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
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
  • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
• • 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
  • B01J37/20—Sulfiding
• • 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
  • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
• • 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
  • C10G2300/1074—Vacuum distillates
• • 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
  • C10G2300/1077—Vacuum residues
• • 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
• • 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
  • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
• • 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
  • C10G2300/70—Catalyst aspects
  • C10G2300/703—Activation
• • 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
  • C10G2300/70—Catalyst aspects
  • C10G2300/708—Coking aspect, coke content and composition of deposits

Definitions

• This invention relates to an improved method of presulfiding a supported metal oxide catalyst for use in hydrotreating and/or hydrocracking hydrocarbon feedstocks, the presulfurized catalytic composition resulting therefrom, and a hydrotreating and/or hydrocracking process utilizing such presulfurized metal oxide catalyst.
• This invention further relates to an improved method for integrating catalyst presulfiding with a residuum hydroconversion process.
• a hydrotreating catalyst may be defined as any catalyst composition which may be used to catalyze the hydrogenation of hydrocarbon feedstocks to increase its hydrogen content and/or remove heteroatom contaminants.
• a hydrocracking catalyst may be defined as any catalyst composition which may be used to catalyze the addition of hydrogen to large or complex hydrocarbon molecules as well as the cracking of the molecules to obtain smaller, lower molecular weight molecules.
• a residuum hydroconversion process may be defined as a process for converting petroleum atmospheric or vacuum residue at conditions of elevated temperatures and pressures in the presence of hydrogen and a hydrotreating and/or hydrocracking catalyst to convert the feedstock to lower molecular weight products with reduced contaminant (such as sulfur and nitrogen) levels.
• Catalyst compositions for use in the residuum hydroconversion process are well known to those skilled in the art and several are commercially available.
• Suitable catalysts include catalysts containing nickel, cobalt, tungsten, molybdenum and combinations thereof supported on a porous substrate such as silica, alumina, titania, or combinations thereof.
• metal oxide catalysts are converted at least in part to metal sulfides.
• the metal oxide catalysts can be sulfided in the reactor by contact at elevated temperatures with hydrogen sulfide or a sulfur-containing oil or feedstock.
• the catalysts may also be provided to the end-user already having sulfur incorporated therein.
• these ex-situ methods of presulfurizing supported metal oxide catalysts have suffered from excessive stripping of sulfur upon start-up of a hydrotreating reactor in the presence of a hydrocarbon feedstock. As a result of sulfur stripping, a decrease in catalyst activity is observed. It is therefore well known in the art that the activity and activity maintenance of the above mentioned metal oxide catalysts is substantially enhanced by presulfiding of the catalysts in the manufacturing process or in- situ during startup of the hydroconversion process.
• Hydroconversion processes can operate in a fixed catalyst bed mode in which a batch of catalyst is utilized in the hydroconversion reactors for periods of typically three months to twenty-four months before the process is shut down to remove and replace the catalyst.
• catalyst can be presulfided during unit startup to achieve maximum levels of catalytic performance (hydrogenation, desulfurization, denitrogenation, conversion, etc.)
• catalyst In hydrotreating/hydrocracking processes, which add and withdraw catalyst on a regular basis (i.e. daily, weekly) while the process operates at normal conditions of temperature and pressure, catalyst is typically added in an as-manufactured state (i.e. containing metal oxides). Processes which operate in this mode include ebullated-bed hydrocrackers (such as H-OilTM Process), moving-bed hydrotreater, Onstream Catalyst Replacement reactors (OCR) and guard reactors used in fixed-bed resid hydrotreaters.
• ebullated-bed hydrocrackers such as H-OilTM Process
• moving-bed hydrotreater moving-bed hydrotreater
• OCR Onstream Catalyst Replacement reactors
• guard reactors used in fixed-bed resid hydrotreaters.
• This invention describes an improved method for achieving the catalyst presulfiding and preconditioning during normal plant operations but prior to addition of the catalyst to the catalytic reactor and can be accomplished in most situations with minimal equipment changes. This provides the benefit of being able to retrofit existing units as well as implementing on grass roots applications. Moreover, the invention allows for the preconditioning of the residuum hydrotreating or hydrocracking catalyst without interrupting the continuous operation of the resid hydroconversion process. Importantly, the resid hydroconversion process of this invention can operate continuously for several years while maintaining high catalyst activity.
• This invention describes an improved method for presulfiding and preconditioning a residuum hydrotreating or hydrocracking catalyst as an integrated part of the hydroconversion process. Moreover, the method allows for catalyst to be added on-stream intermittently or continuously without interruption of the hydroconversion process. The method is used to condition, activate, or presulfide fresh or regenerated catalyst prior to its addition to the hydroconversion reactor utilizing product streams from the hydroconversion process.
• this invention describes a method to improve the activity and activity maintenance of a hydrotreating and/or hydrocracking catalyst utilized in a resid hydroconversion process comprising:
• this invention describes a method to improve the activity and activity maintenance of a hydrotreating and/or hydrocracking catalyst utilized in a resid hydroconversion process which comprises:
• Figure 1 shows a schematic flowsheet of a resid hydroconversion process.
• Figure 2 is a schematic flowsheet of the catalyst preconditioning system.
• Figure 3 is a graph of desulfurization versus time showing the effect of catalyst presulfiding.
• FIG. 2 is a schematic flowsheet of the catalyst preconditioning system.
• Fresh or regenerated catalyst used for this process is added to a catalyst addition vessel 22 from the catalyst feed hopper 20 in the as-received metal oxide state.
• Suitable catalysts for the resid hydroconversion process include catalysts containing nickel, cobalt, tungsten, molybdenum and combinations thereof supported on a porous substrate such as silica, alumina, titania, or combinations thereof.
• the catalyst addition vessel 22 is subsequently evacuated and/or purged with nitrogen to remove oxygen and moisture from the vessel.
• This H 2 S rich hydrogen stream 10 can come from a number of available sources within the resid hydroconversion process flow scheme including: (i) a high pressure cold separator 58, (ii) a warm high pressure separator 56, or (iii) any H and H 2 S rich streams being recovered in the process. These sources are shown in Figure 1.
• the H 2 /H 2 S rich stream 10 is typically available at pressures of 400 to 3,000 PSIG, and at temperatures from 100 to 800°F
• Catalyst presulfiding is preferably earned out at temperatures from about 300 to 750°F with pressure increasing from atmospheric to approaching that of the available stream (i.e. 400-3,000 PSIG). Additionally, H 2 S concentrations in the feed gas of 1 to 10 volume percent are preferred. Moreover, it is desirable to treat the catalyst with a quantity of H 2 S at least 50% greater than that required to convert the metal oxide to the metal sulfide state to assure complete presulfiding.
• the catalyst is subsequently exposed to a stream of hydrocarbons to further enhance the catalyst activity and activity maintenance.
• Distillate hydrocarbon stream 14 supplied from the warm high pressure separator 56 or by using an atmospheric and/or vacuum gas oil, is circulated across the catalyst, along with the H 2 and H S rich stream 10, in the catalyst addition vessel 22.
• the temperature of the hydrocarbon stream is typically 500 to 750°F with pressures from atmospheric to that of the available stream (400-3,000 PSIG).
• This step completes the presulfiding and preconditioning process of this invention.
• a moderately low level of carbon typically 1-5 weight percent
• This coke layer protects the catalyst from surface temperature exotherms when the catalyst is initially added to the high severity (typically 750 to 850°F) resid hydrocracking reactor environment.
• the catalyst addition vessel 22 is filled with liquid hydrocarbon from stream 14 and pressurized to reactor pressure with hydrogen.
• the catalyst is then transported to one of the reactors 50 or 52 with the liquid hydrocarbon and added to said reactor(s) for resid hydrocarbon processing.
• Reactors 50 and 52 are shown both in Figure 2 and in Figure 1, a schematic of the overall resid hydroconversion process.
• FIG. 3 shows commercial resid hydroconversion plant data operating initially with 100 percent presulfided catalyst with no on-stream catalyst addition or withdrawal. Initial actual catalyst desulfurization performance is superior to that predicted from correlations based on small scale testing. It is important to note that the model prediction is based on 100 percent presulfided catalyst.
• the model prediction is 4-5 w% HDS less than the actual data but follows the decreasing trend of HDS.
• fresh or regenerated nickel- molybdenum catalyst at ambient temperature and pressure is fed via lock hopper to a catalyst addition vessel similar to that shown in Figure 2.
• the vessel is then evacuated of air and moisture using one line and purged with nitrogen using another line.
• the catalyst in the catalyst addition vessel is then presulfided by feeding a H 2 S rich hydrogen purge gas from a high pressure cold separator.
• the stream is available at 130°F and 2,760 PSIA and contains 2.2 volume % H 2 S, 75 volume % H 2 , with the remainder mostly light hydrocarbons.
• the catalyst is a nickel-molybdenum on alumina extrudate, and designated as Criterion HDS-2443B catalyst.
• Flow is initiated with the treat gas at 130°F and atmospheric pressure while the stream is heated to the desired presulfiding temperature of between about 300 to 750°F.
• the catalyst addition vessel is slowly pressurized to the pressure of the downstream intermediate pressure amine absorber.
• Flow is then initiated to the amine absorber for H 2 S removal and then to hydrogen recovery.
• Flow of the H 2 S and H 2 rich treat gas is continued until approximately 12 lbs. of sulfur are passed through the catalyst bed per 100 lbs. of fresh nickel-molybdenum catalyst to achieve complete catalyst presulfiding.
• Flow is then discontinued.
• Heavy petroleum transport oil is then allowed to fill the catalyst addition vessel with oil, circulate the oil through the catalyst, and heat the catalyst to the range of 500 to 650°F for transfer to the hydroconversion reactor.
• the catalyst addition vessel is then pressurized to reactor conditions with hydrogen from the hydroconversion process and the catalyst is transported to the hydroconversion reactor. This procedure can typically be carried out within 12 hours. During this time, the resid hydroconversion process operates in a continuous manner at temperature and pressure producing the desired product yields and qualities.
• the catalyst in the catalyst addition vessel is then presulfided by feeding a portion of the H 2 S rich vapor stream leaving the warm high pressure separator (which is illustrated in the Figure 1 schematic as No. 56).
• the stream is at approximately 525°F and 2,800 PSIA, and contains 3 volume % H 2 S and 75 volume % H 2 with the remainder mostly light hydrocarbons.
• the catalyst is a nickel-molybdenum on alumina extrudate having the designation as Grace GR-25 catalyst.
• Flow is initiated to the catalyst addition vessel to pressurize this vessel to the pressure of the downstream intermediate pressure amine absorber.
• Flow is then established through the catalyst addition vessel to the intermediate pressure amine absorber for H 2 S removal and then to hydrogen recovery.
• the catalyst is gradually heated up and presulfided at a temperature of 525°F and a pressure of approximately 400 PSIG with the high pressure H 2 S containing vapor stream. Treatment is continued until approximately 12 lbs. of sulfur are passed through the catalyst bed per 100 lbs. of fresh nickel-molybdenum catalyst to achieve complete catalyst presulfiding. At these conditions, approximately 8 lbs. of sulfur will be retained on the catalyst.
• a portion of the liquid stream from the warm high pressure separator is blended with the vapor stream used for presulfiding (as described above).
• the combined stream is subsequently fed across the catalyst for between 15 minutes to 10 hours to condition the catalyst.
• the catalyst will contain about 1 to 5 weight percent carbon after exposure to the combined stream.

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

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• 2000
  • 2000-06-19 CA CA2412363A patent/CA2412363C/en not_active Expired - Lifetime
  • 2000-06-19 JP JP2002503445A patent/JP4898069B2/ja not_active Expired - Fee Related
  • 2000-06-19 EP EP00945772A patent/EP1299192A1/de not_active Withdrawn
  • 2000-06-19 WO PCT/EP2000/005629 patent/WO2001097971A1/en not_active Ceased

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