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PCT/US2020/042348
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English (en)
Inventor
Mathieu PARENTEAU
Robert A. COCKBURN
Gino CAIONE
Jonathan A. FERGUSON
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Exxonmobil Research And Engineering Company
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Publication of WO2021030003A1 publication Critical patent/WO2021030003A1/fr

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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C10G11/187—Controlling or regulating
    • 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
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • 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
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/36—Controlling or regulating
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This application relates to methods for converting hydrocarbon feedstocks, such as used lubricating oil, into high value products.
  • VGO vacuum gas oil
  • Light VGO includes hydrocarbons having a boiling point less than about 343°C and is typically converted into light, valuable, and clean fuels, such as motor gasoline, kerosene, and olefinic gasses (methane, ethane, propane, butanes).
  • Heavy VGO includes hydrocarbons having a boiling point greater than about 343°C and is typically converted into lubricating oil (e.g., motor oil). While fuels, such as those derived from light VGO, are physically consumed during use, lubricating oils are not. Thus, theoretically, lubricating oil (e.g., used motor oil) could be recycled for reuse.
  • Light VGO is converted into valuable fuels by a process referred to as cracking, which breaks (“cracks”) the hydrocarbons into smaller molecules for incorporating into a fuel distillate pool.
  • a fuel distillate pool may then be subsequently converted into highly valued motor gasoline, kerosene, diesel fuel, jet fuel, and/or liquid petroleum gas.
  • Heavier hydrocarbons, such as those in heavy VGO or lubricating oil may be subjected to a similar cracking process.
  • the chemical structure of lubricating oil remains intact after use, the bulk composition is typically contaminated with material that precludes efficient conversion into smaller hydrocarbons by cracking.
  • the cracking reaction is typically facilitated by a catalyst (thus termed “catalytic cracking”), which is adversely affected by many contaminants found in used lubricating oils. Additionally, some contaminants are corrosive to a cracking unit’s components, while yet others pose an issue if present in a resulting product.
  • a catalyst titanium (thus termed “catalytic cracking”), which is adversely affected by many contaminants found in used lubricating oils. Additionally, some contaminants are corrosive to a cracking unit’s components, while yet others pose an issue if present in a resulting product.
  • This application relates generally to processing and evaluation of hydrocarbon-based feedstocks and, more specifically, to the processing and evaluation of re-refined used lubricating oils for use as feedstock for fluid catalytic cracking.
  • a method comprising: defining a set of disposition criteria comprising a plurality of measurable properties selected from the group consisting of boiling point range, specific gravity, total reactive sulfur, total nitrogen, basic nitrogen, S:N ratio, chlorine, acidity, coking tendency, aniline point, aromaticity, paraffin content, naphthenes, aliphatic unsaturation, sedimentation, water content, flash point, concentration of polychlorinated biphenyls, and the content of one or more of the following elements: S, Ni, V, Fe, Na, Cu, Ca, Si, B, P, Zn, Mg, Mo, K, Sn, Al, Cr, Ag, Ti, Sb, Pb, and Ba, wherein each of the measurable properties has associated therewith a pre-defined value; testing one or more samples of a potential catalytic cracking feedstock to generate a plurality of measured properties corresponding to the plurality of measurable properties, wherein each of the measured properties is characterized by a quantitative measured value;
  • Another example method includes defining a set of disposition criteria comprising a plurality of measurable properties selected from the group consisting of boiling point range, specific gravity, total reactive sulfur, total nitrogen, basic nitrogen, S:N ratio, chlorine, acidity, coking tendency, aniline point, aromaticity, paraffin content, naphthenes, aliphatic unsaturation, sedimentation, water content, flash point, concentration of polychlorinated biphenyls, and the content of one or more of the following elements: S, Ni, V, Fe, Na, Cu, Ca, Si, B, P, Zn, Mg, Mo, K, Sn, Al, Cr, Ag, Ti, Sb, Pb, and Ba, wherein each of the measurable properties has associated therewith a pre-defined value; testing one or more samples of a potential catalytic cracking feedstock to generate a plurality of measured properties corresponding to the plurality of measurable properties, wherein each of the measured properties is characterized by a quantitative measured value; comparing each quantitative measured value to each pre-defined
  • Figure 1 illustrates an example flow diagram of the methods disclosed herein for the assessment and utilization of a potential hydrocarbon-based feedstock in catalytic cracking.
  • the present disclosure relates to methods for reliably characterizing the disposition of a hydrocarbon-based feedstock (e.g., used lubricating oil) to maximize its potential for conversion into highly valuable and clean-burning fuels.
  • a hydrocarbon-based feedstock e.g., used lubricating oil
  • lubricating oil may be cracked under similar conditions employed in cracking VGO.
  • Prior attempts to process used lubricating oil in this fashion have failed, however, as cracking catalysts are highly susceptible to and deactivated by many of the contaminants found in used lubricating oil. Additionally, various refinery components are susceptible to fouling (which is expensive to remedy) by common contaminants ⁇ Thus, it is a common belief in the industry that used lubricating oil poses too high of a risk to be converted by catalytic cracking.
  • Methods are provided herein that reduce such a risk. Described herein are methods for determining if and how a potential catalytic cracking feedstock may be subjected to catalytic cracking.
  • Methods include defining a set of disposition criteria comprising a plurality of measurable properties which may include, but are not limited to, boiling point range, specific gravity, total reactive sulfur, total nitrogen, basic nitrogen, S:N ratio, chlorine, acidity, coking tendency, aniline point, aromaticity, paraffin content, naphthenes, aliphatic unsaturation, sedimentation, water content, flash point, concentration of polychlorinated biphenyls, and the content of one or more of the following elements: S, Ni, V, Fe, Na, Cu, Ca, Si, B, P, Zn, Mg, Mo, K, Sn, Al, Cr, Ag, Ti, Sb, Pb, and Ba. Combinations of the foregoing may also be used.
  • Each of the plurality of measurable properties has associated therewith a pre-defined value.
  • value refers to a numerical value that may be a single value, an upper limit, a lower limit, or a range of values.
  • One or more samples of a potential catalytic cracking feedstock may be tested, generating a plurality of measured properties that correspond to the plurality of measurable properties in the set of disposition criteria.
  • Each of the measured properties is characterized by a quantitative measured value and each of the measurable properties is characterized by a pre-defined value.
  • Each quantitative measured value may then be compared to each pre-defined value, and measured properties whose quantitative measured value do not comport with the corresponding pre-defined value may be identified.
  • a set of disposition criteria may set forth a range of acceptable sulfur levels. The sulfur level of a potential catalytic cracking feedstock may be measured and compared to the range of acceptable sulfur levels defined in the set of disposition criteria.
  • the potential catalytic cracking feedstock may be supplied to a catalytic cracking unit.
  • the potential catalytic cracking feedstock may be subjected to one or more processes to modify the quantitative measured value to comport with the pre-defined value, thereby generating a modified catalytic cracking feedstock; and supplying the modified catalytic cracking feedstock to the catalytic cracking unit.
  • processing may include multiple steps to effectively modify the quantitative measured value of each measured property to generate a potential catalytic cracking feedstock wherein each measured property value comports with each corresponding pre-defined value.
  • the potential catalytic cracking feedstock may be divided into fractions. The dividing may be based on a simple percentage of the potential catalytic cracking feedstock (e.g., 10 wt. %, 20 wt. %, 50 wt. %, 75 wt. % of the potential catalytic cracking feedstock). One or more fractions may be combined with one or more fractions of a second potential catalytic cracking feedstock to generate a combined potential catalytic cracking feedstock having a disposition wherein the quantitative measured value of each measured property comports with the corresponding pre-defined value.
  • a simple percentage of the potential catalytic cracking feedstock e.g. 10 wt. %, 20 wt. %, 50 wt. %, 75 wt. % of the potential catalytic cracking feedstock.
  • One or more fractions may be combined with one or more fractions of a second potential catalytic cracking feedstock to generate a combined potential catalytic cracking feedstock
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.
  • a potential catalytic cracking feedstock may be any hydrocarbon composition, for example, one or more petroleum products derived from crude oil (e.g., shale oil), one or more products derived from pyrolysis oils (e.g., upgraded biocrude), or any blend thereof.
  • suitable potential catalytic cracking feedstocks include lubricating oils (including used lubricating oils), pyrolysis oils, or any blend thereof.
  • lubricating oil and grammatical variations thereof refer to a hydrocarbon composition characterized by a boiling point range from about 300°C to about 400°C.
  • lubricating oil is motor oil.
  • Used lubricating oil may be a mixture of different types and grades of oils derived from different sources. Used lubricating oil may have been optionally re -refined.
  • Used lubricating oil may contain contaminants such as, but not limited to, motor oil additives, water, metals, organometallics, polymeric components, grease, brake fluid, transmission oil, transformer oil, railroad lubricant, crude oil, antifreeze, dry cleaning fluid, degreasing solvents, edible fats and oils, mineral acids, soot, earth, or any combination thereof.
  • pyrolysis oil also called biocrude or bio-oil
  • grammatical variations thereof refer to a hydrocarbon composition derived from the product of heating dried biomass in the absence of oxygen.
  • a potential catalytic cracking feedstock may have been hydroprocessed or desalted before processing by catalytic cracking.
  • hydroprocessing include, but are not limited to, hydrotreating, hydrocracking, catalytic dewaxing, hydrofinishing/aromatic saturation, and combinations thereof.
  • hydrotreating include, but are not limited to, hydrogenolysis (e.g., hydrosulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization, hydrodeasphalteneization), hydrogenation, (e.g., olefin saturation, aromatic saturation), and combinations thereof.
  • a potential catalytic cracking feedstock may be sourced from a re-refinery.
  • a process for re-refining lubricating oil may include partially vaporizing (“dehydrating”) lubricating oil to remove water, gasoline, solvents, glycols, lighter organics, or combinations thereof. This may be carried out at atmospheric pressure at a temperature of about 160°C. Water and/or lighter organics may be condensed and separated from lubricating oil, generating a dehydrated lubricating oil. The dehydrated lubricating oil may then be stripped under vacuum to remove light gasoil and adjust the flash point to generate gasoil. The gasoil may then be distilled under vacuum under conditions effective to recover a VGO fraction. This may be carried out, for example, at a high temperature with a thin film evaporator.
  • the oil When using a thin film evaporator, the oil may experience a short residence time (about 10 seconds) therein, and, when combined with a low wall temperature and high flow turbulence, clean lubricating oil may be recovered as a distillate, separated from heavier components such as additives, metals, and degradation products, which may be concentrated in a residue.
  • a recovered VGO fraction may be further processed to remove various impurities.
  • hydroprocessing or acid washing e.g., with sulfuric acid, hydrochloric acid, nitric acid, and/or acetic acid
  • may remove contaminants such as, but not limited to, chlorinated compounds, sulfurous compounds, oxygenated organic compounds, polyaromatic hydrocarbons, or combinations thereof.
  • Examples of measurable properties comprising a potential catalytic cracking feedstock’ s disposition that influence suitability for catalytic cracking include, but are not limited to, boiling point range, specific gravity, sulfur (S), total nitrogen, basic nitrogen, total chlorine, polychlorinated biphenyl (PCB) content, acidity, reactive sulfur content, coking tendency, aniline point, aromaticity, bromine number, flash point, sedimentation and water levels, cycloparaffin content, paraffin content, pour point, nickel (Ni), vanadium (V), iron (Fe), sodium (Na), calcium (Ca), copper (Cu), arsenic (As), silicon (Si), barium (Ba), boron (B), phosphorus (P), zinc (Zn), magnesium (Mg), molybdenum (Mo), potassium (K), tin (Sn), aluminum (Al), chromium (Cr), and any combinations thereof.
  • S sulfur
  • PCB polychlorinated biphenyl
  • acidity reactive sulfur content
  • the cracking reaction is highly endothermic, driven by extremely high temperatures and entropy change due to fragmenting a large molecule into several small pieces.
  • a catalytic cracking feedstock may be vaporized by a hot catalyst, effectively reducing energy required to break carbon-carbon bonds. Properties of a catalytic cracking feedstock disposition that influence any of these variables will, in turn, affect the efficiency and/or selectivity of the cracking reaction.
  • the molecular weight and relative amount of a particular hydrocarbon in a potential catalytic cracking feedstock may be inferred by boiling point range as well as, to some extent, specific gravity. Light hydrocarbons may vaporize too quickly. Conversely, heavy hydrocarbons may potentially not vaporize at all. Additionally, hydrocarbon molecular weight is linked to tendency for cracking. Thus, the hydrocarbon molecular weight distribution in a potential catalytic cracking feedstock directly affects yield. Molecular weight distribution may be modified by distillation to separate and remove unwanted fractions.
  • Saturation and aromaticity also affect a hydrocarbon’s tendency to crack.
  • unsaturated aliphatic hydrocarbons olefins
  • saturated aliphatic hydrocarbons paraffins, cyclic paraffins
  • aromatic hydrocarbons are resistant to cracking.
  • the aliphatic nature of a potential catalytic cracking feedstock may be characterized by bromine number.
  • Aromaticity may be characterized by aniline number or refractive index. Pour point, a measure of the lowest temperature at which an oil will flow when cooled without stirring under standard cooling conditions, may be indicative of paraffin content.
  • Saturation and aromaticity also affect a potential catalytic cracking feedstocks tendency to coke.
  • highly unsaturated hydrocarbons e.g., aromatics
  • larger hydrocarbons e.g., boiling above about 565°C
  • Other properties that increase coke formation include, but are not limited to, the presence of basic nitrogen, sulfur, zinc, and free elemental iron.
  • Potential catalytic cracking feedstocks may be catalytically hydrotreated to remove basic nitrogen and sulfur. Iron removal is more difficult, and generally requires re-refining for removal.
  • a catalyst may be inactivated by metals such as, but not limited to, nickel, sodium, vanadium, potassium, calcium, iron, barium, phosphorus, and magnesium.
  • Arsenic oxide is also a catalyst poison. Many of these poisons originate in the crude oil from which a catalytic cracking feedstock is derived. Hydrotreating and/or re -refining may remove some of these components, though with variable efficacy. The presence of water in a potential catalytic cracking feedstock breaks apart catalyst particles and may cause vapor locking in furnace passes.
  • Some properties of a potential catalytic cracking feedstock’s disposition affect the logistics of storing and transporting a potential catalytic cracking feedstock. For example, hydrocarbon compositions require proper storage. Flash point measures the temperature at which a feedstock gives off enough vapor to ignite in air. Generally, if the flash point of a potential catalytic cracking feedstock is not within a set range, the potential catalytic cracking feedstock cannot be safely stored and transported and should not be purchased.
  • Some properties of a potential catalytic cracking feedstock’s disposition affect various components of refinery equipment.
  • salts, acid, nitrogen, and sulfur (including total reactive sulfur) in a catalytic cracking feedstock may lead to equipment corrosion.
  • reactive sulfur include, but are not limited to, hydrogen sulfide, mercaptans, aliphatic sulfides, aliphatic disulfides, elemental sulfur, and polysulfides.
  • Equipment integrity may also be compromised by a low sulfur to nitrogen ratio (S:N ratio).
  • Feedstock may be hydrotreated and/or desalted to modify any of these properties, to some extent, but often a corrosive feedstock may be routed for processing elsewhere.
  • a low S:N ratio may be increased by adjusting sulfur, nitrogen, or both.
  • barium may reduce adverse effects of contaminating metals (e.g., vanadium, iron, nickel) on a catalyst.
  • contaminating metals e.g., vanadium, iron, nickel
  • the treating of cracking catalyst with barium for this purpose is disclosed, for example, in U.S. Patent No. 4,377,494, which is incorporated herein by reference with respect to its disclosure of using barium to reduce catalyst poisoning.
  • boron in the form of a boron oxide
  • Antimony is also used as a nickel passivation additive to reduce adverse effects of nickel. However, if the antimony concentration is too high, downstream fouling, in particular, on the main fractionator, may occur. Additionally, nitrogen oxide (NO x ) emissions may be increased.
  • barium may be present in tight oil extraction chemicals as barium sulfate. While it has been documented to have a positive impact, as described above, barium may negatively affect zeolitic catalysts in a similar fashion as other alkali metals such as sodium, magnesium, calcium, and potassium.
  • phosphorus typically does not occur naturally in crude oil (with the possible exception of those crudes from Western Canada), but is present in additives used in oil wells in the form of di-alkyl phosphate ester (DAPE) and decomposes to phosphorus during distillation. Phosphorus may also be present in shale oil. Phosphorus may contribute to fouling, plugging, and hard deposits of catalytic cracking equipment and may contribute to catalyst poisoning in fractionating and hydrotreating downstream of a catalytic cracking unit. Other examples of atypical contaminants where little information regarding the impact on catalytic cracking is known include tin, aluminum, and chromium.
  • Each of the properties defining the disposition of a potential catalytic cracking feedstock may be determined by a plurality of analytical tests.
  • One or more samples of a potential catalytic cracking feedstock may be obtained.
  • One of skill in the art will be familiar with appropriate methods for obtaining, storing, handling, and processing samples of a potential catalytic cracking feedstock.
  • one or more of the samples may then be subjected to plurality of analytical tests comprising a plurality of quantitative and qualitative analyses.
  • Each test is designed to measure one or more properties of the potential catalytic cracking feedstock.
  • Each sample may be subjected to one or more quantitative analyses.
  • qualitative tests include, for example, identification of specific contaminants.
  • quantitative analyses may include, but are not limited to, measuring one or more of the following: contamination concentration, flash point, boiling point range, pour point, acidity, specific gravity, aliphatic unsaturation, aromaticity, and tendency for forming coke.
  • the particular quantitative tests that comprise the plurality of analytical tests may be guided by a potential catalytic cracking feedstock’s origin.
  • a potential catalytic cracking feedstock is derived from virgin source (i. e. , has not been previously used)
  • fewer analyses may be sufficient to adequately determine its suitability for cracking.
  • additional analyses may be necessary to characterize its disposition more thoroughly.
  • a potential catalytic cracking feedstock may be subjected to a plurality of quantitative analyses that measure components commonly added to lubricating oils (e.g., motor oil additives) or introduced during use in a motor (e.g., components of engine wear).
  • the plurality of quantitative analyses may include analytical techniques such as, but not limited to, chromatography (e.g., gas, liquid, high-performance liquid, thin layer, size exclusion), spectrophotometry (e.g., infrared, near infrared, Fourier transform infrared, florescence), and titration (e.g., coulometric, potentiometric).
  • analytical techniques such as, but not limited to, chromatography (e.g., gas, liquid, high-performance liquid, thin layer, size exclusion), spectrophotometry (e.g., infrared, near infrared, Fourier transform infrared, florescence), and titration (e.g., coulometric, potentiometric).
  • chromatography e.g., gas, liquid, high-performance liquid, thin layer, size exclusion
  • spectrophotometry e.g., infrared, near infrared, Fourier transform infrared
  • Each measured property whose value does not comport with the pre-defined value of the corresponding property in the set of disposition criteria may then be identified. If there is no measured property value identified that does not comport the value of the corresponding property in the set of disposition criteria, the potential catalytic cracking feedstock may be considered to be a qualified catalytic cracking feedstock and may be conveyed to a catalytic cracking unit for conversion. In other words, if the value of all measured properties comport with the pre-defined value of all corresponding properties in the set of disposition criteria, the potential catalytic cracking feedstock is deemed a qualified catalytic cracking feedstock and may be conveyed to a catalytic cracking unit.
  • the value of the at least one measured property may be modified. Modification of the at least one measured property may generate a potential catalytic cracking feedstock having a disposition where the value of the at least one measured property comports with the pre-defined value of the corresponding property in the set of disposition criteria. In any embodiment, modification may include multiple steps to modify multiple measured property values so that each modified measured property value comports with each pre-defined value of the corresponding property in the set of disposition criteria.
  • the potential catalytic cracking feedstock may be divided into fractions. The dividing may be based on a simple percentage of the potential catalytic cracking feedstock (e.g., 10 wt. %, 20 wt. %, 50 wt. %, 75 wt. % of the potential catalytic cracking feedstock). One or more fractions may be combined with one or more fractions of a second potential catalytic cracking feedstock to generate a combined potential catalytic cracking feedstock having a disposition such that the value of each measured property comports with each pre-defined value of the corresponding property in the set of disposition criteria.
  • a simple percentage of the potential catalytic cracking feedstock e.g. 10 wt. %, 20 wt. %, 50 wt. %, 75 wt. % of the potential catalytic cracking feedstock.
  • One or more fractions may be combined with one or more fractions of a second potential catalytic cracking feedstock to generate a combined potential
  • non-fixed parameters of a catalytic cracking refinery process may be adjusted or chosen based on the disposition of a potential catalytic cracking feedstock.
  • non-fixed parameters include, but are not limited to, temperature, pressure, catalyst choice, type of catalyst bed (e.g., moving, fixed, fluidized bed), use of additives, and/or the like.
  • One of skill in the art will be familiar with various method and system parameters that may be modified to increase compatibility with a potential catalytic cracking feedstock.
  • the one or more modifications that may be carried out in order to generate a qualified catalytic cracking feedstock may depend on a number of factors, for example, but not limited to, availability of refinery equipment and/or cost to make said modifications. For example, if the value of one or more properties defining a potential catalytic cracking feedstock’s disposition may be modified easily and inexpensively by one or more simple processes, such modifications would be undertaken.
  • catalytic cracking and any grammatical variations thereof refer to the catalyzed breaking of one or more carbon-carbon bonds in a hydrocarbon molecule to generate shorter, smaller hydrocarbons.
  • catalytic cracking processes include, but are not limited to, hydrocracking and fluidized catalytic cracking.
  • suitable catalytic catalysts include any commonly used in the industry, for example (but not limited to) zeolitic catalysts, bauxite, silica-alumina, aluminum hydrosilicate, and the like.
  • Methods are provided herein that include thoroughly characterizing the disposition of a potential catalytic cracking feedstock.
  • the previously perceived high risk associated with using a catalytic cracking feedstock of unknown disposition is substantially reduced if not eliminated.
  • a potential catalytic cracking feedstock may be utilized to its maximum potential.
  • the methods include identifying any measured property of a potential catalytic cracking feedstock whose value does not comport with a pre defined value or range of values in a set of disposition criteria, modifying one or more of those properties and/or combining at least a portion of the potential catalytic cracking feedstock with at least a portion of an additional potential catalytic cracking feedstock to generate a qualified catalytic cracking feedstock.
  • the Figure illustrates a flow diagram for characterizing the disposition of a potential catalytic cracking feedstock to generate a qualified catalytic cracking feedstock.
  • the source of the potential catalytic cracking feedstock is determined at 2.
  • the method proceeds to 4a where one or more samples of the potential catalytic cracking feedstock are subjected to a plurality of quantitative analyses (“Panel A”).
  • the plurality of analytical tests generates a plurality of measured properties that characterizes the potential catalytic cracking feedstock’s disposition.
  • Panel B may include, for example, determination of one or more of boiling point ran, pour point, flash point, specific gravity, aromaticity, aliphatic unsaturation, sulfur, total reactive sulfur, sedimentation, water content, total nitrogen, basic nitrogen, chlorine, acidity, Condradson carbon residue, basic sedimentation and water, Ni, V, Fe, Na, Cu, and Ca.
  • Panel B analyses may include, for example, any or all of Panel A analyses, along with analyses that identify and measure known contaminants of used lubricating oil.
  • Panel B may identify and measure engine wear components and common additives. Examples include, but are not limited to, Si, B, P, Zn, Mg, Mo, K, Sn, Al, Cr, Ag, Ti, Sb, Pb, Ba, PCBs, and any combination thereof.
  • the plurality of qualitative analyses comprising each of Panel A and Panel B may include any combination of the above-described analyses.
  • the value of each measured property in the plurality of measured properties may then be compared to a pre-defined value in a corresponding property in a set of disposition criteria.
  • Each measured property whose value does not comport with the pre-defined value of the corresponding property in the set of disposition criteria may then be identified. If there is no measured property value identified that does not comport with the value of the corresponding property in the set of disposition criteria, the potential catalytic cracking feedstock may be considered to be a qualified catalytic cracking feedstock and may be conveyed to a catalytic cracking unit for conversion.
  • the potential catalytic cracking feedstock is deemed a qualified catalytic cracking feedstock and may be conveyed to a catalytic cracking unit 14.
  • step 8 it is determined whether or not it is economically and/or physically viable to modify each identified measured property whose value does not comport with the pre-defined value of the corresponding property in the set of disposition criteria to generate a qualified catalytic cracking feedstock. If it would not be economically and/or physically viable to modify at least one of each identified measured property whose value does not comport with the pre-defined value of the corresponding property in the set of disposition criteria, the potential catalytic cracking feedstock may be rejected 15.
  • step 8 it may be determined the most economically viable process for generating a qualified catalytic cracking feedstock from the potential catalytic cracking feedstock.
  • a potential catalytic cracking feedstock may be conveyed for processing to modify the disposition of a potential catalytic cracking feedstock 10, generating a modified potential catalytic cracking feedstock having a disposition with fewer properties whose values do not comport with the value or value range of the corresponding property in the set of disposition criteria. If a modified potential catalytic cracking feedstock is generated wherein all measured property values comport with the pre-defined value for each corresponding property in the set of disposition criteria, the modified potential catalytic cracking feedstock may be considered to be a qualified catalytic cracking feedstock and may be conveyed to a catalytic cracking unit for conversion 14.
  • a potential catalytic cracking feedstock may be combined with one or more potential catalytic cracking feedstocks 12 to generate a combined potential catalytic cracking feedstock having a disposition such that the value of each measured property comports with each pre-defined value of the corresponding property in the set of disposition criteria.
  • the combined potential catalytic cracking feedstock may be considered a qualified catalytic cracking feedstock and conveyed to a catalytic cracking unit for conversion 14.
  • the Figure depicts a dashed line with a double arrow between steps 10 and 12 where, optionally, a potential catalytic cracking feedstock may undergo processing at both steps 10 and 12 to generate a qualified catalytic cracking feedstock that is then conveyed to a catalytic cracking unit for conversion 14.
  • the catalytic cracking unit to which a qualified catalytic cracking feedstock is conveyed may be any type of catalytic cracking unit.
  • a catalytic cracking unit may employ fixed catalyst beds, moving catalyst beds, fluidized beds, or any combination thereof.
  • a catalytic cracking unit may comprise an inlet for supplying hydrogen to a catalyst bed.
  • a catalytic cracking unit may comprise apparatus and equipment for catalyst regeneration.
  • catalytic cracking is used herein to illustrate most clearly the advantages gained from use of described methods to maximize the potential of a hydrocarbon feedstock
  • catalytic cracking is merely used as an example of a suitable refining process.
  • the methods disclosed may be used to determine the disposition of any feedstock as it relates to suitability for any refining process.
  • samples of potential catalytic cracking feedstock may be subjected to a plurality of quantitative analyses that measure one or more of boiling point range, specific gravity, pour point, flash point, acidity, Condradson carbon residue, basic sedimentation and water content, total reactive sulfur, total nitrogen, basic nitrogen, aliphatic unsaturation, aromaticity, cycloparaffin content, paraffin content, naphthene content, chlorine, PCBs, S, Ni, V, Fe, Na, Cu, Ca, Si, B, P, Zn, Mg, Mo, K, Sn, Al, Cr, Ag, Ti, Sb, Pb, or Ba.
  • Table 1 lists each of the above properties as well as ASTM or UOP methods that may be employed to measure each.
  • used lubricating oil may be converted into high value, clean-buming fuels through catalytic cracking.
  • the methods disclosed herein are practical and reliable on an industrial scale and may be used as a standard operating procedure for any process in which the disposition of a hydrocarbon feedstock is important to know.
  • the methods disclosed herein provide confidence and reduce risk in using hydrocarbon compositions from various or unknown sources in catalytic cracking.
  • previously underutilized and undervalued hydrocarbon products e.g. , lubricating oil, upgraded pyrolysis oil
  • One nonlimiting example embodiment is a method comprising: defining a set of disposition criteria comprising a plurality of measurable properties selected from the group consisting of boiling point range, specific gravity, total reactive sulfur, total nitrogen, basic nitrogen, S:N ratio, chlorine, acidity, coking tendency, aniline point, aromaticity, paraffin content, naphthenes, aliphatic unsaturation, sedimentation, water content, flash point, concentration of polychlorinated biphenyls, and the content of one or more of the following elements: S, Ni, V, Fe, Na, Cu, Ca, Si, B, P, Zn, Mg, Mo, K, Sn, Al, Cr, Ag, Ti, Sb, Pb, and Ba, wherein each of the measurable properties has associated therewith a pre-defined value; testing one or more samples of a potential catalytic cracking feedstock to generate a plurality of measured properties corresponding to the plurality of measurable properties, wherein each of the measured properties is characterized by a quantitative measured value; comparing each
  • the embodiment may include one or more of the following Elements: Element 1: the method wherein the potential catalytic cracking feedstock is derived from lubricating oil; Element 2: the method wherein the potential catalytic cracking feedstock comprises used lubricating oil; Element 3: the method wherein the potential catalytic cracking feedstock comprises re-refined used lubricating oil; Element 4: the method wherein the potential catalytic cracking feedstock comprises motor oil; Element 5: the method wherein the potential catalytic cracking feedstock comprises a product of biomass pyrolysis; Element 6: the method wherein the potential catalytic cracking feedstock comprises upgraded biocrude; Element 7: the method wherein the potential catalytic cracking feedstock comprises shale oil; Element 8: the method wherein the potential catalytic cracking feedstock comprises used lubricating oil that has been subjected to a re-refining process comprising acid washing; Element 9: the method wherein the potential catalytic cracking feed
  • Another nonlimiting example embodiment is a method comprising: defining a set of disposition criteria comprising a plurality of measurable properties selected from the group consisting of boiling point range, specific gravity, total reactive sulfur, total nitrogen, basic nitrogen, S:N ratio, chlorine, acidity, coking tendency, aniline point, aromaticity, paraffin content, naphthenes, aliphatic unsaturation, sedimentation, water content, flash point, concentration of polychlorinated biphenyls, and the content of one or more of the following elements: S, Ni, V, Fe, Na, Cu, Ca, Si, B, P, Zn, Mg, Mo, K, Sn, Al, Cr, Ag, Ti, Sb, Pb, and Ba, wherein each of the measurable properties has associated therewith a pre-defined value; testing one or more samples of a potential catalytic cracking feedstock to generate a plurality of measured properties corresponding to the plurality of measurable properties, wherein each of the measured properties is characterized by a quantitative measured value; comparing each of the
  • the embodiment may include one or more of the following Elements: Element 1, Element 2, Element 3, Element 4, Element 5, Element 6, Element 7, Element 8, Element 9, Element 10, Element 11, and Element 13: the method further comprising subjecting the potential catalytic cracking feedstock to one or more processes to modify the quantitative measured value prior to supplying the combined catalytic cracking feedstock to a catalytic cracking unit.
  • Examples of suitable combinations include, but are not limited to, Element 1 in combination with one or more of Elements 2-11 and 13; Element 2 in combination with one or more of Elements 3-11, and 13; Element 3 in combination with one or more of Elements 4-11 and 13; Element 4 in combination with one or more of Elements 5-11 and 13; Element 5 in combination with one or more of Elements 6-11 and 13; Element 6 in combination with one or more of Elements 7-11 and 13; Element 7 in combination with one or more of Elements 8-11 and 13; Element 8 in combination with one or more of Elements 9-11 and 13; Element 9 in combination with one or more of Elements 10 and 11; Element 10 in combination with one or more of Elements 11 and 13; and Element 11 in combination with Element 13.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne des procédés d'évaluation du potentiel de conversion d'huile lubrifiante, par exemple, d'huile lubrifiante usagée, par craquage catalytique, comprenant la soumission d'une charge d'alimentation de craquage catalytique potentielle à une pluralité d'essais pour générer une pluralité de propriétés mesurées caractérisées par une valeur mesurée quantitative, la comparaison de chaque valeur mesurée quantitative à chaque valeur prédéfinie ; l'identification de chaque propriété mesurée dont la valeur mesurée quantitative ne correspond pas à la valeur prédéfinie correspondante ; et, si des propriétés mesurées qui ne coïncident pas avec la valeur prédéfinie correspondante sont identifiées, a) le traitement de la charge d'alimentation de craquage catalytique potentielle pour modifier lesdites propriétés mesurées pour qu'elles coïncident avec la valeur prédéfinie ou b) la combinaison d'au moins une partie de la première charge d'alimentation de craquage catalytique potentielle avec au moins une partie d'une seconde charge d'alimentation de craquage catalytique potentielle pour générer une charge d'alimentation de craquage catalytique combinée.
PCT/US2020/042348 2019-08-09 2020-07-16 Procédé d'évaluation de charges d'hydrocarbures pour craquage catalytique WO2021030003A1 (fr)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US5817517A (en) * 1995-02-08 1998-10-06 Exxon Research And Engineering Company Method of characterizing feeds to catalytic cracking process units
US20080105595A1 (en) * 2006-10-20 2008-05-08 Saudi Arabian Oil Company Process for removal of nitrogen and poly-nuclear aromatics from hydrocracker and FCC feedstocks
US20160130510A1 (en) * 2011-07-15 2016-05-12 Robert H. Wombles Distillation of used motor oil with distillate vapors

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Publication number Priority date Publication date Assignee Title
US5817517A (en) * 1995-02-08 1998-10-06 Exxon Research And Engineering Company Method of characterizing feeds to catalytic cracking process units
US20080105595A1 (en) * 2006-10-20 2008-05-08 Saudi Arabian Oil Company Process for removal of nitrogen and poly-nuclear aromatics from hydrocracker and FCC feedstocks
US20160130510A1 (en) * 2011-07-15 2016-05-12 Robert H. Wombles Distillation of used motor oil with distillate vapors

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