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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used

Definitions

• This invention relates to the hydroconversion of heavy hydrocarbon oils. More particularly it relates to a hydrotreating catalyst system which permits operation to yield increased conversion of 1000°F+ charge to lower boiling products.
• USP 4,579,646 discloses a bottoms visbreaking hydroconversion process wherein hydrocarbon charge is partially coked, and the coke is contacted within the charge stock with an oil-soluble metal compound of a metal of Group IV-B, V-B, VII-B, or VIII to yield a hydroconversion catalyst.
• USP 4,724,069 discloses hydrofining in the presence of a supported catalyst bearing a VI-B, VII-B, or VIII metal on alumina, silica, or silica-alumina. There is introduced with the charge oil, as additive, a naphthenate of Co or Fe.
• USP 4,567,156 discloses hydroconversion in the presence of a chromium catalyst prepared by adding a water-soluble aliphatic polyhydroxy compound (such as glycerol) to an aqueous solution of chromic acid, adding a hydrocarbon thereto, and heating the mixture in the presence of hydrogen sulfide to yield a slurry.
• a chromium catalyst prepared by adding a water-soluble aliphatic polyhydroxy compound (such as glycerol) to an aqueous solution of chromic acid, adding a hydrocarbon thereto, and heating the mixture in the presence of hydrogen sulfide to yield a slurry.
• USP 4,564,441 discloses hydrofining in the presence of a decomposable compound of a metal (Cu, Zn, III-B, IV-B, VI-B, VII-B, or VIII) mixed with a hydrocarbon-containing feed stream; and the mixture is then contacted with a "suitable refractory inorganic material" such as alumina.
• USP 4,557,823 discloses hydrofining in the presence of a decomposable compound of a IV-B metal and a supported catalyst containing a metal of VI-B, VII-B, or VIII.
• USP 4,557,824 discloses demetallization in the presence of a decomposable compound of a VI-B, VII-B, or VIII metal admitted with the charge and a heterogeneous catalyst containing a phosphate of Zr, Co, or Fe.
• USP 4,551,230 discloses demetallization in the presence of a decomposable compound of a IV-B, V-B, VI-B, VII-B, or VIII metal admitted with the charge and a heterogeneous catalyst containing NiAs x on alumina.
• USP 4,430,207 discloses demetallization in the presence of a decomposable compound of a V-B, VI-B, VII-B, or VIII metal admitted with the charge and a heterogeneous catalyst containing a phosphate of Zr or Cr.
• USP 4,389,301 discloses hydroprocessing in the presence of added dispersed hydrogenation catalyst (typically ammonium molybdate) and added porous contact particles (typically FCC catalyst fines, alumina, or naturally occurring clay).
• USP 4,352,729 discloses hydrotreating in the presence of a molybdenum blue solution in polar organic solvent introduced with the hydrocarbon charge.
• USP 4,338,183 discloses liquefaction of coal in the presence of unsupported finely divided metal catalyst.
• USP 4,298,454 discloses hydroconversion of a coal-oil mixture in the presence of a thermally decomposable compound of a IV-B, V-B, VI-B VII-B, or VIII metal, preferably Mo.
• USP 4,134,825 discloses hydroconversion of heavy hydrocarbons in the presence of an oil-soluble compound of IV-B, V-B, VI-B, VII-B, or VIII metal added to charge, the compound being converted to solid, non-colloidal form by heating in the presence of hydrogen.
• USP 4,125,455 discloses hydrotreating in the presence of a fatty acid salt of a VI-B metal, typically molybdenum octoate.
• USP 4,077,867 discloses hydroconversion of coal in the presence of oil-soluble compound of V-B, VI-B, VII-B, or VIII metal plus hydrogen donor solvent.
• USP 4,067,799 discloses hydroconversion in the presence of a metal phthalocyanine plus dispersed iron particles.
• USP 4,066,530 discloses hydroconversion in the presence of (i) an iron component and (ii) a catalytically active other metal component prepared by dissolving an oil-soluble metal compound in the oil and converting the metal compound in the oil to the corresponding catalytically active metal component.
• this invention is directed to a method of catalytically hydroconverting a charge hydrocarbon oil containing a substantial quantity of components boiling above about 1000°F to convert a substantial portion thereof to components boiling below 1000°F which comprises passing said charge hydrocarbon oil containing a substantial quantity of components boiling above about 1000°F into contact with (i) a solid heterogeneous catalyst containing, as a hydrotreating component, a metal of Group IV-B, V-B, VI-B, VII-B, or VIII on a support and (ii) as an oil-soluble catalyst a compound of a metal of Group IV-B, V-B, VI-B, VII-B or VIII in a conversion zone; maintaining said charge hydrocarbon oil containing a substantial quantity of components boiling above about 1000°F in said conversion zone at conversion conditions in the presence of hydrogen and mercaptan as a substantial portion of said components boiling above about 1000°F are converted to components boiling below 1000°F thereby forming product containing a substantial portion of components boiling below about 1000°F
• the charge which may be treated by the process of this invention may include high boiling hydrocarbons typically those having an initial boiling point (ibp) above about 650°F. This process is particularly useful to treat charge hydrocarbons containing a substantial quantity of components boiling above about 1000°F to convert a substantial portion thereof to components boiling below 1000°F .
• Typical of these streams are heavy crude oil, topped crude, vacuum resid, asphaltenes, tars, coal liquids, visbreaker bottoms, etc.
• Illustrative of such charge streams may be a vacuum resid obtained by blending vacuum resid fractions from Alaska North Slope Crude (59v%), Arabian Medium Crude (5v%), Arabian Heavy Crude (27%), and Bonny Light Crude (9v%) having the characteristics listed in Table I:
• charge hydrocarbons that they contain undesirable components typified by nitrogen (in amount up to 1w%, typically 0.2-0.8w%, say about 0.52w%), sulfur (in amount up to 10w%, typically 2-6w%, say about 3.64w%), and metals including Ni, V, Fe, Cr, Na, etc. in amounts up to 900 wppm, typically 40-400 wppm, say 198 wppm).
• the undesirable asphaltene content of the charge hydrocarbon may be as high as 22w%, typically 8-16w%, say 11.97w% (analyzed as components insoluble in normal heptane).
• the API gravity of the charge may be as low as minus 5, typically minus 5 - plus 35, say about 5.8.
• the content of components boiling above about 1000°F may be as high as 100w%, typically 50-98+w%, say 93.1w%.
• the Alcor MCR Carbon content may be as high as 30w%, typically 15-25w%, say 19.86%.
• the charge hydrocarbon oil may be passed to a hydroconversion operation wherein conversion occurs in liquid phase at conversion conditions including 700°F-850°F, preferably about 750°F-810°F, say 800°F at hydrogen partial pressure of about 500-5000 psig, preferably about 1500-2500 psig, say 2000 psig.
• hydrocarbon oil there is added to the charge hydrocarbon oil (preferably prior to admission to hydroconversion) a catalytically effective amount of an oil-miscible, preferably an oil-soluble catalyst compound of a metal of Group IV-B, V-B, VI-B, VII-B or VIII of the Periodic Table.
• the metal when it is a Group IV metal, it may be titanium (Ti), Zirconium (Zr) or hafnium (Hf).
• the metal when it is a Group V metal, it may be vanadium (V), niobium (Nb), or tantalum (Ta).
• the metal when it is a Group VI metal, it may be chromium (Cr), molybdenum (Mo), or tungsten (W).
• the metal when it is a Group VII metal, it may be manganese (Mn) or rhenium (Re).
• the metal when it is a Group VIII metal, it may be a non-noble metal such as iron (Fe), cobalt (Co), or nickel (Ni) or a noble metal such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), or platinum (Pt).
• a non-noble metal such as iron (Fe), cobalt (Co), or nickel (Ni) or a noble metal such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), or platinum (Pt).
• the metal is a Group VI metal - most preferably molybdenum (Mo).
• the compound of the metal is an oil-soluble compound typified by:
• the preferred compounds may be cobalt naphthenate, molybdenum hexacarbonyl, molybdenum naphthenate, and molybdenum octoate.
• the impact of the oil-soluble compound may be augmented by use of compounds of more than one metal.
• molybdenum e.g. as the naphthenate
• cobalt e.g. as the naphthenate
• cobalt may be added in amount of 0.2-2 moles, say 0.4 moles per mole of molybdenum.
• the metal compounds to be employed are oil-miscible and preferably oil-soluble i.e. they are soluble in the charge hydrocarbon oil in amount of at least 0.01g/100g typically 0.025-0.25g/100g, say about 0.1g/100g or alternatively they are readily dispersable in the charge hydrocarbon oil in amount of at least those amounts. It is also a feature of these metal compounds that, when activated as hereinafter set forth, the activated compounds are also oil-miscible in the hydrocarbon oils with which they come into contact during practice of the method of this invention.
• Activation of the oil-miscible compound derived from a metal of Group IV-B, V-B, VI-B, VII-B, or VIII in accordance with practice of the process of this invention may be effected either by pre-treatment (prior to hydroconversion) or in situ (during hydroconversion). It is preferred to effect activation in situ in the presence of the hydrogenation catalyst to achieve a highly dispersed catalytic species.
• Activation according to the preferred method may be carried out by adding 10-200 wppm, say 30 parts of metal compound to charge hydrocarbon at 60°F-300°F, say 200°F.
• the mixture is activated by heating to 400°F-835°F, typically 500°F-700°F, say 600°F at partial pressure of hydrogen of 500-5000 psig, typically 1000-3000 psig, say 2000 psig and at partial pressure of a gaseous mercaptan of 5-500 psig, typically 10-300 psig, say 50 psig.
• Total pressure may be 500-5500 psig, typically 1000-3300 psig, say 2050 psig.
• the gas may contain 40-99v%, typically 90-99v%, say 98v% hydrogen and 1-10v%, say 2v% mercaptan such as hydrogen sulfide.
• Time of activation may be 1-12, typically 2-6, say 3 hrs.
• activation may occur at temperature which is lower than the temperature of conversion.
• the mercaptans which may be employed may include hydrogen sulfide, aliphatic mercaptans, typified by methyl mercaptan, lauryl mercaptan, etc. aromatic mercaptans; dimethyl disulfide, carbon disulfide, etc.
• the sulfur content of the charge hydrocarbon is above about 2w%, it may not be necessary to add a mercaptan during activation i.e. hydrodesulfurization of the charge may provide enough mercaptan to properly activate (i.e. sulfide) the oil-miscible decomposable catalyst.
• the oil-miscible metal compound may be activated in the presence of an oil which is compatible with the charge oil i.e. a separate portion of the charge oil or a different oil which is compatible with the charge oil.
• the oil-miscible metal compound may be added to the oil in amount which is substantially greater (e.g. 2-20 times) than is the case when the compound is activated in the presence of the charge stream.
• the compatible oil containing the now activated metal may be admitted to the charge stream in amount sufficient to provide therein activated oil-miscible metal compound in desired amount.
• activation may be carried out by subjecting the charge hydrocarbon oil containing the oil-miscible metal compound to hydroconversion conditions including temperature of 700°F-850°F, preferably about 750°F-810°F, say 800°F at hydrogen partial pressure of about 500-5000 psig, preferably about 1500-2000 psig, say 2000 psig - in the presence of a mercaptan but in the absence of heterogeneous hydroconversion catalyst.
• activation may be carried out during hydroconversion i.e. in the presence of the heterogeneous, hydroconversion catalyst, hydrogen, and mercaptan.
• Hydroconversion is carried out in the presence of solid heterogeneous catalyst containing, as a hydrogenating component, a metal of Group IV-B, V-B, VI-B, VII-B, or VIII on a support which may typically contain carbon or an oxide of aluminum, silicon, titanium, magnesium, or zirconium.
• a metal of Group VI-B and VIII - typically nickel and molybdenum.
• the metal when it is a group IV-B metal, it may be titanium (Ti), zirconium (Zr), or hafnium (Hf).
• the metal when it is a Group V-B metal, it may be vanadium (V), niobium (Nb), or tantalum (Ta).
• the metal when it is a Group VI-B metal, it maybe chromium (Cr), molybdenum (Mo), or tungsten (W).
• the metal when it is a Group VII-B metal, it maybe manganese (Mn) or rhenium (Re).
• the metal when it is a Group VIII metal, it may be a non-noble metal such as iron (Fe), cobalt (Co), or nickel (Ni) or a noble metal such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), or platinum (Pt).
• a non-noble metal such as iron (Fe), cobalt (Co), or nickel (Ni) or a noble metal such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), or platinum (Pt).
• the solid heterogeneous catalyst may also contain, as a promoter, a metal of Groups I-A, I-B, II-A, II-B, or V-A.
• the promoter is a metal of Group I-A, it may preferably be sodium (Na) or potassium (K).
• the promoter is a metal of Group IB, it may preferably be copper (Cu).
• the promoter when it is a metal of Group II-A, it may be beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), or radium (Ra).
• the promoter when it is a metal of Group II-B, it may be zinc (Zn), cadmium (Cd), or mercury (Hg).
• the promoter is a metal of Group V-A, it may preferably be arsenic (As), antimony (Sb), or bismuth (Bi).
• the hydrogenating metal may be loaded onto the solid heterogeneous catalyst by immersing the catalyst support in solution (e.g. ammonium heptamolybdate) for 2-24 hours, say 24 hours, followed by drying at 60°F-300°F, say 200°F for 1-24 hours, say 8 hours and calcining for 1-24 hours, say 3 hours at 750°F-1100°F, say 930°F.
• solution e.g. ammonium heptamolybdate
• the promoter metal may preferably be loaded onto the solid heterogeneous catalyst by immersing the catalyst support (preferably bearing the calcined hydrogenating metal - although they may be added simultaneously or in any order) in solution (e.g. bismuth nitrate) for 2-24 hours, say 24 hours, followed by drying at 60°F-300°F, say 200°F for 1-24 hours, say 3 hours, and calcining at 570°F-1100°F, say 750°F for 1-12 hours, say 3 hours.
• solution e.g. bismuth nitrate
• the solid heterogenous catalyst employed in the method of this invention may be characterized by a Total Pore Volume of 0.2-1.2 cc/g, say 0.77 cc/g; a Surface Area of 50-500 m2/g, say 280 m2/g; and a Pore Size Distribution as follows:
• it may have a pore size distribution as follows:
• the solid heterogeneous catalyst typically may contain 4-30w%, say 9.5w% Mo, 0-6w%, say 3.1w% Ni and 0-6w%, say 3.1w% of promoter metal e.g. bismuth.
• LHSV in the hydroconversion reactors may be 1-2, say 0.7.
• the heterogeneous catalyst may be employed in the form of extrudates of diameter of 0.7-6.5mm, say 1mm and of length of 0.2-25mm, say 5mm.
• Hydroconversion may be carried out in a fixed bed, a moving bed, a fluidized bed, or preferably an ebullated bed.
• hydroconversion may be carried out in one or more beds. It is found that the active form of the catalyst is formed in or accumulates in the first of several reactors; and accordingly increases in conversion and heteroatom removal activities appear to occur in the first of several reactors.
• Effluent from hydroconversion is typically characterized by an increase in the content of liquids boiling below 1000°F.
• the w% conversion of the 1000°F + boiling material is 30%-90%, say 67% which is typically 5%-25%, say 12% better than is attained by the prior art techniques.
• HDS Conversion may be 30-90%, say 65% which is 1%-10%, say 4% higher than the control runs.
• HDN Conversion may be 20%-60%, say 45% which is 1%-10%, say 4% higher than control runs.
• HDNi plus HDV Conversion may be 70%-99%, say 90% which is 5%-20%, say 13% higher than control runs.
• hydrocarbon is a blend of vacuum resid derived from Alaskan North Slope (59v%), Arabian Medium (5v%), Arabian Heavy (27v%), and Bonny Light (9v%).
• the solid heterogeneous catalyst is commercially available hydrotreating catalyst (sold by Criterion Catalyst Company as HDS-1443B catalyt) containing 2.83w% nickel and 8.75w% molybdenum on alumina. This catalyst is 1/32 ⁇ diameter extrudates ⁇ 5mm long of Surface Area 285.2 m2/g and Total Pore Volume of 0.78 cc/g. Pore Size Distribution is: 0.28 cc/g >250A; 0.21 cc/g >500A; 0.19 cc/g >1500A; 0.11 cc/g >4000A.
• Results are set forth in the following Table which shows conversion of 1000°F, HDS Conversion, HDV Conversion, HDNi Conversion, and Cyclohexane Insolubles - all expressed in w%.
• Example I In this series of Examples, the procedure of Example I is duplicated except that the concentration of molybdenum (ppm) is varied. Temperature of operation is 785°F in Examples I-V*.
• cobalt naphthenate is an effective oil-miscible catalytic metal, although it appears to be less preferred than molybdenum.
• Example II the procedure of Example I is followed except that, in place of molybdenum naphthenate, there is added molybdenum hexacarbonyl to yield 100 ppm of molybdenum metal. Temperature of operation is 800°F.
• Example IX the procedure of Example I is followed except that the supported catalyst (Ni/Mo/Alumina in Example I) did not bear Ni or Mo i.e. it was only non-catalytic alumina.
• Example X the procedure of Example III is followed except that 13 ppm cobalt (as cobalt naphthenate) is blended with 60 ppm molybdenum (as molybdenum naphthenate).

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• 1992
  • 1992-05-01 CA CA 2067878 patent/CA2067878A1/en not_active Abandoned
  • 1992-05-01 EP EP19920304001 patent/EP0512778B1/de not_active Expired - Lifetime
  • 1992-05-01 DE DE1992606314 patent/DE69206314T2/de not_active Expired - Fee Related
  • 1992-05-04 MX MX9202076A patent/MX9202076A/es unknown
  • 1992-05-06 JP JP4139625A patent/JP3051566B2/ja not_active Expired - Lifetime

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