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WO2005061668A2 - Systemes, procedes, et catalyseurs pour la production d'un produit brut - Google Patents

Systemes, procedes, et catalyseurs pour la production d'un produit brut Download PDF

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Publication number
WO2005061668A2
WO2005061668A2 PCT/US2004/042332 US2004042332W WO2005061668A2 WO 2005061668 A2 WO2005061668 A2 WO 2005061668A2 US 2004042332 W US2004042332 W US 2004042332W WO 2005061668 A2 WO2005061668 A2 WO 2005061668A2
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WO
WIPO (PCT)
Prior art keywords
crude
catalyst
crude feed
grams
crude product
Prior art date
Application number
PCT/US2004/042332
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English (en)
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WO2005061668A3 (fr
Inventor
Opinder Kishan Bhan
Scott Lee Wellington
Original Assignee
Shell Internationale Research Maatschappij B.V.
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34713792&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2005061668(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP04814508A priority Critical patent/EP1702033A2/fr
Priority to JP2006545449A priority patent/JP2007514837A/ja
Publication of WO2005061668A2 publication Critical patent/WO2005061668A2/fr
Publication of WO2005061668A3 publication Critical patent/WO2005061668A3/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/04—Metals, or metals deposited on a carrier
    • 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
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic 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
    • 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
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203—Naphthenic acids, TAN
    • 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
    • C10G2300/205—Metal content

Definitions

  • Disadvantaged crudes may include acidic components that contribute to the total acid number ("TAN") of the crude feed.
  • Disadvantaged crudes with a relatively high TAN may contribute to corrosion of metal components during transporting and/or processing of the disadvantaged crudes.
  • Removal of acidic components from disadvantaged crudes may involve chemically neutralizing acidic components with various bases.
  • corrosion-resistant metals may be used in transportation equipment and/or processing equipment. The use of corrosion-resistant metal often involves significant expense, and thus, the use of corrosion-resistant metal in existing equipment may not be desirable.
  • Another method to inhibit corrosion may involve addition of corrosion inhibitors to disadvantaged crudes before transporting and/or processing of the disadvantaged crudes.
  • inventions described herein generally relate to systems, methods and catalysts for conversion of a crude feed to a total product comprising a crude product and, in some embodiments, non-condensable gas. Inventions described herein also generally relate to compositions that have novel combinations of components therein. Such compositions can be obtained by using the systems and methods described herein.
  • the invention also provides a method of producing a catalyst, comprising: combining a support with one or more metals to form a support/metal mixture, wherein the support comprises theta alumina, and one or more of the metals comprising one or more metals from Column 5 of the Periodic Table, one or more compounds of one or more metals from Column 5 of the Periodic Table, or mixtures thereof; heat treating the theta alumina support/metal mixture at a temperature of at least 400 °C; and forming the catalyst, wherein the catalyst has a pore size distribution with a median pore diameter of at least 230 A, as determined by ASTM Method D4282.
  • the invention also provides a method of producing a catalyst, comprising: combining a support with one or more metals to form a support/metal mixture, wherein the support comprises theta alumina, and one or more of the metals comprising one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table, or mixtures thereof; heat treating the theta alumina support/metal mixture at a temperature of at least 400 °C; and forming the catalyst, wherein the catalyst has a pore size distribution with a median pore diameter of at least 230 A, as determined by ASTM Method D4282.
  • the invention also provides a method of producing a crude product, comprising: contacting a crude feed with one or more catalysts in the presence of a hydrogen source to produce a total product that includes the crude product, wherein the crude product is a liquid mixture at 25 °C and 0.101 MPa, the crude feed having a TAN of at least 0.1, the crude feed having a sulfur content of at least 0.0001 grams of sulfur per gram of crude feed, and at least one of the catalysts comprising one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table, or mixtures thereof; and controlling contacting conditions such that, during contacting, the crude feed uptakes molecular hydrogen at a selected rate to inhibit phase separation of the crude feed during contacting, liquid hourly space velocity in one or more contacting zones is over 10 h "1 , the crude product having a TAN of at most 90% of the TAN of the crude feed, and the crude product having a sulfur content of 70-130% of the sulfur content
  • the invention also provides a method of producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product that includes the crude product, wherein the crude product is a liquid mixture at 25 °C and 0.101 MPa, the crude feed having a viscosity of at least 10 cSt at 37.8 °C (100 °F), the crude feed having an API gravity of at least 10, and at least one of the catalysts comprising one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table, or mixtures thereof; and controlling contacting conditions such that the crude product has a viscosity at 37.8 °C of at most 90% of the viscosity of the crude feed at 37.8 °C, and the crude product having an API gravity of 70-130% of the API gravity of the crude feed, wherein API gravity is as determined by ASTM Method D6822, and viscosity is as determined by ASTM Method D2669.
  • the invention also provides a method of producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product that mcludes the crude product, wherein the crude product is a liquid mixture at 25 °C and 0.101 MPa, the crude feed having a TAN of at least 0.1, and at least one of the catalysts comprising vanadium, one or more compounds of vanadium, or mixtures thereof; providing a gas comprising a hydrogen source during contacting, the gas flow being provided in a direction that is counter to the flow of the crude feed; and controlling contacting conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is as determined by ASTM Method D664.
  • the invention also provides a method of producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product that includes the crude product, wherein the crude product is a liquid mixture at 25 °C and 0.101 MPa, the crude feed comprising one or more alkali metal salts of one or more organic acids, one or more alkaline-earth metal salts of one or more organic acids, or mixtures thereof, the crude feed having, per gram of crude feed, a total content of alkali metal, and alkaline- earth metal, in metal salts of organic acids of at least 0.00001 grams, and a residue content of at least 0.1 grams of residue, and at least one of the catalysts comprising one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table, or mixtures thereof; and controlling contacting conditions such that the crude product has a total content of alkali metal, and alkaline-earth metal, in metal salts of organic acids of at most
  • the invention also provides a method of producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product that includes the crude product, wherein the crude product is a liquid mixture at 25 °C and 0.101 MPa, the crude feed comprising one or more alkali metal salts of one or more organic acids, one or more alkaline-earth metal salts of one or more organic acids, or mixtures thereof, the crude feed having, per gram of crude feed, a vacuum gas oil (“VGO") content of at least 0.1 grams, and a total content of alkali metal, and alkaline-earth metal, in metal salts of organic acids of 0.0001 grams, and at least one of the catalysts comprises one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table, or mixtures thereof; and controlling contacting conditions such that the crude product has a total content of alkali metal, and alkaline-earth metal, in metal salts of organic acids of
  • the invention also provides, in combination with one or more of the methods or compositions according to the invention, a method that comprises contacting a crude feed with one or more catalysts to produce a total product that includes a crude product, the method further comprising: (a) combining the crude product with a crude that is the same or different from the crude feed to form a blend suitable for transporting; (b) combining the crude product with a crude that is the same or different from the crude feed to form a blend suitable for treatment facilities; (c) fractionating the crude product; and/or (d) fractionating the crude product into one or more distillate fractions, and producing transportation fuel from at least one of the distillate fractions.
  • Pore diameter refers to pore diameter, median pore diameter, and pore volume, as determined by ASTM Method D4284 (mercury porosimetry at a contact angle equal to 140°).
  • a micromeritics ® A9220 instrument may be used to determine these values.
  • Residue refers to components that have a boiling range distribution above 538 °C (1000 °F), as determined by ASTM Method D5307.
  • SCFB refers to standard cubic feet of gas per barrel of crude feed.
  • Surface area of a catalyst is as determined by ASTM Method D3663.
  • TAN refers to a total acid number expressed as milligrams ("mg") of KOH per gram ("g") of sample. TAN is as determined by ASTM Method D664.
  • VGO refers to hydrocarbons with a boiling range distribution between 343 °C (650 °F) and 538 °C (1000 °F) at 0.101 MPa. VGO content is as determined by ASTM Method D5307.
  • Viscosity refers to kinematic viscosity at 37.8 °C (100 °F). Viscosity is as determined using ASTM Method D445.
  • Stabilized crudes typically have not been distilled and/or fractionally distilled in a treatment facility to produce multiple components with specific boiling range distributions (for example, naphtha, distillates, VGO, and/or lubricating oils).
  • Distillation includes, but is not limited to, atmospheric distillation methods and/or vacuum distillation methods.
  • Undistilled and/or unfractionated stabilized crudes may include components that have a carbon number above 4 in quantities of at least 0.5 grams of components per gram of crude. Examples of stabilized crudes include whole crudes, topped crudes, desalted crudes, desalted topped crudes, or combinations thereof.
  • TAN, viscosity, Ni/N/Fe content, heteroatoms content, residue content, API gravity, or combinations of these properties of the crude product change by at least 10% relative to the same properties of the crude feed after contact of the crude feed with one or more catalysts.
  • a volume of catalyst in the contacting zone is in a range from 10-60 vol%, from 20-50 vol%, or from 30-40 vol% of a total volume of crude feed in the contacting zone.
  • a ratio of the gaseous hydrogen source to the crude feed typically ranges from 0.1-100,000 Nm 3 /m 3 , 0.5-10,000 Nm 3 /m 3 , 1-8,000 NmW, 2-5,000 Nm 3 /m 3 , 5-3,000 Nm 3 /m 3 , or 10-800 Nm 3 /m 3 contacted with the catalyst(s).
  • the hydrogen source in some embodiments, is combined with carrier gas(es) and recirculated through the contacting zone.
  • Carrier gas may be, for example, nitrogen, helium, and/or argon. The carrier gas may facilitate flow of the crude feed and/or flow of the hydrogen source in the contacting zones(s).
  • Product specifications include, but are not limited to, a range of or a limit of API gravity, TAN, viscosity, or combinations thereof.
  • the blended product exits blending zone 130 via conduit 134 to be transported or processed.
  • the disadvantaged crude enters separation zone 120 through conduit 122, and the disadvantaged crude is separated as previously described to form the crude feed.
  • the crude feed then enters contacting system 100 through conduit 126. At least some components from the disadvantaged crude exit separation zone 120 via conduit 124. At least a portion of the crude product exits contacting system 100 and enters blending zone 130 through conduit 128.
  • Other process streams and/or crudes enter blending zone 130 directly or via conduit 132 and are combined with the crude product to form a blended product.
  • the oxygen content of the crude product may be at most 90%, at most 50%, at most 30%, at most 10%, or at most 5% of the oxygen content of the crude feed.
  • the crude product has an oxygen content of at least 1%, at least 30%, at least 80%, or at least 99% of the oxygen content of the crude feed.
  • the oxygen content of the crude product is in a range from 1-80%, 10- 70%, 20-60%, or 30-50% of the oxygen content of the crude feed.
  • the total content of carboxylic acid compounds of the crude product may be at most 90%, at most 50%, at most 10%, at most 5% of the content of the carboxylic acid compounds in the crude feed.
  • the crude product has a MCR content of 70-130%, 80- 120%, or 90-110% of the MCR content of the crude feed, while the crude product has a C 5 asphaltenes content of at most 90%, at most 80%, or at most 50% of the C 5 asphaltenes content of the crude feed.
  • the G 5 asphaltenes content of the crude feed is at least 10%, at least 60%, or at least 70% of the C 5 asphaltenes content of the crude feed while the MCR content of the crude product is within 10-30% of the MCR content of the crude feed.
  • decreasing the C 5 asphaltenes content of the crude feed while maintaining a relatively stable MCR content may increase the stability of the crude feed/total product mixture.
  • Catalysts used in one or more embodiments of the inventions may include one or more bulk metals and/or one or more metals on a support.
  • the metals may be in elemental form or in the form of a compound of the metal.
  • the catalysts described herein may be introduced into the contacting zone as a precursor, and then become active as a catalyst in the contacting zone (for example, when sulfur and/or a crude feed containing sulfur is contacted with the precursor).
  • the catalyst or combination of catalysts used as described herein may or may not be commercial catalysts.
  • a theta alumina support may be combined with Columns 5-10 metals to form a theta alumina support/Columns 5-10 metals mixture.
  • the theta alumina support/Columns 5-10 metals mixture may be heat treated at a temperature of at least 400 °C to form the catalyst having a pore size distribution with a median pore diameter of at least 230 A. Typically, such heat treating is conducted at temperatures of at. most 1200 °C.
  • the Column 6 metal(s) are substantially randomly ordered in the crystal structure.
  • molybdenum trioxide and the alumina support having a median pore diameter of at least 180 A may be combined to form an alumina/molybdenum trioxide mixture.
  • the molybdenum trioxide has a definite pattern (for example, definite Dooi, D 002 and/or D 003 peaks).
  • the catalyst has a pore size distribution with a median pore diameter in a range from 180-500 A, 200-400 A, or 230-300 A, with at least 60% of a total number of pores in the pore size distribution having a pore diameter within 50 A, 70 A, or 90 A of the median pore diameter.
  • pore volume of pores may be at least 0.3 cm /g, at least 0.7 cm 3 /g or at least 0.9 cm 3 /g. In certain embodiments, pore volume of pores may range from 0.3-0.99 cm 3 /g, 0.4-0.8 cm 3 /g, or 0.5-0.7 cm 3 /g.
  • the first catalyst is capable of removing a portion of the Ni/N/Fe from a crude feed, removing a portion of the components that contribute to TAN of a crude feed, removing at least a portion of the C 5 asphaltenes from a crude feed, removing at least a portion of the metals in metal salts of organic acids in the crude feed, or, combinations thereof.
  • Other properties for example, sulfur content, NGO • content, API gravity, residue content, or combinations thereof
  • Being able to selectively change properties of a crude feed while only changing other properties in relatively small amounts may allow the crude feed to be more efficiently treated.
  • one or more first catalysts may be used in any order.
  • the second type of catalyst (“second catalyst”) includes Columns 5-10 metal(s) in combination with a support, and has a pore size distribution with a median pore diameter in a range from 90 A to 180 A. At least 60% of the total number of pores in the pore size distribution of the second catalyst have a pore diameter within 45 A of the median pore diameter.
  • Contact of the crude feed with the second catalyst under suitable contacting conditions may produce a crude product that has selected properties (for example, TAN) significantly changed relative to the same properties of the crude feed while other properties are only changed by a small amount.
  • a hydrogen source in some embodiments, may be present during contacting.
  • the catalyst precursor may be heated in the presence of one or more sulfur containing compounds at a temperature below 500 °C (for example, below 482 °C) for a relatively short period of time to form the uncalcined third catalyst.
  • the catalyst precursor is heated to at least 100 °C for 2 hours.
  • the third catalyst may, per gram of catalyst, have a Column 15 element content in a range from 0.001-0.03 grams, 0.005-0.02 grams, or 0.008-0.01 grams.
  • the third catalyst may exhibit significant activity and stability when used to treat the crude feed as described herein.
  • the catalyst precursor is heated at temperatures below 500 °C in the presence of one or more sulfur compounds.
  • the third catalyst may reduce at least a portion of the components that contribute to the TAN of the crude feed, reduce at least a portion of the metals in metal salts of organic acids, reduce a NiN/Fe content of the crude product, and reduce the viscosity of the crude product. Additionally, contact of crude feeds with the third catalyst may produce a crude product with a relatively small change in the sulfur content relative to the sulfur content of the crude feed and with relatively minimal net hydrogen uptake by the crude feed. For example, a crude product may have a sulfur content of 70%- 130% of the sulfur content of the crude feed.
  • the crude product produced using the third catalyst may also exhibit relatively small changes in API gravity, distillate content, NGO content, and residue content relative to the crude feed.
  • the ability to reduce the TAN, the metals in metal salts of organic salts, the NiN/Fe content, and the viscosity of the crude product while also only changing by a small amount the API gravity, distillate content, NGO content, and residue contents relative to the crude feed, may allow the crude product to be used by a variety of treatment facilities .
  • the third catalyst in some embodiments, may reduce at least a portion of the MCR content of the crude feed, while maintaining crude feed/total product stability.
  • the order and/or number of catalysts may be selected to minimize net hydrogen uptake while maintaining the crude feed/total product stability.
  • Minimal net hydrogen uptake allows residue content, VGO content, distillate content, API gravity, or combinations thereof of the crude feed to be maintained within 20% of the respective properties of the crude feed, while the TAN and/or the viscosity of the crude product is at most 90% of the TAN and/or the viscosity of the crude feed.
  • Reduction in net hydrogen uptake by the crude feed may produce a crude product that has a boiling range distribution similar to the boiling point distribution of the crude feed, and a reduced TAN relative to the TAN of the crude feed.
  • the atomic H/C of the crude product may also only change by relatively small amounts as compared to the atomic H/C of the crude feed.
  • Such controlling of contacting conditions may include controlling LHSV, temperature, pressure, hydrogen uptake, crude feed flow, or combinations thereof.
  • contacting temperatures are controlled such that C 5 asphaltenes and/or other asphaltenes are removed while maintaining the MCR content of • the crude feed. Reduction of the MCR content through hydrogen uptake arid/or higher contacting temperatures may result in formation of two phases that may reduce the stability of the crude feed/total product mixture and/or life of one or more of the catalysts. Control of contacting temperature and hydrogen uptake in combination with the catalysts described herein allows the C 5 asphaltenes to be reduced while the MCR content of the crude feed only changes by a relatively small amount.
  • Temperatures of the three contacting zones were then increased and maintained in the following sequence: 379 °C (715 °F) for 500 hours, and then 388 °C (730 °F) for 500 hours, then 390 °C (734 °F) for 1800 hours, and then 394 °C (742 °F) for 2400 hours.
  • the total product (that is, the crude product and gas) exited the catalyst bed.
  • the total product was introduced into a gas-liquid phase separator. In the gas-liquid separator, the total product was separated into the crude product and gas. Gas input to the system was measured by a mass flow controller. Gas exiting the system was measured by a wet test meter.
  • the crude product was periodically analyzed to determine a weight percentage of components of the crude product.
  • FIG. 12 is a graphical representation of P-value of the crude product ("P") versus run time ("t") for each of the catalyst systems of Examples 8-11.
  • the crude feed had a P- value of at least 1.5.
  • Plots 140, 142, 144, and 146 represent the P-value of the crude product obtained by contacting the crude feed with the four catalyst systems of Examples 8-11 respectively. For 2300 hours, the P-value of the crude product remained of at least 1.5 for catalyst systems of Examples 8-10.
  • Plots 148, 150 152, 154 represent net hydrogen uptake obtained by contacting the crude feed with each of the catalyst systems of Examples 8-11, respectively.
  • Net hydrogen uptake by a crude feed over a run time period of 2300 hours was in a range between 7-48 Nm /m (43.8-300 SCFB).
  • the net hydrogen uptake of the crude feed was relatively constant during each trial.
  • FIG. 14 is a graphical representation of residue content, expressed in weight percentage, of crude product ("R") versus run time ("t") for each of the catalyst systems of Examples 8-11. In each of the four trials, the crude product had a residue content of 88- 90% of the residue content of the crude feed.
  • Example 12 net hydrogen uptake was -10.7 Nm 3 /m 3 (-65 SCFB), and the crude product had a TAN of 6.75.
  • Example 13 net hydrogen uptake was in a range from 2.2- 3.0 NmV (13.9-18.7 SCFB), and the crude product had a TAN in a range from 0.3-0.5.
  • Example 14 during contacting of the crude feed with the molybdenum/vanadium catalyst, net hydrogen uptake was in a range from -0.05 Nm 3 /m 3 to 0.6 N Vm 3 (-0.36 SCFB to 4.0 SCFB), and the crude product had a TAN in a range from 0.2-0.5.
  • Examples 15-18 Contact of a Crude Feed With a Vanadium Catalyst and an Additional Catalyst.
  • Each reactor apparatus except for number and content of contacting zones), each catalyst sulfiding method, each total product separation method, and each crude product analysis were the same as described in Example 5. All catalysts were mixed with silicon carbide in a volume ratio of 2 parts silicon carbide to 1 part catalyst unless otherwise indicated.
  • the crude feed flow to each reactor was from the top of the reactor to the bottom of the reactor. Silicon carbide was positioned at the bottom of each reactor to serve as a bottom support. Each reactor had a bottom contacting zone and a top contacting zone.
  • Example 16 an additional catalyst/silicon carbide mixture (30 cm ) was positioned in the bottom contacting zone, with the additional catalyst being the molybdenum catalyst prepared by the method described in Example 3.
  • the vanadium catalyst/silicon carbide mixture (30 cm 3 ) was positioned in the top contacting zone.
  • Example 17 an additional catalyst/silicone mixture (30 cm ) was positioned in the bottom contacting zone, with the additional catalyst being the molybdenum vanadium catalyst as prepared in Example 4.
  • the vanadium catalyst/silicon carbide mixture (30 cm 3 ) was positioned in the top contacting zone.
  • Pyrex ® Glass Works Corporation, New York, U.S.A.
  • Examples 19 Contact of a Crude Feed at Various LHSV.
  • the contacting systems and the catalysts were the same as described in Example 6.
  • the properties of the crude feeds are listed in Table 6 in FIG. 18.
  • the contacting conditions were as follows: a ratio of hydrogen gas to the crude feed provided to the reactor was 160 ⁇ m /m (1000 SCFB), pressure was 6.9 MPa (1014.7 psi), and temperature of the contacting zones was 371 °C (700 °F) for the total run time.
  • Example 20 Contact of a Crude Feed at Various Contacting Temperatures.
  • the contacting systems and the catalysts were the same as described in Example 6.
  • the crude feed having the properties listed in Table 7 in FIG. 19 was added to the top of the reactor and contacted with the two catalysts in the two contacting zones in the presence of hydrogen to produce a crude product.
  • the two contacting zones were operated at different temperatures. . ⁇ ; • Contacting conditions in the top contacting zone were as follows: LHSV was 1 h "1 ; temperature in the top contacting zone was 260 °C (500 °F); a ratio of hydrogen to crude feed was 160 NmV (1000 SCFB); and pressure was 6.9 MPa (1014.7 psi).
  • a bulk metal catalyst and/or a catalyst of the application may, in some embodiments, be slurried with the crude feed and reacted under the following conditions: temperature in a range from 85-425 °C (185- 797 °F), pressure in a range from 0.5-10 MPa, and ratio of hydrogen source to crude feed of 16-1600 NmV for a period of time.
  • a separation apparatus such as a filter and/or centrifuge.

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Abstract

La présente invention a trait à un procédé dans lequel la mise en contact d'une charge brute avec un ou des catalyseurs produit un produit total comportant un produit brut. Le produit brut est un mélange liquide à 25 °C et 0,101 MPa. Une ou des propriété(s) du produit brut peut/peuvent être modifiée(s) par rapport aux propriétés respectives de la charge brute.
PCT/US2004/042332 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut WO2005061668A2 (fr)

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EP04814508A EP1702033A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
JP2006545449A JP2007514837A (ja) 2003-12-19 2004-12-16 原油生成物を製造するためのシステム、方法及び触媒

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PCT/US2004/042429 WO2005061670A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042309 WO2005061666A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs permettant de produire un produit brut
PCT/US2004/042338 WO2005063926A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs utiles pour produire un produit brut
PCT/US2004/042343 WO2005063927A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs utiles pour produire un produit brut
PCT/US2004/042655 WO2005063937A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs permettant de produire un produit brut
PCT/US2004/042224 WO2005066310A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042426 WO2005061669A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042333 WO2005063925A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs destines a produire un produit brut
PCT/US2004/042125 WO2005065189A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs destines a la production d'un produit brut
PCT/US2004/042310 WO2005061667A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042241 WO2005063924A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs pour la production d'un produit brut
PCT/US2004/042332 WO2005061668A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042651 WO2005063934A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs pour obtenir un produit brut
PCT/US2004/042137 WO2005066306A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs pour la fabrication de produits bruts
PCT/US2004/042653 WO2005063935A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs permettant de produire un produit brut
PCT/US2004/042432 WO2005063931A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs destines a produire un produit brut
PCT/US2004/042640 WO2005063933A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042427 WO2005063930A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs destines a produire un produit brut
PCT/US2004/042139 WO2005066307A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042225 WO2005066311A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042088 WO2005066301A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs de production d'un produit brut
PCT/US2004/042399 WO2005063929A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs pour obtenir un produit brut
PCT/US2004/042656 WO2005063938A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs permettant de produire un produit brut
PCT/US2004/042647 WO2005061678A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs de production de produit brut
PCT/US2004/042121 WO2005066303A2 (fr) 2003-12-19 2004-12-16 Systemes, produits et catalyseurs destines a la production d'un produit brut
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PCT/US2004/042429 WO2005061670A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042309 WO2005061666A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs permettant de produire un produit brut
PCT/US2004/042338 WO2005063926A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs utiles pour produire un produit brut
PCT/US2004/042343 WO2005063927A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs utiles pour produire un produit brut
PCT/US2004/042655 WO2005063937A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs permettant de produire un produit brut
PCT/US2004/042224 WO2005066310A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042426 WO2005061669A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042333 WO2005063925A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs destines a produire un produit brut
PCT/US2004/042125 WO2005065189A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs destines a la production d'un produit brut
PCT/US2004/042310 WO2005061667A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
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PCT/US2004/042137 WO2005066306A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs pour la fabrication de produits bruts
PCT/US2004/042653 WO2005063935A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs permettant de produire un produit brut
PCT/US2004/042432 WO2005063931A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs destines a produire un produit brut
PCT/US2004/042640 WO2005063933A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042427 WO2005063930A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs destines a produire un produit brut
PCT/US2004/042139 WO2005066307A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042225 WO2005066311A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes, et catalyseurs pour la production d'un produit brut
PCT/US2004/042088 WO2005066301A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs de production d'un produit brut
PCT/US2004/042399 WO2005063929A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs pour obtenir un produit brut
PCT/US2004/042656 WO2005063938A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs permettant de produire un produit brut
PCT/US2004/042647 WO2005061678A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs de production de produit brut
PCT/US2004/042121 WO2005066303A2 (fr) 2003-12-19 2004-12-16 Systemes, produits et catalyseurs destines a la production d'un produit brut
PCT/US2004/042430 WO2005063939A2 (fr) 2003-12-19 2004-12-16 Systemes, procedes et catalyseurs destines a produire un produit brut

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