EP0732389A2 - Complete catalytic hydroconversion process for heavy petroleum feedstocks - Google Patents

Complete catalytic hydroconversion process for heavy petroleum feedstocks Download PDF

Info

Publication number
EP0732389A2
EP0732389A2 EP96103874A EP96103874A EP0732389A2 EP 0732389 A2 EP0732389 A2 EP 0732389A2 EP 96103874 A EP96103874 A EP 96103874A EP 96103874 A EP96103874 A EP 96103874A EP 0732389 A2 EP0732389 A2 EP 0732389A2
Authority
EP
European Patent Office
Prior art keywords
stage
reactor
catalyst
catalytic
feedstock
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96103874A
Other languages
German (de)
French (fr)
Other versions
EP0732389B1 (en
EP0732389A3 (en
Inventor
James J. Colyar
James B. Macarthur
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP0732389A2 publication Critical patent/EP0732389A2/en
Publication of EP0732389A3 publication Critical patent/EP0732389A3/en
Application granted granted Critical
Publication of EP0732389B1 publication Critical patent/EP0732389B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/10Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps

Definitions

  • This invention pertains to a catalytic two-stage hydroconversion process for achieving essentially complete hydroconversion of heavy petroleum-based feedstocks to produce lower-boiling hydrocarbon liquid products. It pertains particularly to such a process utilizing a high temperature first stage ebullated bed catalytic reactor and lower temperature second stage ebullated bed catalytic reactor, with extinction recycle of all distilled vacuum bottoms material back to the first stage reactor to provide 90-100 vol% hydroconversion of the feedstocks.
  • U.S. No. 3,549,517 to Lehman discloses a single stage catalytic process in which a vacuum distillation side stream is recycled to the reactor.
  • U.S. Patent No. 3,184,402 to Kozlowski, et al discloses a two-stage catalytic hydrocracking process with intermediate fractionation and some recycle of a distillation bottoms fraction to either a first or second catalytic cracking zone.
  • U.S. Patent No. 3,254,017 to Arey, Jr. et al discloses a two-stage process for hydrocracking heavy oils utilizing small pore zeolite catalyst in the second stage reactor.
  • 3,775,293 to Watkins discloses a two-stage catalytic desulfurization process with recycle of some heavy oil fraction boiling above diesel fuel oil to a second stage fixed bed type reactor.
  • U.S. No. 4,457,831 to Gendler discloses a two-stage catalytic hydroconversion process in which vacuum bottoms residue material is recycled to the second stage reactor for further hydroconversion reactions.
  • U.S. No. 4,576,710 to Nongbri et al discloses a two-stage catalytic desulfurization process for petroleum residua feedstocks utilizing catalyst regeneration.
  • the present invention advantageously overcomes the concerns of potential users and provides a desirable improvement over the known prior art hydroconversion processes for heavy petroleum feedstocks.
  • This invention provides a catalytic two-stage ebullated bed hydroconversion process for heavy petroleum, residual oil and bitumen feedstocks, which process effectively hydroconverts essentially all of the high boiling residue material in the feedstock to desirable high quality lower boiling hydrocarbon liquid products.
  • the process is particularly useful for those feedstocks containing 40-100 vol% 975°F + petroleum resid and 10-50 wt% Conradson carbon residue (CCR), and containing up to 1000 wppm total metals (V+Ni).
  • Preferred feedstocks should contain 75-100 vol% 975°F + residual material with 15-40 wt% CCR, and 100-600 wppm total metals (V+Ni).
  • Such feedstocks may include but are not limited to heavy crudes, atmospheric bottoms and vacuum resid materials from Alaska, Athabasca, Ba skilletro, Cold Lake, Lloydminster, Orinoco and Saudi Arabia.
  • the fresh feedstock is introduced together with hydrogen into a first stage catalytic ebullated bed type reactor, which is essentially a high temperature hydroconversion reactor utilizing a particulate supported hydroconversion catalyst.
  • the reactor is maintained at operating conditions of 820-875°F temperature, 1500-3500 psig hydrogen partial pressure, and space velocity of 0.30-1.0 volume feed per hour per volume of reactor (V f /hr/V r ).
  • the catalyst replacement rate should be 0.15-0.90 pound catalyst/barrel of fresh oil feed.
  • the first stage reactor hydroconverts 70-95 vol.% of the fresh feed material and recycled residue material to form lower boiling hydrocarbon materials.
  • the first stage reactor effluent material is phase separated, a gas fraction is removed and the resulting liquid fraction is passed together with additional hydrogen on to a second stage catalytic ebullated bed type reactor containing a particulate high activity catalyst and which is maintained at lower temperature conditions of 700-800°F temperature and 0.10-0.80 V f /hr/V f , space velocity, so as to effectively hydrogenate the unconverted residue material therein.
  • the second stage reactor catalyst replacement rate should be 0.15-0.90 pound catalyst/barrel feed to the second stage, which hydroconverts 10-50 vol% of the second stage feed material to lower boiling hydrocarbon materials.
  • the second stage reactor effluent material is passed to gas/liquid separation and distillation steps, from which hydrocarbon liquid product and distillation vacuum bottoms fraction materials are removed.
  • the vacuum bottoms material boiling above at least 850°F temperature and preferably above 900°F is recycled back to the first stage catalytic reactor inlet at a volume ratio to the fresh feedstock of 0.2-1.5/1, and preferably at 0.5-1.0/1 recycle ratio for further hydroconversion extinction reactions therein.
  • Particulate catalyst materials which are useful in this petroleum hydroconversion process may contain 2-25 wt. percent total active metals selected from the group consisting of cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof deposited on a support material selected from the group of alumina, silica and combinations thereof. Also, catalysts having the same characteristics may be used in both the first stage and second stage reactors.
  • Catalysts having unimodal, bimodal and trimodal pore size distribution are useful in this process.
  • Preferred catalysts should contain 5-20 wt.% total active metals consisting of combinations of cobalt, molybdenum and nickel deposited on alumina support material.
  • the heavy petroleum feedstock is first catalytically hydroconverted in the first stage catalytic higher temperature reactor, and the remaining resid fraction is catalytically hydrogenated in the second stage catalytic lower temperature reactor, after which a vacuum distilled 850°F + fraction is recycled back to the first stage reactor for further hydrocracking reactions at the higher temperature maintained therein.
  • Passing the first stage reactor liquid phase effluent material to the second stage reactor operated at lower temperature and space velocity conditions concentrates unconverted residue material, minimizes any gas velocity related problems in the second stage reactor, and reduces contaminant partial pressures (H 2 S, NH 3 , H 2 O).
  • the second stage catalytic reactions increase the hydrogen/carbon ratio of the residue being processed therein, thereby decreasing aromaticity and increasing the hydrogen donor capability of the residue, so that by its recycle back to the first stage reactor the hydrogenated residue can donate hydrogen to the fresh feedstock and the hydrogenated residue can also be more readily hydroconverted to desirable lower boiling fractions.
  • This approach is more selective to producing high yields of desirable hydrocarbon liquid fuel products, i.e. reduced hydrocarbon gas contributes to high conversion operations.
  • This catalytic hydroconversion process can also be further improved by selectively feeding fresh hydrogen to the second stage reactor and recycling hydrogen gas to the first stage reactor, so as to maximize hydrogen partial pressure in the more catalytic second stage hydrogenation reactor.
  • used catalyst in the second stage ebullated bed reactor can be withdrawn, treated to remove undesired fines, etc., and introduced into the first stage ebullated bed reactor for further use therein, before the used catalyst is withdrawn from the first stage reactor and discarded.
  • utilizing used second stage catalyst material in the first stage reactor is appropriate and beneficial, because use of fresh, high activity catalyst in the higher temperature mainly thermal type reactor would not provide substantially improved catalytic activity therein.
  • any disposition problems usually related to an unconverted bottoms fraction material are eliminated.
  • This process advantageously provides for improved matching of the reaction conditions and the catalytic activity needed in each stage reactor, by providing higher reaction temperature and lower catalyst activity in the first stage reactor and lower temperature and higher catalyst activity in the second stage reactor, so as to achieve a more complete hydroconversion of the feedstock and effective use of the catalyst.
  • This combination of the two staged reaction conditions is unexpectedly beneficial and results in essentially complete hydroconversion of heavy petroleum feedstocks to produce desirable lower boiling hydrocarbon liquid products, without substantially increasing reactor volume over the single stage approach to achieving high hydroconversion of the feedstock.
  • Fig. 1 is a schematic flow diagram of a catalytic two-stage hydroconversion process for processing heavy petroleum feedstocks to produce lower-boiling liquid and gas products according to the invention.
  • a catalytic two-stage ebullated bed reaction process and system which is adapted for achieving substantially complete hydroconversion and destruction of residue material (975°F + fraction) contained in heavy petroleum oil, residual oil, or bitumen feedstocks, and for producing desirable low-boiling hydrocarbon liquid products.
  • a pressurized heavy petroleum feedstock such as Cold Lake vacuum resid is provided at 10, combined with hydrogen at 12 and mixed with recycled hydrogenated heavy vacuum bottoms material at 13, and the combined stream 14 is fed upwardly through flow distributor 15 in first stage catalytic ebullated bed upflow reactor 16 containing catalyst ebullated bed 18.
  • the total feedstock consists of the fresh hydrocarbon feed material at 10 plus the recycled vacuum bottoms material at 13.
  • the recycle rate for the vacuum bottoms material at 13 to the first stage reactor 16 is selected so as to completely destroy or extinct this residue material in two staged catalytic reactors, with the recycle volume ratio of the vacuum bottoms material to the fresh oil feedstock being in the range of 0.2-1.5/1, and preferably 0.50-1.0/1 recycle ratio.
  • the hydrocracking reactions are primarily thermal type as the reactor is maintained at a relatively high temperature of 820-875°F, at 1,500-3,500 psig hydrogen partial pressure, and liquid hourly space velocity of 0.30-1.0 volume feed/hr/volume of reactor (V f /hr/V r ).
  • the feedstock hydroconversion achieved therein is typically 70-95 vol %, with about 75-90 vol. % conversion usually being preferred.
  • Preferred first stage reaction conditions are 825-850°F temperature, 2000-3000 psig, hydrogen partial pressure, and 0.40-0.80 V f /hr/V r space velocity.
  • the catalyst bed 18 in first stage reactor 16 is expanded by the upflowing gas and reactor liquid to 30-60% above its settled height and is ebullated as described in more detail in U.S. Patent No. 3,322,665 which is incorporated herein by reference to the extent needed to describe operation of the reactor ebullated catalyst beds.
  • first stage reactor 16 From first stage reactor 16, overhead effluent stream 19 is withdrawn and passed to phase separator 20. A liquid stream is withdrawn from the separator 20 through downcomer conduit 22, and is recirculated through conduit 24 by ebullating or recycle pump 25 back to the reactor 16.
  • the particulate catalyst material added at 17 is preferably used extrudate catalyst withdrawn at 36 from second stage reactor 30, and usually treated at zone 38 as desired to remove particulate fines, etc. at 37.
  • Fresh make-up catalyst can be added as needed at 17a, and spent catalyst is withdrawn at connection 17b from catalyst bed 18.
  • gaseous material at 21 is passed to a gas purification section 42, which is described further herein below. Also from the separator 20, a liquid portion 26 from the liquid stream 22 provides the liquid feed ( ⁇ 700°F + ) material upwardly through flow distributor 27 into the second stage catalytic ebullated bed reactor 30.
  • the second stage catalytic reactor 30 which preferably has larger volume and provides lower space velocity than for the first-stage reactor 16, less hydroconversion and more catalytic hydrogenation type reactions occur.
  • the second stage reactor 30 contains ebullated catalyst bed 28 and is operated at conditions of 700-800°F temperature 1,500-3,500 psig hydrogen partial pressure, and 0.10-0.80 V f /hr/V r space velocity, and thereby maximizes resid hydrogenation reactions which occur therein.
  • Preferred second stage reaction conditions are 730-780°F temperature, and 0.20-0.60 V f /hr/V r space velocity. Additional fresh hydrogen is provided at 32 to the second stage reactor 30, so that a high level of hydrogen partial pressure is maintained in the reactor.
  • the catalyst bed 28 is expanded by 30-60% above its settled height by the upflowing gas and liquid therein.
  • Reactor liquid is withdrawn from an internal phase separator 33 through downcomer conduit 34 to recycle pump 35, and is reintroduced upwardly through the flow distributor 27 into the ebullated bed 28.
  • Used particulate catalyst is withdrawn at 36 from the second stage reactor bed 28 and fresh catalyst is added at 36 a as needed to maintain the desired catalyst volume and catalytic activity therein.
  • This used catalyst withdrawn which is relatively low in metal contaminant concentration, is passed to a treatment unit 38 where it is washed, and screened to remove undesired fines at 37, and the recovered catalyst at 39 provides the used catalyst addition at 17 to the first stage reactor bed 18, together with any fresh make-up catalyst added at connection 17a as needed.
  • the catalyst particles in ebullated beds 18 and 28 usually have a relatively narrow size range for uniform bed expansion under controlled upward liquid and gas flow conditions. While the useful catalyst size range is between 6 and 60 mesh (U.S. Sieve Series), the catalyst size is preferably particles between 8 and 40 mesh size including beads, extrudates, or spheres of approximately 0.020-0.100 inch effective diameter. In the reactor, the density of the catalyst particles, the liquid upward flow rate, and the lifting effect of the upflowing hydrogen gas are important factors in the desired expansion and operation of the catalyst bed.
  • an effluent stream is withdrawn at 31 and passed to a phase separator 40.
  • a hydrogen-containing gas stream 41 is passed to the purification section 42 for removal of contaminants such as CO 2 , H 2 S, and NH 3 at 43.
  • Purified hydrogen at 44 is recycled back to each reactor 16 and 30 as desired as the H 2 streams 12 and 32, respectively, while fresh hydrogen is added at 45 as needed.
  • a liquid fraction 46 is withdrawn, pressure-reduced at 47 to 0-100 psig, and is introduced into fractionation unit 48.
  • a gaseous product stream is withdrawn at 49 and a light hydrocarbon liquid product normally boiling between 400-850°F are withdrawn at 50.
  • a bottoms 850°F + fraction is withdrawn at 52, reheated at heater 53, and passed to vacuum distillation step at 54.
  • a vacuum gas oil liquid product is withdrawn overhead at 55.
  • Vacuum bottoms stream 56 which has been hydrogenated in the second stage catalyst reactor 30, is completely recycled back to the first stage catalytic reactor 16 for predominantly thermal hydrocracking reactions therein using the low activity catalyst provided at 17.
  • the recycle volume ratio for vacuum bottoms stream 56 to fresh feed 10 should be 0.2-1.5/1, and preferably should be 0.50-1.0/1. It is pointed out that by utilizing this two stage catalytic hydroconversion process, the thermal reactions and catalytic activity in each stage reactor are effectively matched, so that there is essentially no net 975°F + hydrocarbon material produced from the process.
  • a typical heavy vacuum resid feedstock such as Cold Lake vacuum resid is processed by using the catalytic two-stage hydroconversion process with vacuum bottoms recycle arrangement of the present invention.
  • This Cold Lake vacuum resid feedstock contains 90 vol % 975°F + material, 5.1 wt.% sulfur, 19 wt.% CCR, and 350 wppm metals (V+Ni), with the vacuum bottoms fraction normally boiling above 975°F being recycled back to the first stage catalytic reactor of the two-reactor system for further hydroconversion reactions and extinction recycle therein.
  • the reaction conditions used and overall conversion results are summarized in Table 1 below.

Landscapes

  • 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)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for high catalytic hydroconversion of heavy liquid hydrocarbon feedstocks, such as petroleum resid containing at least about 40 vol% material boiling above 975°F+, using two-staged catalytic reactors operated at elevated temperature and pressure conditions so as to produce increased yields of lower boiling hydrocarbon liquids and gas products. In the process, the feedstock is reacted with hydrogen in a first stage catalytic ebullated bed reactor operated at 820-875°F temperature, 1500-3500 hydrogen partial pressure, and 0.30-1.0 Vf/Hr/Vr space velocity. The first stage reactor effluent liquid portion is fed into a second stage catalytic reactor maintained at lower temperature of 700-800°F, 0.10-0.80 Vf/hr/Vr space velocity. The particulate catalyst material used in each stage reactor contains 2-25 wt.% active metals, and has 0.30-1.50 cm2/gm total pore volume and 100-400 m2/gm surface area. From the second stage reactor effluent, a vacuum bottoms fraction normally boiling above about 850°F and preferably above 900°F is removed and recycled back to the first stage reactor, so as to provide a recycle volume ratio to fresh feedstock of 0.2-1.5/1 and achieve increased hydroconversion to produce lower boiling liquid products. If desired, used catalyst withdrawn from the second stage reactor can be treated and passed back to the first stage catalytic reactor for further use therein before being discarded, so as to provide for matched reaction conditions and catalytic activity in each stage reactor.

Description

    BACKGROUND OF INVENTION
  • This invention pertains to a catalytic two-stage hydroconversion process for achieving essentially complete hydroconversion of heavy petroleum-based feedstocks to produce lower-boiling hydrocarbon liquid products. It pertains particularly to such a process utilizing a high temperature first stage ebullated bed catalytic reactor and lower temperature second stage ebullated bed catalytic reactor, with extinction recycle of all distilled vacuum bottoms material back to the first stage reactor to provide 90-100 vol% hydroconversion of the feedstocks.
  • For H-Oil® catalytic hydroconversion processes for heavy petroleum feedstocks, effective use of the catalyst, poor product quality and disposition of unconverted residue material have been concerns for potential users. The catalytic hydroconversion of petroleum residua in a single-stage ebullated bed catalytic reactor with recycle of a vacuum bottoms fraction to the reactor is well known, having been previously disclosed in U.S. Patents No. 2,987,465 to Johanson and U.S. 3,412,010 to Alpert, et al. Also, U.S. Patent No. 3,322,665 to Chervenak et al discloses a process for catalytic treatment of heavy gas oil, in which a fractionator bottoms material is recycled to the reactor for further extinction reactions therein. U.S. No. 3,549,517 to Lehman discloses a single stage catalytic process in which a vacuum distillation side stream is recycled to the reactor. U.S. Patent No. 3,184,402 to Kozlowski, et al discloses a two-stage catalytic hydrocracking process with intermediate fractionation and some recycle of a distillation bottoms fraction to either a first or second catalytic cracking zone. U.S. Patent No. 3,254,017 to Arey, Jr. et al discloses a two-stage process for hydrocracking heavy oils utilizing small pore zeolite catalyst in the second stage reactor. U.S. No. 3,775,293 to Watkins, discloses a two-stage catalytic desulfurization process with recycle of some heavy oil fraction boiling above diesel fuel oil to a second stage fixed bed type reactor. U.S. No. 4,457,831 to Gendler discloses a two-stage catalytic hydroconversion process in which vacuum bottoms residue material is recycled to the second stage reactor for further hydroconversion reactions. Also. U.S. No. 4,576,710 to Nongbri et al discloses a two-stage catalytic desulfurization process for petroleum residua feedstocks utilizing catalyst regeneration.
  • However, further process improvements are needed to achieve higher hydroconversion of heavy high boiling hydrocarbon liquid feedstocks, such as petroleum residua normally boiling above about 800°F, to produce desired low-boiling hydrocarbon liquid products. The present invention advantageously overcomes the concerns of potential users and provides a desirable improvement over the known prior art hydroconversion processes for heavy petroleum feedstocks.
  • SUMMARY OF INVENTION
  • This invention provides a catalytic two-stage ebullated bed hydroconversion process for heavy petroleum, residual oil and bitumen feedstocks, which process effectively hydroconverts essentially all of the high boiling residue material in the feedstock to desirable high quality lower boiling hydrocarbon liquid products. The process is particularly useful for those feedstocks containing 40-100 vol% 975°F+ petroleum resid and 10-50 wt% Conradson carbon residue (CCR), and containing up to 1000 wppm total metals (V+Ni). Preferred feedstocks should contain 75-100 vol% 975°F+ residual material with 15-40 wt% CCR, and 100-600 wppm total metals (V+Ni). Such feedstocks may include but are not limited to heavy crudes, atmospheric bottoms and vacuum resid materials from Alaska, Athabasca, Bachaquero, Cold Lake, Lloydminster, Orinoco and Saudi Arabia.
  • In the process, the fresh feedstock is introduced together with hydrogen into a first stage catalytic ebullated bed type reactor, which is essentially a high temperature hydroconversion reactor utilizing a particulate supported hydroconversion catalyst. The reactor is maintained at operating conditions of 820-875°F temperature, 1500-3500 psig hydrogen partial pressure, and space velocity of 0.30-1.0 volume feed per hour per volume of reactor (Vf/hr/Vr). The catalyst replacement rate should be 0.15-0.90 pound catalyst/barrel of fresh oil feed. The first stage reactor hydroconverts 70-95 vol.% of the fresh feed material and recycled residue material to form lower boiling hydrocarbon materials.
  • The first stage reactor effluent material is phase separated, a gas fraction is removed and the resulting liquid fraction is passed together with additional hydrogen on to a second stage catalytic ebullated bed type reactor containing a particulate high activity catalyst and which is maintained at lower temperature conditions of 700-800°F temperature and 0.10-0.80 Vf/hr/Vf, space velocity, so as to effectively hydrogenate the unconverted residue material therein. The second stage reactor catalyst replacement rate should be 0.15-0.90 pound catalyst/barrel feed to the second stage, which hydroconverts 10-50 vol% of the second stage feed material to lower boiling hydrocarbon materials.
  • The second stage reactor effluent material is passed to gas/liquid separation and distillation steps, from which hydrocarbon liquid product and distillation vacuum bottoms fraction materials are removed. The vacuum bottoms material boiling above at least 850°F temperature and preferably above 900°F is recycled back to the first stage catalytic reactor inlet at a volume ratio to the fresh feedstock of 0.2-1.5/1, and preferably at 0.5-1.0/1 recycle ratio for further hydroconversion extinction reactions therein.
  • Particulate catalyst materials which are useful in this petroleum hydroconversion process may contain 2-25 wt. percent total active metals selected from the group consisting of cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof deposited on a support material selected from the group of alumina, silica and combinations thereof. Also, catalysts having the same characteristics may be used in both the first stage and second stage reactors.
  • The particulate catalyst will usually be in the form of extrudates or spheres and have the following useful and preferred characteristics:
    Figure imgb0001
  • Catalysts having unimodal, bimodal and trimodal pore size distribution are useful in this process. Preferred catalysts should contain 5-20 wt.% total active metals consisting of combinations of cobalt, molybdenum and nickel deposited on alumina support material.
  • Thus for the present process, the heavy petroleum feedstock is first catalytically hydroconverted in the first stage catalytic higher temperature reactor, and the remaining resid fraction is catalytically hydrogenated in the second stage catalytic lower temperature reactor, after which a vacuum distilled 850°F+ fraction is recycled back to the first stage reactor for further hydrocracking reactions at the higher temperature maintained therein. Passing the first stage reactor liquid phase effluent material to the second stage reactor operated at lower temperature and space velocity conditions concentrates unconverted residue material, minimizes any gas velocity related problems in the second stage reactor, and reduces contaminant partial pressures (H2S, NH3, H2O). The second stage catalytic reactions increase the hydrogen/carbon ratio of the residue being processed therein, thereby decreasing aromaticity and increasing the hydrogen donor capability of the residue, so that by its recycle back to the first stage reactor the hydrogenated residue can donate hydrogen to the fresh feedstock and the hydrogenated residue can also be more readily hydroconverted to desirable lower boiling fractions. This approach is more selective to producing high yields of desirable hydrocarbon liquid fuel products, i.e. reduced hydrocarbon gas contributes to high conversion operations. This catalytic hydroconversion process can also be further improved by selectively feeding fresh hydrogen to the second stage reactor and recycling hydrogen gas to the first stage reactor, so as to maximize hydrogen partial pressure in the more catalytic second stage hydrogenation reactor.
  • Also if desired, used catalyst in the second stage ebullated bed reactor can be withdrawn, treated to remove undesired fines, etc., and introduced into the first stage ebullated bed reactor for further use therein, before the used catalyst is withdrawn from the first stage reactor and discarded. Because of the presence of metal contaminants in the fresh heavy feedstock and the more thermal nature of the first stage reactions, utilizing used second stage catalyst material in the first stage reactor is appropriate and beneficial, because use of fresh, high activity catalyst in the higher temperature mainly thermal type reactor would not provide substantially improved catalytic activity therein. Also, by providing complete extinction of the feedstock resid fraction, any disposition problems usually related to an unconverted bottoms fraction material are eliminated.
  • This process advantageously provides for improved matching of the reaction conditions and the catalytic activity needed in each stage reactor, by providing higher reaction temperature and lower catalyst activity in the first stage reactor and lower temperature and higher catalyst activity in the second stage reactor, so as to achieve a more complete hydroconversion of the feedstock and effective use of the catalyst. This combination of the two staged reaction conditions is unexpectedly beneficial and results in essentially complete hydroconversion of heavy petroleum feedstocks to produce desirable lower boiling hydrocarbon liquid products, without substantially increasing reactor volume over the single stage approach to achieving high hydroconversion of the feedstock.
  • Other advantages of this catalytic two stage hydroconversion process for heavy petroleum feedstocks include complete destruction of the feedstock heavy residue fraction utilizing the selected catalytic reaction conditions, without producing undesired cokes, sediment or other such carbonaceous material in the reactors. The process also provides effective use of the catalyst by cascading used catalyst from the second stage ebullated bed reactor back to the first stage higher temperature ebullated bed reactor for further use therein. Optimal selection of reactor operating conditions and reactor volumes minimizes gas production and hydrogen consumption. After achieving effective hydrogenation of the unconverted residue in the second stage reactor, recycle of the hydrogenated residue material back to the first stage reactor provides effective hydroconversion with minimal gas and light ends production and with minimal additional hydrogen consumption. Passing the first stage reactor effluent liquid fraction to the second stage reactor concentrates liquid residue in the second stage reactor, and minimizes any operating problems therein due to incompatibility (light end fractions already being removed) and due to excessive gas velocity. Distillate (700-975°F) product quality is superior relative to that obtained from typical high conversion single stage H-Oil process operations due to the selective hydrogenation of the feedstock resid fractions in the second stage reactor.
  • BRIEF DESCRIPTION OF DRAWING
  • Fig. 1 is a schematic flow diagram of a catalytic two-stage hydroconversion process for processing heavy petroleum feedstocks to produce lower-boiling liquid and gas products according to the invention.
  • DESCRIPTION OF INVENTION
  • This invention will now be described in greater detail for a catalytic two-stage ebullated bed reaction process and system which is adapted for achieving substantially complete hydroconversion and destruction of residue material (975°F+ fraction) contained in heavy petroleum oil, residual oil, or bitumen feedstocks, and for producing desirable low-boiling hydrocarbon liquid products. As shown by Fig. 1, a pressurized heavy petroleum feedstock such as Cold Lake vacuum resid is provided at 10, combined with hydrogen at 12 and mixed with recycled hydrogenated heavy vacuum bottoms material at 13, and the combined stream 14 is fed upwardly through flow distributor 15 in first stage catalytic ebullated bed upflow reactor 16 containing catalyst ebullated bed 18. The total feedstock consists of the fresh hydrocarbon feed material at 10 plus the recycled vacuum bottoms material at 13. The recycle rate for the vacuum bottoms material at 13 to the first stage reactor 16 is selected so as to completely destroy or extinct this residue material in two staged catalytic reactors, with the recycle volume ratio of the vacuum bottoms material to the fresh oil feedstock being in the range of 0.2-1.5/1, and preferably 0.50-1.0/1 recycle ratio.
  • In the first stage reactor 16, the hydrocracking reactions are primarily thermal type as the reactor is maintained at a relatively high temperature of 820-875°F, at 1,500-3,500 psig hydrogen partial pressure, and liquid hourly space velocity of 0.30-1.0 volume feed/hr/volume of reactor (Vf/hr/Vr). The feedstock hydroconversion achieved therein is typically 70-95 vol %, with about 75-90 vol. % conversion usually being preferred. Preferred first stage reaction conditions are 825-850°F temperature, 2000-3000 psig, hydrogen partial pressure, and 0.40-0.80 Vf/hr/Vr space velocity. The catalyst bed 18 in first stage reactor 16 is expanded by the upflowing gas and reactor liquid to 30-60% above its settled height and is ebullated as described in more detail in U.S. Patent No. 3,322,665 which is incorporated herein by reference to the extent needed to describe operation of the reactor ebullated catalyst beds.
  • From first stage reactor 16, overhead effluent stream 19 is withdrawn and passed to phase separator 20. A liquid stream is withdrawn from the separator 20 through downcomer conduit 22, and is recirculated through conduit 24 by ebullating or recycle pump 25 back to the reactor 16. For the first stage reactor 16, the particulate catalyst material added at 17 is preferably used extrudate catalyst withdrawn at 36 from second stage reactor 30, and usually treated at zone 38 as desired to remove particulate fines, etc. at 37. Fresh make-up catalyst can be added as needed at 17a, and spent catalyst is withdrawn at connection 17b from catalyst bed 18.
  • From the phase separator 20, gaseous material at 21 is passed to a gas purification section 42, which is described further herein below. Also from the separator 20, a liquid portion 26 from the liquid stream 22 provides the liquid feed (∼700°F+) material upwardly through flow distributor 27 into the second stage catalytic ebullated bed reactor 30.
  • In the second stage catalytic reactor 30, which preferably has larger volume and provides lower space velocity than for the first-stage reactor 16, less hydroconversion and more catalytic hydrogenation type reactions occur. The second stage reactor 30 contains ebullated catalyst bed 28 and is operated at conditions of 700-800°F temperature 1,500-3,500 psig hydrogen partial pressure, and 0.10-0.80 Vf/hr/Vr space velocity, and thereby maximizes resid hydrogenation reactions which occur therein. Preferred second stage reaction conditions are 730-780°F temperature, and 0.20-0.60 Vf/hr/Vr space velocity. Additional fresh hydrogen is provided at 32 to the second stage reactor 30, so that a high level of hydrogen partial pressure is maintained in the reactor.
  • The catalyst bed 28 is expanded by 30-60% above its settled height by the upflowing gas and liquid therein. Reactor liquid is withdrawn from an internal phase separator 33 through downcomer conduit 34 to recycle pump 35, and is reintroduced upwardly through the flow distributor 27 into the ebullated bed 28. Used particulate catalyst is withdrawn at 36 from the second stage reactor bed 28 and fresh catalyst is added at 36 a as needed to maintain the desired catalyst volume and catalytic activity therein. This used catalyst withdrawn, which is relatively low in metal contaminant concentration, is passed to a treatment unit 38 where it is washed, and screened to remove undesired fines at 37, and the recovered catalyst at 39 provides the used catalyst addition at 17 to the first stage reactor bed 18, together with any fresh make-up catalyst added at connection 17a as needed.
  • The catalyst particles in ebullated beds 18 and 28 usually have a relatively narrow size range for uniform bed expansion under controlled upward liquid and gas flow conditions. While the useful catalyst size range is between 6 and 60 mesh (U.S. Sieve Series), the catalyst size is preferably particles between 8 and 40 mesh size including beads, extrudates, or spheres of approximately 0.020-0.100 inch effective diameter. In the reactor, the density of the catalyst particles, the liquid upward flow rate, and the lifting effect of the upflowing hydrogen gas are important factors in the desired expansion and operation of the catalyst bed.
  • From the second stage reactor 30, an effluent stream is withdrawn at 31 and passed to a phase separator 40. From this separator 40, a hydrogen-containing gas stream 41 is passed to the purification section 42 for removal of contaminants such as CO2, H2S, and NH3 at 43. Purified hydrogen at 44 is recycled back to each reactor 16 and 30 as desired as the H2 streams 12 and 32, respectively, while fresh hydrogen is added at 45 as needed.
  • Also from separator 40, a liquid fraction 46 is withdrawn, pressure-reduced at 47 to 0-100 psig, and is introduced into fractionation unit 48. A gaseous product stream is withdrawn at 49 and a light hydrocarbon liquid product normally boiling between 400-850°F are withdrawn at 50. A bottoms 850°F+ fraction is withdrawn at 52, reheated at heater 53, and passed to vacuum distillation step at 54. A vacuum gas oil liquid product is withdrawn overhead at 55. Vacuum bottoms stream 56, which has been hydrogenated in the second stage catalyst reactor 30, is completely recycled back to the first stage catalytic reactor 16 for predominantly thermal hydrocracking reactions therein using the low activity catalyst provided at 17. The recycle volume ratio for vacuum bottoms stream 56 to fresh feed 10 should be 0.2-1.5/1, and preferably should be 0.50-1.0/1. It is pointed out that by utilizing this two stage catalytic hydroconversion process, the thermal reactions and catalytic activity in each stage reactor are effectively matched, so that there is essentially no net 975°F+ hydrocarbon material produced from the process.
  • The process of the present invention will be further described by use of the following examples, which are illustrative only and should not be construed as limiting the scope of the invention.
  • EXAMPLE 1
  • A typical heavy vacuum resid feedstock such as Cold Lake vacuum resid is processed by using the catalytic two-stage hydroconversion process with vacuum bottoms recycle arrangement of the present invention. This Cold Lake vacuum resid feedstock contains 90 vol % 975°F+ material, 5.1 wt.% sulfur, 19 wt.% CCR, and 350 wppm metals (V+Ni), with the vacuum bottoms fraction normally boiling above 975°F being recycled back to the first stage catalytic reactor of the two-reactor system for further hydroconversion reactions and extinction recycle therein. The reaction conditions used and overall conversion results are summarized in Table 1 below. Table 1
    Hydroconversion of Cold Lake Vacuum Resid Feedstock
    Catalyst Used 16-20 wt.% Cobalt-moly on alumina
    Hydroconversion, Vol% up to 100%
    Reactor 1 Reactor 2 Overall
    Reaction Temperature, °F 827 760 --
    H2 Partial Pressure, psig 2,000 2,000 --
    Reactor Space velocity, Vf/hr/Vr 0.40 0.20 --
    H2 Consumption, SCF/Bbl Feed -- -- 2570
    Recycle Ratio 0.75 -- --
    Catalyst Repl. Rate, Lb/Bbl Feed 0.435 (from 2nd reactor) 0.40 (fresh catalyst) 0.40
    Residue (975°F+) Conversion, V% 76 26 99.6
    Hydrodesulfurization, W% 80 58 93.5
    Hydrodemetallization, W% 84 57 99
    Hydrodenitrogenation, W% 35 20 67
    Product Yields, % of Fresh Feed
    C1-C3 Gas, W% -- -- 3.9
    C4-350°F, Naphtha, V% -- -- 21.0
    350-650°F Mid Distillate, V% -- -- 52.2
    650-975°F Gas Oil, V% -- -- 39.1
    975°F+ Residue, V% -- -- 0.4
    C4-975°F Distillate, V% -- -- 112.3
  • As seen from the Table 1 results, by using the selected operating conditions and matching catalyst activity for the two staged reactors, the overall hydroconversion of the feedstock obtained by recycling the vacuum bottoms fraction back to the first stage reactor is 99.6 vol%, along with high percentage demetallization and desulfurization of the feedstock. A comparable improvement is also shown for the distillate product yields, with the total yield of the 975°F+ material being only 0.4% by volume.
  • Although this invention has been described broadly and in terms of preferred embodiments, it will be understood that modifications and variations of the process can be made all within the spirit and scope of the invention, which is defined by the following claims.

Claims (14)

  1. A process for catalytic two-stage hydroconversion of heavy petroleum-based feedstocks to provide high hydroconversion of the feed and produce lower-boiling hydrocarbon liquids and gases, said process comprising:
    (a) feeding a heavy hydrocarbon liquid feedstock containing at least 40 vol, % normally boiling above 975°F together with hydrogen into a first stage catalytic ebullated bed reactor containing a bed of particulate catalyst, said catalyst containing active 2-25 wt.% total metal oxides selected from the group consisting of cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof deposited on a support material selected from the group of alumina, silica and combinations thereof, said reactor being maintained at 820-875°F temperature, 1500-3500 psig hydrogen partial pressure, and 0.30-1.0 volume feed/hr/volume reactor (Vf/hr/Vr) overall space velocity, and catalyst replacement rate of 0.15-0.90 pound catalyst per barrel of fresh feedstock, for partially hydroconverting the feedstock and producing an effluent material containing gaseous and liquid fractions;
    (b) phase separating said partially hydroconverted effluent material, withdrawing the gaseous fraction and passing the liquid fraction on to a second stage catalytic ebullated bed reactor containing a bed of particulate catalyst, said catalyst containing 2-25 wt.% total active metal oxides selected from the group consisting of cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof deposited on a support material selected from the group of alumina, silica and combinations thereof, said reactor being maintained at 700-800°F temperature, 1500-3500 psi hydrogen partial pressure, and 0.10-0.80 volume feed/hr/volume reactor (Vf/hr/Vr) space velocity, and catalyst replacement rate of 0.15-0.90 pound catalyst per barrel of the feedstock for maximizing catalytic hydrogenation reactions and further hydroconverting the liquid fraction therein to produce hydrocarbon gases and lower boiling liquid fractions;
    (c) removing said hydrocarbon gases and liquid fractions from said second stage reactor, separating the hydrocarbon gases from said liquid fractions and withdrawing the liquid fractions;
    (d) distilling said liquid fractions to produce a medium boiling hydrocarbon liquid product having normal boiling range of 400-850°F and a vacuum bottoms material having a normal boiling point above about 850°F; and
    (e) recycling said vacuum bottoms material directly to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of vacuum bottoms material to fresh feedstock of 0.2-1.5/1, so as to achieve at least about 75 vol % conversion of the 975°F+ fraction in the feed to lower boiling hydrocarbon material and produce increased yields of said medium boiling hydrocarbon liquid product.
  2. A hydroconversion process according to claim 1, wherein said first stage reaction conditions are 825-850°F temperature, 2000-3000 psig hydrogen partial pressure, and 0.40-0.80 Vf/Hr/Vr space velocity.
  3. A hydroconversion process according to claim 1, wherein said second stage reaction conditions are 730-780°F temperature, 2000-3000 psig hydrogen partial pressure, and 0.20-0.60 Vf/Hr/Vr space velocity.
  4. A hydroconversion process according to claim 1, wherein said recycled vacuum bottoms material has a normal boiling point above about 900°F.
  5. A hydroconversion process according to claim 1, wherein the volume ratio of vacuum bottoms material recycled to said first stage reactor to the fresh feedstock fed to said first stage reactor is about 0.5-1.0/1.
  6. A hydroconversion process according to claim 1, wherein the catalyst used in said first stage and second stage reactors contains 5-20 wt.% total active metals and have total pore volume of 0.30-1.50 cc/gm, total surface area of 100-400 m2/gm and average pore diameter of at least 50 angstrom units.
  7. A hydroconversion process according to claim 1, wherein the catalyst used in the first stage and second stage reactors has total pore volume of 0.50-1.20 cc/gm, total surface area of 150-350 m2/gm and average pore diameter of 100-250 angstrom units.
  8. A hydroconversion process according to claim 1, wherein the catalyst used in said second stage catalytic reactor contains 5-20 wt.% cobalt-molybdenum on alumina support material.
  9. A hydroconversion process according to claim 1, wherein the catalyst used in said second stage catalytic reactor contains 5-20 wt.% nickel-molybdenum on alumina support material.
  10. A hydroconversion process according to claim 1, wherein used catalyst is withdrawn from said second stage catalytic reactor and passed to said first stage catalytic reactor as the catalyst addition therein and catalyst replacement rate is 0.20-0.80 pound catalyst per barrel of the fresh feedstock to said first stage reactor.
  11. A hydroconversion process according to claim 1, wherein the feedstock is petroleum residua material having 75-100 vol % normally boiling above 975°F and containing 10-50 wt.% Conradson Carbon Residue (CCR) and up to 1,000 wppm total metals.
  12. A hydroconversion process according to claim 1, wherein the feedstock is bitumen derived from tar sands.
  13. A hydroconversion process according to claim 9, wherein the feedstock contains 15-40 wt.% Conradson Carbon Residue (CCR) and 100-600 wppm total metals (Va + Ni).
  14. A process for catalytic two-stage hydroconversion of heavy petroleum feedstocks to provide high hydroconversion of the feed and produce increased yields of lower boiling hydrocarbon liquids and gases, said process comprising:
    (a) feeding a petroleum resid feedstock having 40-90 vol % boiling above 975°F and containing 15-40 wt.% Conradson Carbon Residue (CCR) and 100-600 wppm total metals (Va + Ni) together with hydrogen into a first stage catalytic reactor containing an ebullated bed of particulate catalyst, said catalyst containing 5-20 wt.% total active metal oxides selected from the group consisting of cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof deposited on a support material selected from the group of alumina, silica and combinations thereof, said catalyst having 0.30-1.50 cc/gm total pore volume and 100-400 m2/gm surface area, said reactor being maintained at 825-850°F temperature, 2000-3000 psig hydrogen partial pressure, and 0.40-0.80 volume feed per hour per volume of reactor (Vf/Hr/Vr) overall space velocity for partially hydroconverting the feedstock to produce an effluent material containing gaseous and liquid fractions;
    (b) phase separating said partially hydroconverted effluent material, withdrawing the gaseous fraction and passing the liquid fraction on to a second stage catalytic ebullated bed reactor containing a bed of particulate catalyst, said catalyst containing 5-20 wt.% total active metal oxides selected from the group consisting of cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof deposited on a support material selected from the group of alumina, silica and combinations thereof, said catalyst having 0.30-1.50 cc/gm total pore volume and 100-400 m2/gm surface area, said reactor being maintained at 730-780°F temperature, 2000-3000 psig hydrogen partial pressure, and 0.20-0.60 Vf/Hr/Vr overall space velocity, and catalyst replacement rate of 0.15-0.90 pound fresh catalyst per barrel of the feedstock for maximizing catalytic hydrogenation reactions and further hydroconverting the liquid material therein to produce hydrocarbon gases and lower boiling liquid fractions;
    (c) removing said hydrocarbon gas and liquid fractions from said second stage reactor, separating said hydrocarbon gases from said liquid fractions, and withdrawing the liquid fractions;
    (d) distilling said liquid fractions to produce a medium boiling hydrocarbon liquid product having a normal boiling range of 400-900°F and also a vacuum bottoms material having a normal boiling point above 900°F; and
    (e) recycling said vacuum bottoms material directly back to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of recycled vacuum bottoms material to fresh feedstock of about 0.5-1.0/1, and withdrawing used catalyst from said second stage catalytic reactor and passing it to said first stage catalytic reactor as catalyst addition therein at a catalyst replacement rate of 0.15-0.90 pounds catalyst per barrel of feedstock, so as to achieve substantially complete overall conversion of the 975°F+ fraction to lower boiling hydrocarbon material and produce increased yields of said medium boiling hydrocarbon liquid product.
EP96103874A 1995-03-16 1996-03-12 Complete catalytic hydroconversion process for heavy petroleum feedstocks Expired - Lifetime EP0732389B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40601695A 1995-03-16 1995-03-16
US406016 1995-03-16

Publications (3)

Publication Number Publication Date
EP0732389A2 true EP0732389A2 (en) 1996-09-18
EP0732389A3 EP0732389A3 (en) 1996-12-18
EP0732389B1 EP0732389B1 (en) 2001-08-01

Family

ID=23606192

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96103874A Expired - Lifetime EP0732389B1 (en) 1995-03-16 1996-03-12 Complete catalytic hydroconversion process for heavy petroleum feedstocks

Country Status (5)

Country Link
EP (1) EP0732389B1 (en)
JP (1) JP3864319B2 (en)
CA (1) CA2171894C (en)
DE (1) DE69614165T2 (en)
ZA (1) ZA961830B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001098436A1 (en) * 2000-06-19 2001-12-27 Institut Francais Du Petrole Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors
EP1466958A2 (en) * 2003-02-26 2004-10-13 Institut Francais Du Petrole Process and installation for the treatment of hydrocarbons and for the separation of the phases produced by this treatment
US7060228B2 (en) 2001-07-06 2006-06-13 Institut Francais Du Petrole Internal device for separating a mixture that comprises at least one gaseous phase and one liquid phase
WO2009141703A2 (en) * 2008-05-20 2009-11-26 I F P Selectively heavy gas oil recycle for optimal integration of heavy oil conversion and vaccum gas oil treating
ITMI20130131A1 (en) * 2013-01-30 2014-07-31 Luigi Patron IMPROVED PRODUCTIVITY PROCESS FOR THE CONVERSION OF HEAVY OILS
CN105441126A (en) * 2014-09-24 2016-03-30 中国石油化工股份有限公司 Residual oil hydrotreating method
CN105524653A (en) * 2014-09-29 2016-04-27 中国石油化工股份有限公司 Hydrotreatment method for residual oil
US11732203B2 (en) 2017-03-02 2023-08-22 Hydrocarbon Technology & Innovation, Llc Ebullated bed reactor upgraded to produce sediment that causes less equipment fouling

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2412363C (en) * 2000-06-19 2010-03-30 James B. Mac Arthur Method for presulfiding and preconditioning of residuum hydroconversion catalyst
JP5318410B2 (en) 2004-04-28 2013-10-16 ヘッドウォーターズ ヘビー オイル リミテッド ライアビリティ カンパニー Boiling bed hydroprocessing method and system and method for upgrading an existing boiling bed system
US10941353B2 (en) 2004-04-28 2021-03-09 Hydrocarbon Technology & Innovation, Llc Methods and mixing systems for introducing catalyst precursor into heavy oil feedstock
AU2005265004A1 (en) 2004-06-17 2006-01-26 Exxonmobil Research And Engineering Company Catalyst combination and two-step hydroprocessing method for heavy hydrocarbon oil
US20070140927A1 (en) * 2005-12-16 2007-06-21 Chevron U.S.A. Inc. Reactor for use in upgrading heavy oil admixed with a highly active catalyst composition in a slurry
EP2234710A2 (en) 2007-11-28 2010-10-06 Saudi Arabian Oil Company Process for catalytic hydrotreating of sour crude oils
US8372267B2 (en) 2008-07-14 2013-02-12 Saudi Arabian Oil Company Process for the sequential hydroconversion and hydrodesulfurization of whole crude oil
US9260671B2 (en) 2008-07-14 2016-02-16 Saudi Arabian Oil Company Process for the treatment of heavy oils using light hydrocarbon components as a diluent
FR2940313B1 (en) * 2008-12-18 2011-10-28 Inst Francais Du Petrole HYDROCRACKING PROCESS INCLUDING PERMUTABLE REACTORS WITH LOADS CONTAINING 200PPM WEIGHT-2% WEIGHT OF ASPHALTENES
EP2445997B1 (en) 2009-06-22 2021-03-24 Saudi Arabian Oil Company Demetalizing and desulfurizing virgin crude oil for delayed coking
CN103857771B (en) * 2011-07-29 2016-06-01 沙特阿拉伯石油公司 For the ebullated bed method of the raw material containing the hydrogen dissolved
US9790440B2 (en) 2011-09-23 2017-10-17 Headwaters Technology Innovation Group, Inc. Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker
US9644157B2 (en) 2012-07-30 2017-05-09 Headwaters Heavy Oil, Llc Methods and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking
US11414607B2 (en) 2015-09-22 2022-08-16 Hydrocarbon Technology & Innovation, Llc Upgraded ebullated bed reactor with increased production rate of converted products
US11414608B2 (en) 2015-09-22 2022-08-16 Hydrocarbon Technology & Innovation, Llc Upgraded ebullated bed reactor used with opportunity feedstocks
US11421164B2 (en) 2016-06-08 2022-08-23 Hydrocarbon Technology & Innovation, Llc Dual catalyst system for ebullated bed upgrading to produce improved quality vacuum residue product
US11118119B2 (en) 2017-03-02 2021-09-14 Hydrocarbon Technology & Innovation, Llc Upgraded ebullated bed reactor with less fouling sediment
CA3057131C (en) 2018-10-17 2024-04-23 Hydrocarbon Technology And Innovation, Llc Upgraded ebullated bed reactor with no recycle buildup of asphaltenes in vacuum bottoms

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1193213A (en) * 1967-04-25 1970-05-28 Atlantic Richfield Co Petroleum Purification
GB2066287A (en) * 1980-12-09 1981-07-08 Lummus Co Hydrogenation of high boiling hydrocarbons
US4457831A (en) * 1982-08-18 1984-07-03 Hri, Inc. Two-stage catalytic hydroconversion of hydrocarbon feedstocks using resid recycle
EP0244244A2 (en) * 1986-04-30 1987-11-04 Exxon Research And Engineering Company Process for catalytic-slurry hydroconversion of hydrocarbons

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1193213A (en) * 1967-04-25 1970-05-28 Atlantic Richfield Co Petroleum Purification
GB2066287A (en) * 1980-12-09 1981-07-08 Lummus Co Hydrogenation of high boiling hydrocarbons
US4457831A (en) * 1982-08-18 1984-07-03 Hri, Inc. Two-stage catalytic hydroconversion of hydrocarbon feedstocks using resid recycle
EP0244244A2 (en) * 1986-04-30 1987-11-04 Exxon Research And Engineering Company Process for catalytic-slurry hydroconversion of hydrocarbons

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001098436A1 (en) * 2000-06-19 2001-12-27 Institut Francais Du Petrole Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors
US7060228B2 (en) 2001-07-06 2006-06-13 Institut Francais Du Petrole Internal device for separating a mixture that comprises at least one gaseous phase and one liquid phase
EP1466958A2 (en) * 2003-02-26 2004-10-13 Institut Francais Du Petrole Process and installation for the treatment of hydrocarbons and for the separation of the phases produced by this treatment
EP1466958A3 (en) * 2003-02-26 2005-10-19 Institut Francais Du Petrole Process and installation for the treatment of hydrocarbons and for the separation of the phases produced by this treatment
RU2495086C2 (en) * 2008-05-20 2013-10-10 Ифп Энержи Нувелль Selective recycling of heavy gasoil for purpose of optimal integration of heavy crude oil and vacuum gas oil refining
WO2009141703A3 (en) * 2008-05-20 2010-06-17 I F P Selectively heavy gas oil recycle for optimal integration of heavy oil conversion and vaccum gas oil treating
WO2009141703A2 (en) * 2008-05-20 2009-11-26 I F P Selectively heavy gas oil recycle for optimal integration of heavy oil conversion and vaccum gas oil treating
ITMI20130131A1 (en) * 2013-01-30 2014-07-31 Luigi Patron IMPROVED PRODUCTIVITY PROCESS FOR THE CONVERSION OF HEAVY OILS
WO2014118814A3 (en) * 2013-01-30 2015-03-05 Luigi Patron Process with improved productivity for the conversion of heavy oils
US9884999B2 (en) 2013-01-30 2018-02-06 Luigi Patron Process with improved productivity for the conversion of heavy oils
CN105441126A (en) * 2014-09-24 2016-03-30 中国石油化工股份有限公司 Residual oil hydrotreating method
CN105441126B (en) * 2014-09-24 2017-05-24 中国石油化工股份有限公司 Residual oil hydrotreating method
CN105524653A (en) * 2014-09-29 2016-04-27 中国石油化工股份有限公司 Hydrotreatment method for residual oil
CN105524653B (en) * 2014-09-29 2017-05-24 中国石油化工股份有限公司 Hydrotreatment method for residual oil
US11732203B2 (en) 2017-03-02 2023-08-22 Hydrocarbon Technology & Innovation, Llc Ebullated bed reactor upgraded to produce sediment that causes less equipment fouling

Also Published As

Publication number Publication date
EP0732389B1 (en) 2001-08-01
JPH08325580A (en) 1996-12-10
EP0732389A3 (en) 1996-12-18
ZA961830B (en) 1997-10-31
CA2171894C (en) 2006-06-06
JP3864319B2 (en) 2006-12-27
DE69614165T2 (en) 2001-11-22
DE69614165D1 (en) 2001-09-06
CA2171894A1 (en) 1996-09-17

Similar Documents

Publication Publication Date Title
EP0732389B1 (en) Complete catalytic hydroconversion process for heavy petroleum feedstocks
US6841062B2 (en) Crude oil desulfurization
US6277270B1 (en) Process for converting heavy petroleum fractions that comprise a fixed-bed hydrotreatment stage, an ebullated-bed conversion stage, and a catalytic cracking stage
JP6474461B2 (en) Integrated ebullated bed method for whole crude oil improvement
US5925238A (en) Catalytic multi-stage hydrodesulfurization of metals-containing petroleum residua with cascading of rejuvenated catalyst
US6270654B1 (en) Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors
US6190542B1 (en) Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds
US4427535A (en) Selective operating conditions for high conversion of special petroleum feedstocks
US5522983A (en) Hydrocarbon hydroconversion process
KR20190082994A (en) Multi-stage resid hydrocracking
US4176048A (en) Process for conversion of heavy hydrocarbons
US9920264B2 (en) Process of hydroconversion-distillation of heavy and/or extra-heavy crude oils
US4576710A (en) Catalyst desulfurization of petroleum residua feedstocks
JPH0753967A (en) Hydrotreatment of heavy oil
AU714130B2 (en) Hydroconversion process
US6280606B1 (en) Process for converting heavy petroleum fractions that comprise a distillation stage, ebullated-bed hydroconversion stages of the vacuum distillate, and a vacuum residue and a catalytic cracking stage
KR100188422B1 (en) Method of upgrading residua
JP4271585B2 (en) Oil refining method and refiner
EP1299507B1 (en) Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors
US4469587A (en) Process for the conversion of asphaltenes and resins in the presence of steam, ammonia and hydrogen
JPH05230473A (en) Treatment of heavy hydrocarbon oil
JPH05239472A (en) Method of processing heavy hydrocarbon oil
KR100552610B1 (en) Process for converting heavy petroleum fractions that comprise a distillation stage, ebullated-bed hydroconversion stages of the vacuum distillate, and a vacuum residue and a catalytic cracking stage
JPH05230474A (en) Treatment of heavy hydrocarbon oil
JPH07166176A (en) Production of low-sulfur gas oil

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE GB IT NL

17P Request for examination filed

Effective date: 19970430

17Q First examination report despatched

Effective date: 19991115

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE GB IT NL

REF Corresponds to:

Ref document number: 69614165

Country of ref document: DE

Date of ref document: 20010906

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20030224

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20030321

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040312

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040331

BERE Be: lapsed

Owner name: INSTITUT FRANCAIS DU *PETROLE

Effective date: 20040331

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20040312

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 69614165

Country of ref document: DE

Owner name: IFP ENERGIES NOUVELLES, FR

Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, RUEIL-MALMAISON, HAUTS-DE-SEINE, FR

Effective date: 20110331

Ref country code: DE

Ref legal event code: R081

Ref document number: 69614165

Country of ref document: DE

Owner name: IFP ENERGIES NOUVELLES, FR

Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, RUEIL-MALMAISON, FR

Effective date: 20110331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20150227

Year of fee payment: 20

Ref country code: NL

Payment date: 20150319

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20150330

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69614165

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20160311