Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3901792 A
Publication typeGrant
Publication dateAug 26, 1975
Filing dateJun 24, 1974
Priority dateMay 22, 1972
Publication numberUS 3901792 A, US 3901792A, US-A-3901792, US3901792 A, US3901792A
InventorsGovanon Nongbri, William C Rovesti, Ronald H Wolk
Original AssigneeHydrocarbon Research Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Multi-zone method for demetallizing and desulfurizing crude oil or atmospheric residual oil
US 3901792 A
Abstract  available in
Images(1)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent (1 1 Wolk et al.

[ Aug. 26, 1975 MULTLZONE METHOD FOR Primary ExaminerDelbert E. Gantz DEMETALLIZIN AND E L UB N Assistant Examiner-G. J. Crasanakis CRUDE OIL R ATMOSPHERIC RESIDUAL 57 T T OIL The high level desulfurization of petroleum residuums [75] lnventorsi Rflnald wolk, Lawrence P, normally having at least 100 ppm of metals from the Mercer n y, GOYaIIOIl groups of vanadium and nickel is accomplished by an g Levitlow"; William initial contact stage with a contact material such as NeWtOWn, both 0f Porocel, having extensive macroporosity with more [73] Assigneez Hydrocarbon Research, Inc" New than 0.l5 cc/gram pore volume in pores greater than York N Y lA in diameter operating as an ebullated bed under optimum demetallization conditions in the range of [22] File Jun 24, 1 4 730825F (preferably 760780F), and hydrogen 2] A L N 482,322 partial pressure of l0OO-2500 psi (preferably 1 pp 0 1500-2000 psi), followed by a removal of effluent vapors and a further ebullated bed contact of the liquid Relmed Application Data with a highly active hydrodesulfurization catalyst [63] Continuation of Ser. No. 255,452, May 22, 1972, which would ordinarily be rapidly poisoned by these abandoned, residuums. By control of the first stage reaction conditions including space velocity, in the range of 0.20 to [52] S. Cl- 208/210; 208/2l3; 208/216; 1.5 volume of feed per hour per volume of reactor, 208/25] H and obtaining a high degree of demetallization in the [5 l Int. Cl ClOg 23/02 order of -80% or more deposit of metals on the first Fifld Search 25! stage contact particles, so that the amount of vana- 21 1 dium removed from the oil and taken up on the catalyst in the second stage was no more than 20 ppm, the [56] References Cited life of the catalyst in the second stage was very greatly lengthened. The catalyst in the second stage has little UNITED STATES PATENTS macroporosity with no more than 0.l0 cc/gram in 3,322,666 5/1967 Beuthcr et al. 208/[12 pores greater than 125A in diameter so as to exclude 3.413.234 /1 68 Ch rv nak t all.v 208/210 most of the metal containing molecules which were 3.530.066 9 u ala el a 203/251 H not contacted in the first stage. This combination of the reaction steps makes it possible to achieve in exe e a c v 3,788,973 H1974 wolk ct a]. I g I 208/25] H cess of desulfurization of these residuums. 3,844,933 l0/l974 Wolk et al. 208/25l H 4 Claims, 3 Drawing Figures Gas Products,

Heavy 24 32 Products Contact Portlcles Catalyst i ll I6 2 l0 Feed g- 25 Hydrogen Hydrogen Fraction of PATENTEDAUBZBIQYB 2.901192 Gas Products Heavy 32 Prod ucts Contact Particles l0 Feed l2- Hydrogen 25 Hydrogen Demetulized Feed l I J- o 2 4 s B IO Catalyst Age, Bbl/Lb E 20 'E C 00.9 296 gee 62 Fe?) e 3 :15 U a s 2%" 03in u.|

V ,Vonodium Content of Feed ppm MULTI-ZONE METHOD FOR DEMETALLIZING AND DESULFURIZING CRUDE OIL OR ATMOSPHERIC RESIDUAL OIL This is a continuation of application Ser. No. 255,452, filed May 22, 1972 and now abandoned.

BACKGROUND OF THE INVENTION The ebullated bed hydrodesulfurization of petroleum residuum is disclosed in the Chervenak et a1. U.S. Pat. No. 3,418,234. It is also known that many residuum stocks contain substantial amounts of metals.

However, it has also been observed that in an ebullated bed hydrodesulfurization of a high metals containing residuum, the desulfurization catalyst was rapidly rendered inactive by the deposit of metals on and in the catalyst. This requires a frequent and expensive replacement of the catalyst which is otherwise expressed as low average catalyst life. Previous disclosures of two stage operations in which the second stage was a hydroconversion do not satisfactorily meet the requirements when the object is a desulfurization of high metals containing residuum in that the catalyst replacement cost for the first stage is too high. The maximum vanadium loading without severe activity loss on a catalyst is on the order of 0.3 lbs. vanadium per pound of fresh catalyst. This would be equivalent to limiting the catalyst life on a 400 ppm vanadium feed to less than 3 bbl/lb which is economically prohibitive.

SUMMARY OF THE INVENTION It has now been determined that extremely long catalyst life can be obtained by careful maintenance of the metals content in the feed to a second stage catalyst desulfurization zone below a level in which the amount of vanadium that the second stage catalyst will remove is less than 20 ppm when obtaining desulfurization levels of 75% or more.

By selecting the pore size distribution of the first stage contact particles to be of a larger average size than the second stage catalyst then the vanadium con taining molecules left after the first stage treatment are excluded from entering the pores of the second stage catalyst.

It appears that the vanadium compounds contained in the virgin residuum differ in character in terms of their ability to be removed from the oil. What is done is to take out most of the easily removed vanadium compounds and leave just a few of the more difficult to remove compounds in the feed to the catalytic stage. This reduces the poisoning rate in that catalytic stage to almost a trivial amount.

DESCRIPTION OF THE DRAWING FIG. I is a schematic view of a multiple stage hydrogenation process.

FIG. 2 is a graph of sulfur removal against catalyst age for both virgin and demetallized light Venezuelan atmospheric residuum, and a graph of sulfur removal against catalyst age for both virgin and demetallized heavy Venezuelan atmospheric residuum.

FIG. 3 is a graph showing the amount of desulfurization as a function of the vanadium content of the feed.

DESCRIPTION OF THE PREFERRED EMBODIMENT In accordance with the disclosed invention, a heavy hydrocarbon charge such as a metals containing Venezuelan residuum at 10, together with hydrogen at 12 is introduced into a reactor 14 of the type shown in the US. Pat. No. 25,770. Such a reactor will be suitably charged with a demetallization contact material such as porous alumina, the particles being of an average size between about 60 mesh and 270 mesh. A small makeup of fresh contact particles is combined with the feed at 16. Alternately, contact particles in the form of extrudates of 4 inch to 1/32 inch diameter may be used, or granules of 10 to 60 mesh may be used.

The liquid and gas upflow through the bed of contact particles should be such that it will tend to expand the bed at least 10% based on the bed volume without fluid flow, and such that the particles are all in a random motion in the liquid. Such conditions are described as ebullated in the aforementioned Johanson patent.

Recycle of liquid effluent from above the contact particle interface 15 to below the distributor deck 38 is usually desirable to give proper temperature control and to establish a sufficient upflow velocity to assist in maintaining the particles in random motion in the case of particles in the form of 1/32 to 4 inch diameter ex trudates. This recycle may be accomplished either externally utilizing pump 40, or internally as described in Johanson, supra.

Under the preferred conditions of temperature, pressure, throughput and product composition as hereinafter set forth, a vapor effluent is removed at 18 and a liquid effluent is removed at 20 from the upper portion 22 of the reaction zone 14. The liquid is then conducted to the second stage reactor 24.

In the second stage reactor the liquid feed at 20 joins with additional hydrogen at 26 and passes upwardly through a bed of desulfurization catalyst from the group of nickel, cobalt, molybdenum and tungsten on a carrier from the group of silica, alumina and mixtures thereof. Small amounts of desulfurization makeup catalyst may also be added at 28. A gaseous effluent is removed at 30, and a liquid is removed at 32 from the upper portion 34 of the reactor 24. The catalyst loading used in the second stage reactor 24 is about the same as that used for the contact particles in the first stage reactor 14.

EXAMPLE 1 Desulfurization of Demetallized Feeds Catalyst Deactivation Demetallized Light Venezuelan atmospheric resid (17.3API, 2.09% S, 235 ppm V and 28 ppm Ni) was prepared by passing this feed over porous alumina having more than 0.15 cc/gram of pores greater than A in diameter, operating temperature was 760F and hydrogen partial pressure was 2000 psi. Demetallized feed prepared in this manner was subsequently run over 1/32 inch cobalt molybdate on alumina catalyst having a pore size distribution such that the pore volume in pores having a diameter greater than 125A is less than 0.10 cc/gram. The demetallized Light Vene zuelan stock had an average metals content of about 55 ppm (40 ppm V and 15 ppm Ni).

Results of the desulfurization runs are presented in FIG. 2. The line A in FIG. 2 represents the deactivation curve for a high activity cobalt molybdate on alumina catalyst wherein the feed has been pretreated for demetallization while line A represents the same high activity cobalt molybdate on alumina catalyst when un- Light Venezuelan atmospheric resid was run over H32 inch cobalt molybdenum extrudates where only 1.03 and L97 weight percent, respectively, on a fresh catalyst basis at catalyst age of 9.0 bbl/lb.

EXAMPLE 2 Demetallized Heavy Venezuelan atmospheric resid (12.6APl, 2.8% S, 375 ppm V and 57 ppm Ni) was prepared by passing this feed over porous alumina at 780F and 2000 psi. The resulting demetallized feed,

line B in FIG. 2, having a metals content of 139 ppm 104 ppm V and 35 ppm Ni) was run over 1/32 inch cobalt molybdate on alumina extrudates in order to compare the catalyst deactivation rate of this 139 ppm metals feed with the virgin feed line B. Results of the two desulfurization runs over the same catalyst as used in Example 1 are presented in FIG. 2.

Despite the considerably higher metals level, the de metallized Heavy Venezuelan run up to an age of 2.75 B/lb showed no sign of rapid deactivation. Furthermore, the vanadium removed in this run was only about l8-22 ppm out of 104 ppm compared to 22 ppm out of 36 ppm in the case of Kuwait atmospheric resid over the same catalyst and at the same level of desulfurization.

This last observation is extremely important since it demonstrates that high metals-feeds need not be demetallized to the level of Kuwait atmospheric residuum (an economically prohibitive requirement in many cases) in order to effect a rate of vanadium deposition that will not rapidly deactivate a nonporous high activity desulfurization catalyst.

Table I presents data on the amount of demetallization that occurs when desulfurizing the residuums indicated to 75%. When desulfurizing the virgin feed about 60% demetallization occurs. However, if the feed is demetallized according to our invention before desulfurization, then the amount of dcmetallization that occurs in the desulfurization step is a function ofthc vanadium content of the feed.

The graph of FIG. 3, on log-log scale, for the ordinate, shows the fraction ofvanadium removed from the feed when undergoing a 75% desulfurization. The scale is from O to L0.

The abscissae is the vanadium content of the feed in parts per million to the desulfurization stage and the scale is from 0 to I000.

Lines 50, 52, 54 and 56 represent experimental runs on feeds as folows:

is for a Kuwait atmospheric residuum originally having 36 ppm of vanadium after undergoing demetallization in the first stage.

52 is for a Khafji atmospheric residuum originally having lOO ppm of vanadium after undergoing demetallization in the first stage.

54 is for a Light Venezuelan atmospheric residuum originally having 200 ppm of vanadium after undergoing demetallization in the first stage.

56 is for a Heavy Venezuelan atmospheric residuum originally having 398 ppm of vanadium after undergo ing demetallization in the first stage.

Lines 60, 62, 64 and 66 are mathematical calculations showing the parts per million of vanadium removed from the feed in the second or desulfurization stage as follows:

60 shows 10 ppm vanadium removal.

62 shows 20 ppm vanadium removal.

64 shows 40 ppm vanadium removal.

66 shows 100 ppm vanadium removal.

It is thus possible to determine the extent of demetallization in the first stage necessary to permit second stage demetallization at the rate without depositing more than 20 ppm of vanadium on the catalyst.

For example, it would be necessary to demetallize Heavy Venezuelan atmospheric residuum from 398 ppm to 92 ppm vanadium (Point Z) in a demetallization step in order not to exceed 20 ppm of vanadium deposition on the desulfurization stage catalyst. Analogous values would be 72 for Light Venezuelan atmospheric (Point Y), 53 for Khafii atmospheric residuum (Point X) and 34 Kuwait atmospheric residuum. Since the value for Kuwait atmospheric residuum is so close to the feed value of 36 ppm, it would not be practical to put in a demetallization step for this feed.

TABLE I Vanadium Removal Vanadium When Undergoing 75% Feed Content Desulfurivation Virgin Heavy Venezuelan AB. 400 ppm 45.5 Dcmetallized I72 326 l04 28.8 Virgin Light Venezuelan AB. 200 60.0 Demetal lized 98 26.1 56 32.1 42 166 Virgin Khafji AB. I00 6L0 Virgin Kuwait AB. 36 6 l .3

AB. Atmospheric Bottoms 'lhc preferred operating conditions for the two stages are 1st 2nd Temperature "F 730 v 825 700 K00 Preferred 760 780 720 760 Hydrogen Partial Pressure (psi) 1000 2500 l000 2500 Preferred I500 2000 i500 2000 Space Velocity V/hr/V 0.20 l5 0.3 i 5 Preferred 0.3 0.) 0.5 l l) While we have shown and described a preferred form of embodiment of our invention, we are aware that modifications may be made thereto within the scope and spirit of the description herein and of the claims appended hereinafter.

We claim:

1. A multi-zone method for desulfurizing a crude pe troleum charge or atmospheric residual charge containing at least lUO ppm of metals from the group consisting of vanadium and nickel wherein said charge, in liquid phase, is passed upwardly with hydrogen-rich gas through a first reaction zone containing a particulate contact material and the effluent from said first reaction zone is then passed with hydrogen-rich gas upwardly through a second reaction zone containing a particulate hydrodesulfurization catalyst; under conditions in which said contact material and said hydrodesulfurization catalyst are maintained in random motion in the liquid, and wherein the temperature in said first reaction zone is maintained in the range of 730 to 825F and the hydrogen partial pressure is in the range of lO002500 psi and space velocity in the order of 0.2-1.5 volume of feed/hr/volume of reaction zone, the improvement which comprises:

a. maintaining porous alumina as said contact material in said first reaction zone, said alumina having a pore volume of more than 0.15 cc/gram of pores having a diameter in excess of l25A;

b. maintaining reaction conditions in said second reaction zone substantially at the same pressure as in said first reaction zone with a maximum hydrogen rate of 5000 SCF/barrel, the temperature being between 700 and 800F, the space velocity being between 0.3

and 1.5 volume of feed/hour/volume of reaction space wherein no more than 20 ppm of vanadium is removed in said second zone while a desulfurization of at least percent is achieved in said second zone, said catalyst in said second reaction zone comprising a Group Vl-B metal and iron group metal on alumina, said catalyst having a pore structure with less than 010 cc/gram in pores larger than 125A.

2. The method as claimed in claim 1 wherein said atmospheric residual charge is a heavy Venezuelan atmospheric bottoms containing in the order of 400 ppm of metals and the first stage operation is conducted under conditions to remove approximately 75% of the metals.

3. The method as claimed in claim 1 wherein said atmospheric residual charge is a light Venezuelan atmospheric bottoms containing in the order of 200 ppm of metals and the first stage operation is conducted under conditions to remove approximately 70% of the metals.

4. The method as claimed in claim 1 wherein said atmospheric residual charge is a Khatji atmospheric bottoms having in the order of ppm of metals and the first stage operation is conducted under conditions to remove approximately 60% of the metals.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3322666 *Aug 25, 1964May 30, 1967Gulf Research Development CoChemical process for hydrocracking and hydrorefining of hydrocarbon oils
US3418234 *Feb 16, 1967Dec 24, 1968Hydrocarbon Research IncHigh conversion hydrogenation
US3530066 *Jul 29, 1968Sep 22, 1970Nippon Oil Co LtdCatalytic hydrotreating process of petroleum hydrocarbons containing asphaltenes
US3623974 *Dec 10, 1969Nov 30, 1971Cities Service Res & Dev CoHydrotreating a heavy hydrocarbon oil in an ebullated catalyst zone and a fixed catalyst zone
US3725251 *Nov 8, 1971Apr 3, 1973Hydrocarbon Research IncTwo-stage hydrodesulfurization of a high metal content hydrocarbon feed
US3788973 *Dec 23, 1971Jan 29, 1974Hydrocarbon Research IncHigh conversion hydrogenation
US3844933 *Oct 16, 1972Oct 29, 1974Hydrocarbon Research IncHydroconversion of coal-derived oils
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3964995 *Jun 21, 1974Jun 22, 1976Hydrocarbon Research, Inc.Hydrodesulfurization process
US3980551 *Dec 18, 1975Sep 14, 1976Hydrocarbon Research, Inc.Refining of waste lube oil to prepare usable lubestock
US4217206 *Jul 20, 1977Aug 12, 1980Hydrocarbon Research, Inc.Extending life of demetallization catalyst
US4301037 *Apr 1, 1980Nov 17, 1981W. R. Grace & Co.Extruded alumina catalyst support having controlled distribution of pore sizes
US4317711 *Sep 12, 1980Mar 2, 1982Mobil Oil CorporationCoprocessing of residual oil and coal
US4334976 *Jan 13, 1981Jun 15, 1982Mobil Oil CorporationUpgrading of residual oil
US4378308 *Nov 26, 1980Mar 29, 1983Mobil Oil CorporationPoison-resistant hydrodesulfurization catalyst
US4431526 *Jul 6, 1982Feb 14, 1984Union Oil Company Of CaliforniaMultiple-stage hydroprocessing of hydrocarbon oil
US4452911 *Aug 10, 1983Jun 5, 1984Hri, Inc.Frangible catalyst pretreatment method for use in hydrocarbon hydrodemetallization process
US4457831 *Aug 18, 1982Jul 3, 1984Hri, Inc.Two-stage catalytic hydroconversion of hydrocarbon feedstocks using resid recycle
US4460707 *Dec 28, 1982Jul 17, 1984Union Oil Company Of CaliforniaHydroprocessing catalyst and method for preparing it
US4498972 *Dec 30, 1983Feb 12, 1985Institut Francais Du PetroleHydrotreatment process for converting a heavy hydrocarbon fraction containing sulfur impurities and metal impurities to a lighter oil, in at least two steps
US4548710 *Mar 30, 1984Oct 22, 1985Union Oil Company Of CaliforniaHydrocarbon processing
US4564439 *Jun 29, 1984Jan 14, 1986Chevron Research CompanyTwo-stage, close-coupled thermal catalytic hydroconversion process
US4576710 *Nov 9, 1984Mar 18, 1986Hri, Inc.Catalyst desulfurization of petroleum residua feedstocks
US4761220 *Oct 31, 1984Aug 2, 1988Chevron Research CompanyHydroprocessing catalyst fines as a first-stage catalyst in a two-stage, close-coupled thermal catalytic hydroconversion process
US4802974 *Mar 12, 1987Feb 7, 1989Phillips Petroleum CompanyHydrofining employing treated alumina material in fixed beds
US4828683 *Feb 6, 1987May 9, 1989Phillips Petroleum CompanyHydrofining employing a support material for fixed beds
US4846962 *Feb 12, 1987Jul 11, 1989Exxon Research And Engineering CompanyRemoval of basic nitrogen compounds from extracted oils by use of acidic polar adsorbents and the regeneration of said adsorbents
US4870044 *Oct 13, 1988Sep 26, 1989Phillips Petroleum CompanyTreated alumina material for fixed hydrofining beds
US4895816 *Jan 9, 1989Jan 23, 1990Gardner Lloyd ESupport material containing catalyst for fixed hydrofining beds
US4925554 *Feb 5, 1988May 15, 1990Catalysts & Chemicals Industries Co., Ltd.Hydrotreating process for heavy hydrocarbon oils
US5320741 *Apr 9, 1992Jun 14, 1994Stone & Webster Engineering CorporationCombination process for the pretreatment and hydroconversion of heavy residual oils
US5417846 *Apr 14, 1993May 23, 1995Institut Francais Du PetroleHydrotreatment method for a petroleum residue or heavy oil with a view to refining them and converting them to lighter fractions
US7390869 *Jun 13, 2005Jun 24, 2008Eastman Chemical CompanyProcess for removing metal species in the presence of hydrogen and a porous material and polyester polymer containing reduced amounts of metal species
US7402547Dec 16, 2004Jul 22, 2008Shell Oil CompanySystems and methods of producing a crude product
US7413646Dec 16, 2004Aug 19, 2008Shell Oil CompanySystems and methods of producing a crude product
US7416653Dec 16, 2004Aug 26, 2008Shell Oil CompanySystems and methods of producing a crude product
US7534342Dec 16, 2004May 19, 2009Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7588681Dec 16, 2004Sep 15, 2009Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7591941Dec 16, 2004Sep 22, 2009Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7615196Nov 10, 2009Shell Oil CompanySystems for producing a crude product
US7625481Dec 1, 2009Shell Oil CompanySystems and methods of producing a crude product
US7628908Dec 8, 2009Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7648625Jan 19, 2010Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7651604Jul 9, 2003Jan 26, 2010Instituto Mexicano Del PetroleoProcess for the catalytic hydrotreatment of heavy hydrocarbons of petroleum
US7674368Mar 9, 2010Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7674370Mar 9, 2010Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7678264Mar 16, 2010Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7736490Dec 16, 2004Jun 15, 2010Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7745369Jun 29, 2010Shell Oil CompanyMethod and catalyst for producing a crude product with minimal hydrogen uptake
US7749374Oct 3, 2007Jul 6, 2010Shell Oil CompanyMethods for producing a crude product
US7763160Jul 27, 2010Shell Oil CompanySystems and methods of producing a crude product
US7780844Aug 24, 2010Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7807046Dec 16, 2004Oct 5, 2010Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7811445Oct 12, 2010Shell Oil CompanySystems and methods of producing a crude product
US7828958Nov 9, 2010Shell Oil CompanySystems and methods of producing a crude product
US7837863Nov 23, 2010Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7854833May 12, 2008Dec 21, 2010Shell Oil CompanySystems and methods of producing a crude product
US7879223Feb 1, 2011Shell Oil CompanySystems and methods of producing a crude product
US7918992Apr 7, 2006Apr 5, 2011Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7955499Jun 7, 2011Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7959796Jun 14, 2011Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US7959797Jun 14, 2011Shell Oil CompanySystems and methods of producing a crude product
US8025791Sep 27, 2011Shell Oil CompanySystems and methods of producing a crude product
US8025794Sep 27, 2011Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US8070936Jan 27, 2009Dec 6, 2011Shell Oil CompanySystems and methods of producing a crude product
US8070937Dec 6, 2011Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US8163166May 12, 2008Apr 24, 2012Shell Oil CompanySystems and methods of producing a crude product
US8241489Aug 14, 2012Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US8268164Sep 18, 2012Shell Oil CompanySystems and methods of producing a crude product
US8372267Feb 12, 2013Saudi Arabian Oil CompanyProcess for the sequential hydroconversion and hydrodesulfurization of whole crude oil
US8394254Mar 12, 2013Shell Oil CompanyCrude product composition
US8475651Mar 25, 2009Jul 2, 2013Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US8481450Mar 9, 2011Jul 9, 2013Shell Oil CompanyCatalysts for producing a crude product
US8491779Jun 21, 2010Jul 23, 2013Saudi Arabian Oil CompanyAlternative process for treatment of heavy crudes in a coking refinery
US8506794Dec 16, 2004Aug 13, 2013Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US8608938Apr 14, 2011Dec 17, 2013Shell Oil CompanyCrude product composition
US8608946Dec 16, 2004Dec 17, 2013Shell Oil CompanySystems, methods, and catalysts for producing a crude product
US8613851Apr 14, 2011Dec 24, 2013Shell Oil CompanyCrude product composition
US8632673Nov 26, 2008Jan 21, 2014Saudi Arabian Oil CompanyProcess for catalytic hydrotreating of sour crude oils
US8663453Apr 14, 2011Mar 4, 2014Shell Oil CompanyCrude product composition
US9260671Jul 14, 2009Feb 16, 2016Saudi Arabian Oil CompanyProcess for the treatment of heavy oils using light hydrocarbon components as a diluent
US20030229583 *Dec 7, 2001Dec 11, 2003Sandra CottenMethods of coordinating products and service demonstrations
US20050167323 *Dec 16, 2004Aug 4, 2005Wellington Scott L.Systems and methods of producing a crude product
US20060006556 *Jun 27, 2005Jan 12, 2006Chen Hung YGas supply device by gasifying burnable liquid
US20060278039 *Jun 13, 2005Dec 14, 2006Zhufang LiuProcess for removing metal species in the presence of hydrogen and a porous material and polyester polymer containing reduced amounts of metal species
US20070187294 *Jul 9, 2003Aug 16, 2007Jorge Ancheyta JuarezProcess for the catalytic hydrotretment of heavy hydrocarbons of petroleum
US20090139902 *Nov 26, 2008Jun 4, 2009Saudi Arabian Oil CompanyProcess for catalytic hydrotreating of sour crude oils
US20100018904 *Jan 28, 2010Saudi Arabian Oil CompanyPrerefining Process for the Hydrodesulfurization of Heavy Sour Crude Oils to Produce Sweeter Lighter Crudes Using Moving Catalyst System
US20100025291 *Jul 14, 2009Feb 4, 2010Saudi Arabian Oil CompanyProcess for the Treatment of Heavy Oils Using Light Hydrocarbon Components as a Diluent
US20100025293 *Jul 10, 2009Feb 4, 2010Saudi Arabian Oil CompanyProcess for the Sequential Hydroconversion and Hydrodesulfurization of Whole Crude Oil
US20110083996 *Apr 14, 2011Saudi Arabian Oil CompanyAlternative Process for Treatment of Heavy Crudes in a Coking Refinery
US20110192762 *Aug 11, 2011Scott Lee WellingtonCrude product composition
WO2005005581A1 *Jul 9, 2003Jan 20, 2005Instituto Mexicano Del PetróleoMethod for the catalytic hydroprocessing of heavy petroleum hydrocarbons
Classifications
U.S. Classification208/210, 208/213, 208/216.0PP, 208/216.00R, 208/251.00H
International ClassificationC10G45/16
Cooperative ClassificationC10G45/16, C10G2300/107
European ClassificationC10G45/16
Legal Events
DateCodeEventDescription
Oct 17, 1983ASAssignment
Owner name: HRI, INC., 1313 DOLLEY MADISON BLVD, MC LEANN, VA.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HYDROCARBON RESEARCH, INC.;REEL/FRAME:004180/0621
Effective date: 19830331