EP0577413A1 - Improved hydroconversion process - Google Patents

Improved hydroconversion process Download PDF

Info

Publication number
EP0577413A1
EP0577413A1 EP93305127A EP93305127A EP0577413A1 EP 0577413 A1 EP0577413 A1 EP 0577413A1 EP 93305127 A EP93305127 A EP 93305127A EP 93305127 A EP93305127 A EP 93305127A EP 0577413 A1 EP0577413 A1 EP 0577413A1
Authority
EP
European Patent Office
Prior art keywords
oil
metal
molybdenum
catalyst
compound
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.)
Withdrawn
Application number
EP93305127A
Other languages
German (de)
English (en)
French (fr)
Inventor
Michael Kevin Porter
Glenn Allen Clausen
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.)
Texaco Development Corp
Original Assignee
Texaco Development Corp
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 Texaco Development Corp filed Critical Texaco Development Corp
Publication of EP0577413A1 publication Critical patent/EP0577413A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used

Definitions

  • This invention relates to the hydroconversion of heavy hydrocarbon oils. More particularly, it relates to a hydrotreating catalyst system with improved cumulative pore volume properties and to processes for producing and using such material.
  • US-A-4,579,646 discloses a bottoms visbreaking hydroconversion process wherein hydrocarbon charge is partially coked, and the coke is contacted within the charge stock with an oil-soluble metal compound of a metal of Group IV-B, V-B, VII-B, or VIII to yield a hydroconversion catalyst.
  • US-A-4,226,742 discloses catalyst for the hydroconversion of heavy hydrocarbon oils formed in situ from oil-soluble metal compound by heating in the presence of hydrogen.
  • Oil soluble metal compound is added in amounts 10-950 ppm, preferably 50-200, to feedstock.
  • This mixture is converted to a solid, noncolloidal form by heating the mixture at 325-415°C in the presence of hydrogen gas.
  • Hydroconversion is effected at 26-482°C and then the catalytic solids are separated from the hydroconversion effluent.
  • US-A-4,564,441 discloses hydrofining in the presence of a decomposable compound of a metal (Cu, Zn, III-B, IV-B, VI-B, VII-B, or VIII) mixed with a hydrocarbon-containing feed stream; and the mixture is then contacted with a "suitable refractory inorganic material" such as alumina.
  • a decomposable compound of a metal Cu, Zn, III-B, IV-B, VI-B, VII-B, or VIII
  • US-A-4,557,824 discloses demetallization in the presence of a decomposable compound of a VI-B, VII-B, or VIII metal admitted with the charge and a heterogeneous catalyst containing a phosphate of Zr, Co, or Fe.
  • US-A-4,134,825 discloses hydroconversion of heavy hydrocarbons in the presence of an oil-soluble compound of IV-B, V-B, VI-B, VII-B, or VIII metal added to charge, the compound being converted to solid, non-colloidal form by heating in the presence of hydrogen.
  • US-A-4,066,530 discloses hydroconversion in the presence of (i) an iron component and (ii) a catalytically active other metal component prepared by dissolving an oil-soluble metal compound in the oil and converting the metal compound in the oil to the corresponding catalytically active metal component.
  • EP-A-512778 teaches that under the conditions of operation disclosed therein, such as in Examples II-IV* and related Table II in particular, it is possible to attain improvements in, for example, conversion and other factors, by adding 10-200 wppm oil-soluble catalyst to the heterogeneous catalyst. In particular, Example I shows that it is possible to attain much higher conversion when using 160 wppm of molybdenum additive.
  • Step (a) involves contacting hydrocarbon oil containing a substantial quantity of high boiling compounds, boiling above about 538°C, in a conversion zone with (1) solid heterogenous catalyst containing hydrotreating metal on a porous support and (2) oil-miscible compound comprising an effective porosity modifying amount of metal compound.
  • Step (b) involves converting a substantial portion of high boiling compounds in the hydrocarbon oil at conversion conditions in the presence of hydrogen and mercaptan to low boiling compounds, boiling below about 538°C, to make hydrocarbon oil containing a substantial portion of low boiling point compounds.
  • Step (c) involves producing solid heterogeneous catalyst with: (1) hydrocarbonaceous deposits having a higher ratio of hydrogen to carbon; and (2) a greater cumulative pore volume; than is correspondingly produced in the absence of the oil-miscible compound.
  • a process is also provided for increasing the effective porosity of a solid heterogeneous catalyst in situ while catalytically hydroconverting hydrocarbon oil comprising such steps.
  • the charge which may be treated by the process of this invention may include high boiling hydrocarbons typically those having an initial boiling point (ibp) above about 343°C. This process is particularly useful to treat charge hydrocarbons containing a substantial quantity of components boiling above about 538°C to convert a substantial portion thereof to components boiling below 538°C.
  • Typical hydrocarbon oils include, among others, one or more of the following: heavy crude oil; topped crude; atmospheric resid; vacuum resid; asphaltenes; tars; coal liquids; visbreaker bottoms; and the like.
  • Illustrative of such charge streams may be a vacuum resid obtained by blending vacuum resid fractions from Alaska North Slope Crude (59 vol%), Arabian Medium Crude (5 vol%), Arabian Heavy Crude (27%), and Bonny Light Crude (9 vol%) having the following characteristics: API Gravity 5.8 538°C +, wt% 93.1 Composition, wt% C 84.8 H 10.09 N 0.52 S 3.64 Alcor Microcarbon Residue (McR), wt% 19.86 n-C7 insolubles, wt% 11.97 Metals content, wppm Ni 52 V 131 Fe 9 Cr 0.7 Na 5
  • the hydrocarbon oil generally contains undesirable components, for example: up to about 1 wt%, typically about 0.2-0.8 wt%, say 0.52 wt%, nitrogen; up to about 10 wt%, typically about 2-6 wt%, say 3.64 wt%, sulfur; and metals, such as Ni, V, Fe, Cr, Na, and others, in amounts up to about 900 wppm, typically about 40-400 wppm, say 198 wppm.
  • the undesirable asphaltene content of the hydrocarbon oil may be as high as about 22 wt%, typically about 8-16 wt%, say 11.97 wt%, analyzed as components insoluble in normal heptane.
  • the API gravity of the charge may be as low as about -5, typically from about -5 to about 35, say 5.8.
  • the content of components boiling above about 538°C may be as high as 100 wt%, typically about 50-98+ wt%, say 93.1 wt%.
  • the Alcor MCR Carbon content may be as high as about 30 wt%, typically about 15-25 wt%, say 19.86 wt%.
  • the charge hydrocarbon oil may be passed to a hydroconversion operation wherein conversion occurs in liquid phase at any effective, including known, conversion conditions.
  • Typical operating conditions include about 371°C-454°C, preferably about 398°C-432°C, say 427°C; and hydrogen partial pressure of about 107-1038 MPa, preferably about 314-521 MPa, say 417 MPa.
  • a catalytically effective amount of oil-miscible, preferably oil-soluble, compound, typically of a metal of Group IV-B, V-B, VI-B, VII-B or VIII of the Periodic Table, is added to the charge hydrocarbon oil, preferably prior to hydroconversion.
  • the metal When the metal is a Group IV-B metal, it may be titanium (Ti), zirconium (Zr), or hafnium (Hf).
  • the metal When the metal is a Group V-B metal, it may be vanadium (V), niobium (Nb), or tantalum (Ta).
  • the metal is a Group VI-B metal, it may be chromium (Cr), molybdenum (Mo), or tungsten (W).
  • the metal when the metal is a Group VII-B metal, it may be manganese (Mn) or rhenium (Re).
  • the metal when the metal is a Group VIII metal, it may be a non-noble metal such as iron (Fe), cobalt (Co), or nickel (Ni) or a noble metal such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), or platinum (Pt).
  • the metal is a Group VI-B metal, and most preferably molybdenum (Mo).
  • Typical oil-miscible or oil-soluble compounds include, among others, one or mixtures of the following: metal salts of aliphatic carboxylic acids like molybdenum stearate, molybdenum palmitate, molybdenum myristate and molybdenum octoate; metal salts of naphthenic carboxylic acids like cobalt naphthenate, iron naphthenate and molybdenum naphthenate; metal salts of alicyclic carboxylic acids like molybdenum cyclohexane carboxylate; metal salts of aromatic carboxylic acids like cobalt benzoate, cobalt o-methyl benzoate, cobalt m-methyl benzoate, cobalt phthalate and molybdenum p-methyl benzoate; metal salts of sulfonic acids like molybdenum benzene sulfonate, cobalt p-toluene sulfonate and iron x
  • the metal compounds to be employed are oil-miscible and preferably oil-soluble, in that they are readily dispersible, and preferably soluble, in the charge hydrocarbon oil in amount of at least 0.01 g/100g typically 0.025-0.25 g/100g, say about 0.1 g/100g.
  • the metal compounds, when activated as hereinafter set forth, are also oil-miscible in the hydrocarbon oils during the hydroconversion process.
  • the oil-miscible compound is generally present in small amounts, typically about 60 wppm or less, of metal, say 10-60 wppm based on hydrocarbon oil to be hydroconverted, unexpected results may be achieved. It is unexpectedly found, if the noted amount is 15-60, preferably 15-45, most preferably 15 wppm, that the cumulative pore volume of the catalyst is improved. Specifically, the cumulative pore volume increases generally at least about 1%, preferably from about 5% to about 50% or more, say 31 %, when compared to the baseline pore volume in the absence of oil-miscible compound.
  • Conversion is calculated from the ratio of the percentage of 538°C+ material in the feed minus the percentage of 538°C+ material in the product divided by the percentage of 538°C+ material in the feed.
  • the level of miscible metal, in the 15-60 wppm range, which will be employed will depend upon the particular charge to the ebullated bed and the desired cumulative pore volume for the catalyst. In any instance, an economic study will permit a ready determination of the desired level of metal to be employed.
  • the oil-miscible compound may be added by any effective means, such as a solution or mixture thereof with a highly aromatic heavy oil.
  • the highly aromatic heavy oil which may be employed, typically those oils which contain sulfur such as a heavy cycle gas oil (HCGO), may be characterized as follows: Broad Narrow Typical API Gravity -5 to 20 0-10 2 Temperature, °C ibp 260-538 343-454 343 50% 427-482 441-468 454 ep 538-649 538-593 566 Aromatics Content, wt% 25-90 30-85 85 Sulfur Content, wt% 0.5-5 2-4 3.5
  • Illustrative highly aromatic heavy oils which may be employed may include: A - Heavy Cycle Gas Oil API Gravity -3.0 Temperature, °C ibp 224 10% 333 50% 406 90% 483 ep 569 Aromatics Content, wt% 85 Sulfur Content, wt% 2.5-3.5 B - MP Extract API Gravity 8 Temperature, °C ibp 316 ep 538 Aromatics Content, wt% 50-90 Sulfur Content, wt% 3 C - Decant Oil API Gravity -2.7 Temperature, °C ibp 274 10% 376 50% 502 90% 524 ep 593 Aromatics Content, wt% 80 Sulfur Content, wt% 1.75
  • the oil-miscible compound may be added in an amount to form a solution or mixture with the heavy oil typically of about 0.01-0.04 wt%, preferably about 0.01-0.03 wt%, say 0.02 wt%.
  • the compound may be added to the heavy oil and stored and used in such form.
  • the amount added may be about 5-20 wt%, preferably about 15 wt%, say 13 wt% of solution or mixture which will provide the 10-60 wppm of metal desired to effect the results noted previously.
  • the oil-miscible compound is added continuously, such as with the charge hydrocarbon.
  • the oil-miscible compound may be added at any stage of the hydroconversion reaction, preferably during the first stage of multi-stage, such as two-stage reactions.
  • Activation of the oil-miscible compound may be effected either by pre-treatment (prior to hydroconversion) or in situ (during hydroconversion). It is preferred to effect activation in situ in the presence of the hydrogenation catalyst to achieve a highly dispersed catalytic species.
  • Activation according to the preferred method may be carried out by adding metal compound, in amount to provide desired metal content, to charge hydrocarbon at about 16°C-149°C, say 93°C.
  • the mixture is activated by heating to about 204°C-446°C, typically about 260°C-371°C, say 316°C at partial pressure of hydrogen of about 25-218 MPa, typically about 210-624 MPa, say 417 MPa and at partial pressure of a gaseous mercaptan of about 4-107 MPa, typically about 5-65 MPa, say 13 MPa.
  • Total pressure may be about 107-1142 MPa, typically about 210-686 MPa, say 552 MPa.
  • the gas may contain about 40-99 vol%, typically about 90-99 vol%, say 98 vol% hydrogen and about 1-10 vol%, say 2 vol% mercaptan, such as hydrogen sulfide.
  • the time for conducting activation may be about 1-12, typically about 2-6, say 3 hours. Activation may occur at a temperature which is lower than the temperature of conversion.
  • the mercaptans which may be employed may include, among others, one or more: hydrogen sulfide; aliphatic mercaptans, typified by methyl mercaptan, lauryl mercaptan, and the like; aromatic mercaptans; dimethyl disulfide; carbon disulfide; and the like. These mercaptans apparently decompose during the activation process. It is not clear why this treatment activates the metal compound. It may be possible that the activity is generated as a result of metal sulfides formed during the treatment.
  • activation may be carried out by subjecting the charge hydrocarbon oil containing the oil-miscible compound to hydroconversion conditions including temperature of about 371°C-454°C, preferably about 399°C-432°C, say 427°C at hydrogen partial pressure of about 107-1038 MPa, preferably about 314-417 MPa, say 417 MPa, in the presence of a mercaptan but in the absence of heterogeneous hydroconversion catalyst.
  • activation may be carried out during hydroconversion in the presence of the heterogeneous, hydroconversion catalyst, hydrogen, and mercaptan.
  • Hydroconversion is carried out in the presence of solid heterogeneous catalyst generally containing, as a hydrogenating component, a metal of Group IV-B, V-B, VI-B, VII-B, or VIII on a porous support which may typically contain carbon or metal oxide, such as of aluminum, silicon, titanium, magnesium, zirconium or the like.
  • the catalyst may contain a metal of Group VI-B and VIII, typically nickel and molybdenum.
  • the metal is a Group IV-B metal, it may be titanium (Ti) or zirconium (Zr).
  • the metal When the metal is a Group V-B metal, it may be vanadium (V), niobium (Nb), or tantalum (Ta).
  • the metal when the metal is a Group VI-B metal, it maybe chromium (Cr), molybdenum (Mo), or tungsten (W). When the metal is a Group VII-B metal, it maybe manganese (Mn) or rhenium (Re). When the metal is a Group VIII metal, it may be a non-noble metal such as iron (Fe), cobalt (Co), or nickel (Ni) or a noble metal such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), or platinum (Pt).
  • the solid heterogeneous catalyst may also contain, as a promoter, a metal of Groups I-A, I-B, II-A, II-B, or V-A.
  • a metal of Groups I-A, I-B, II-A, II-B, or V-A When the promoter is a metal of Group I-A, it may preferably be sodium (Na) or potassium (K).
  • the promoter When the promoter is a metal of Group IB, it may preferably be copper (Cu).
  • the promoter is a metal of Group II-A, it may be beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), or radium (Ra).
  • the promoter When the promoter is a metal of Group II-B, it may be zinc (Zn), cadmium (Cd), or mercury (Hg).
  • the promoter when the promoter is a metal of Group IV-B, it may be titanium (Ti), zirconium (Zr), or hafnium (Hf).
  • the promoter when the promoter is a metal of Group V-A, it may preferably be arsenic (As), antimony (Sb), or bismuth (Bi).
  • the hydrogenating metal may be loaded onto the solid heterogeneous catalyst by any effective, including known, technique, such as by immersing the catalyst support in solution, say ammonium heptamolybdate, for about 2-24 hours, say 24 hours, followed by drying at about 16°C-149°C, say 93°C, for about 1-24 hours, say 8 hours, and calcining for about 1-24 hours, say 3 hours, at about 399°C-593°C, say 499°C.
  • any effective, including known, technique such as by immersing the catalyst support in solution, say ammonium heptamolybdate, for about 2-24 hours, say 24 hours, followed by drying at about 16°C-149°C, say 93°C, for about 1-24 hours, say 8 hours, and calcining for about 1-24 hours, say 3 hours, at about 399°C-593°C, say 499°C.
  • the promoter metal may be loaded onto the solid heterogeneous catalyst by any effective, including known, technique, such as by immersing the catalyst support, preferably bearing the calcined hydrogenating metal - although they may be added simultaneously or in any order, in solution, of for example bismuth nitrate, for about 2-24 hours, say 24 hours, followed by drying at about 16°C-149°C, say 93°C for about 1-24 hours, say 3 hours, and calcining at about 299°C-593°C, say 399°C for about 1-12 hours, say 3 hours.
  • Fresh, solid heterogenous catalyst employed in the method of this invention may be characterized by a total pore volume of about 0.2-1.2 cc/g, say 0.77 cc/g; a surface area of about 50-500 m2/g, say 280 m2/g; and a pore size distribution as follows: Pore Diameter, ⁇ Volume cc/g 30-100 0.15-0.8, say 0.42 100-1000 0.10-0.50, say 0.19 1,000-10,000 0.01-0.40, say 0.16
  • it may have a pore size distribution as follows: Pore Diameter, ⁇ Pore Volume, cc/g Typical >250 0.12-0.35 0.28 >500 0.11-0.29 0.21 >1,500 0.08-0.26 0.19 >4,000 0.04-0.18 0.11
  • the solid heterogeneous catalyst typically may contain about 4-30 wt%, say 9.5 wt% Mo, about 0-6 wt%, say 3.1 wt% Ni and about 0-6 wt%, say 3.1 wt% of promoter metal, say bismuth.
  • Liquid hourly space velocity (LHSV) in the hydroconversion reactors may be about 0.1-2, say 0.7.
  • the heterogeneous catalyst may be employed in the form of extrudates of diameter of 0.7-6.5 mm, say 1 mm and of length of 0.2-25 mm, say 5 mm.
  • hydroconversion may be carried out in one or more beds. It is found that the active form of the catalyst is formed in or accumulates in the first of several reactors and accordingly increases in conversion and heteroatom removal activities appear principally to occur in the first of several reactors.
  • Effluent from hydroconversion is typically characterized by an increase in the content of liquids boiling below 538°C.
  • the wt% conversion of the 538°C + boiling material is about 30%-90%, say 67% which is typically about 5%-25%, say 12% better than is attained by prior art techniques.
  • HDS Conversion may be about 30-90%, say 65% which is about 1%-10%, say 4% higher than the control runs.
  • HDN Conversion may be about 20%-60%, say 45% which is about 1%-10%, say 4% higher than control runs.
  • HDNi plus HDV Conversion may be about 70%-99%, say 90% which is about 5%-20%, say 13% higher than control runs.
  • This invention provides improved solid heterogeneous catalyst having (1) hydrocarbonaceous deposits having a higher ratio of hydrogen to carbon than is produced when operating outside the conditions of this invention; as well as (2) a correspondingly greater cumulative pore volume.
  • hydrocarbonaceous deposits having a higher ratio of hydrogen to carbon than is produced when operating outside the conditions of this invention; as well as (2) a correspondingly greater cumulative pore volume.
  • oil-miscible compound with hydrocarbon oil permits the attainment of hydrocarbonaceous deposits characterized by a hydrogen to carbon ratio typically up to about 30% greater than those obtained in the absence of oil-miscible compound.
  • the hydrogen to carbon ratio may increase from a base ratio of about 0.062 to an experimental ratio as high as about 0.0885.
  • Increased total pore volume will increase the activity of the aged catalyst in situ since the number of micropores are increased when compared to the baseline catalyst. This increase in micropores will increase the ability of the catalyst to perform hydrogenation reactions, such as sulfur removal.
  • the oil miscible compound is molybdenum naphthenate added in an amount to provide from 15 to 60 wppm molybdenum in the feed to the unit.
  • the feedstock is a blend of (i) vacuum resid, (ii) visbreaker bottoms, (iii) vacuum bottoms recycle (iv) and heavy cycle gas oil having the following properties: VR+VB Bottoms HCGO Gravity, API (ASTM D-287) 4.7 -3.5 X-Ray Sulfur, wt% (ASTM D-4294) 5.52 3.41 Carbon Residue, wt% (ASTM D-189) 21.98 10.9 Total Nitrogen, wppm (Chemiluminescence) 4,348 1,582 CHN Analysis, wt% (Leco Combustion Analysis) Carbon 85.65 88.23 Hydrogen 10.47 7.67 Nitrogen 0.6 0.18 Metals, wppm V 170 Ni 40.8 Fe 15.5 Cr 0.2 Na 5.5 Kinematic Viscosity, Cst (
  • the supported catalyst in the ebullated bed is cylinders (0.8 mm diameter and 5 mm length) of commercially available catalyst containing 2.83 wt% nickel and 8.75 wt% molybdenum on alumina, having a surface area of 285.2 m2/g, a total pore volume of 0.78 cc/g, and a pore size distribution of 0.28 cc/g at >250 ⁇ , 0.21 cc/g at >500 ⁇ , 0.19 cc/g at >1,550 ⁇ and 0.11 cc/g at >4,000 ⁇ .
  • the catalyst is activated in situ during hydroconversion.
  • Example 1C A base line, prior to oil-miscible compound addition, analysis of the weight ratio of hydrogen to carbon in the hydrocarbonaceous deposits and catalyst porosity, in total pore volume, is taken in Example 1C; and similar determinations are made at the end of each addition, with the results given in Tables I through V.
  • a baseline was run to determine the product qualities as well as the solid catalyst properties prior to adding the liquid molybdenum compounds.
  • the baseline conditions were LHSV of 0.39 based on total feed, reactor temperatures of 416°C and 421°C, first and second stage respectively, and at a system pressure of 521 MPa.
  • Daily catalyst withdrawals were conducted to maintain the catalyst inventory at the required age. After 5 test periods, each one 24 hours apart, a portion of the withdrawn catalyst was submitted for analyses to determine pore volume, carbon, hydrogen, sulfur as well as other qualities to develop a reference point for comparison purposes.
  • Baseline data indicated the equilibrated, solid heterogenous catalyst had a H/C ratio of 0.062 in the first stage reactor and 0.0574 in the second stage reactor. Surface area for the baseline case was approximately 95 m2/g.
  • Molybdenum naphthenate is mixed with heavy cycle gas oil in amounts to result in 15 ppm molybdenum in the fresh feed to the reactor.
  • the feedstock consists of a blend of vacuum resid, visbroken bottoms, and vacuum bottoms recycle.
  • the molybdenum naphthenate is fed to the process for 9 successive days. Catalyst withdrawals are conducted daily. The catalyst withdrawn from day 9 is submitted for analysis. Comparisons between the analyses from day 9 and the baseline indicate increasing amounts of carbon, molybdenum, vanadium and sulfur depositing on the surface of the catalyst when the molybdenum is injected.
  • Molybdenum naphthenate is mixed with heavy cycle gas oil in amounts to result in 30 ppm molybdenum in the fresh feed to the reactor.
  • the feedstock consists of a blend of vacuum resid, visbroken bottoms, and vacuum bottoms recycle.
  • the molybdenum naphthenate is fed to the process for 8 successive days. Catalyst withdrawals are conducted daily.
  • the catalyst withdrawn from day 8 is submitted for analysis. Comparisons between the analyses from day 8 and the baseline indicate increasing amounts of carbon, molybdenum and sulfur depositing on the surface of the catalyst when the molybdenum is injected.
  • the hydrogen to carbon weight ratio in the first and second stages was higher than the baseline ratio by 18.8 and 2.9% respectively. This indicates increased hydrogen loading in the coke formed on the catalyst.
  • HDS MAT activity tests shows a drop in sulfur removal when compared to the MAT activity for Example 2.
  • Molybdenum naphthenate is mixed with heavy cycle gas oil in amounts to result in 45 ppm molybdenum in the fresh feed to the reactor.
  • the feedstock consists of a blend of vacuum resid, visbroken bottoms, and vacuum bottoms recycle.
  • the molybdenum naphthenate is fed to the process for 4 successive days. Catalyst withdrawals are conducted daily.
  • the catalyst withdrawn from day 8 is submitted for analysis. Comparisons between the analyses from day 4 and the baseline indicated increasing amounts of carbon, molybdenum, vanadium and sulfur depositing on the surface during the period the molybdenum is injected.
  • the hydrogen to carbon weight ratio in the first and second stages increases over the baseline by 20.7 and 2.9% respectively. This would indicate higher levels of hydrogen in the coke formed on the catalyst.
  • Molybdenum naphthenate is mixed with heavy cycle gas oil in amounts to result in 60 ppm molybdenum in the fresh feed to the reactor.
  • the feedstock consists of a blend of vacuum resid, visbroken bottoms, and vacuum bottoms recycle.
  • the molybdenum naphthenate is fed to the process for 11 successive days. Catalyst withdrawals are conducted daily. The catalyst withdrawn from day 11 is submitted for analysis. Comparisons between the analyses from day 11 and the baseline indicate increasing amounts of carbon, molybdenum, vanadium and sulfur depositing on the catalyst surface during the period of molybdenum injection.
  • the hydrogen to carbon weight ratio in the first stage decreases by 4.4% when compared to the baseline.
  • the hydrogen to carbon weight ratio on the second stage catalyst actually increases by 10% over the baseline. It would appear that the coke formed in the first stage during the 60 ppm injection period was of the same type as would normally be formed during resid hydrotreating operations. The second stage catalyst might not have been affected as much since the molybdenum was injected into the first stage only.

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)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP93305127A 1992-07-02 1993-06-30 Improved hydroconversion process Withdrawn EP0577413A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US90788092A 1992-07-02 1992-07-02
US907880 1992-07-02

Publications (1)

Publication Number Publication Date
EP0577413A1 true EP0577413A1 (en) 1994-01-05

Family

ID=25424796

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93305127A Withdrawn EP0577413A1 (en) 1992-07-02 1993-06-30 Improved hydroconversion process

Country Status (3)

Country Link
EP (1) EP0577413A1 (ja)
JP (1) JPH06100871A (ja)
CA (1) CA2095664A1 (ja)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2146274C1 (ru) * 1998-12-18 2000-03-10 Скибицкая Наталья Александровна Способ переработки высокомолекулярного углеводородного сырья
RU2181751C2 (ru) * 1996-02-14 2002-04-27 Тексако Дивелопмент Корпорейшн Способ гидроконверсии тяжелых углеводородов при низком давлении (варианты)
RU2219220C2 (ru) * 1996-04-01 2003-12-20 Закрытое акционерное общество "Грозненский нефтяной научно-исследовательский институт" Способ гидрогенизационной переработки остаточных нефтепродуктов
RU2309974C1 (ru) * 2006-07-25 2007-11-10 Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" Способ переработки нефтяных остатков

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4638610B2 (ja) * 2001-01-05 2011-02-23 日本ケッチェン株式会社 水素化処理用触媒並びに水素化処理方法
US6790803B2 (en) * 2001-08-17 2004-09-14 Intevep, S.A. Catalytic system for hydroconversion of naphtha
FR3116830B1 (fr) * 2020-11-27 2023-11-03 Ifp Energies Now Procédé d’hydrodésulfuration d’une coupe essence mettant en œuvre un catalyseur contenant un matériau graphitique caractérisé par son rapport H/C

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3237037A1 (de) * 1981-10-16 1983-04-28 Chevron Research Co., 94105 San Francisco, Calif. Verfahren zum hydroprocessing eines schweren kohlenwasserstoffhaltigen oelausgangsmaterials
EP0064429B1 (fr) * 1981-04-09 1985-06-19 Institut Français du Pétrole Procédé d'hydrotraitement d'une charge hydrocarbonée en présence d'un catalyseur soumis à une présulfuration
EP0512778A1 (en) * 1991-05-02 1992-11-11 Texaco Development Corporation Hydroconversion process
EP0546686A1 (en) * 1991-11-22 1993-06-16 Texaco Development Corporation Improved hydroconversion process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0064429B1 (fr) * 1981-04-09 1985-06-19 Institut Français du Pétrole Procédé d'hydrotraitement d'une charge hydrocarbonée en présence d'un catalyseur soumis à une présulfuration
DE3237037A1 (de) * 1981-10-16 1983-04-28 Chevron Research Co., 94105 San Francisco, Calif. Verfahren zum hydroprocessing eines schweren kohlenwasserstoffhaltigen oelausgangsmaterials
EP0512778A1 (en) * 1991-05-02 1992-11-11 Texaco Development Corporation Hydroconversion process
EP0546686A1 (en) * 1991-11-22 1993-06-16 Texaco Development Corporation Improved hydroconversion process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2181751C2 (ru) * 1996-02-14 2002-04-27 Тексако Дивелопмент Корпорейшн Способ гидроконверсии тяжелых углеводородов при низком давлении (варианты)
RU2219220C2 (ru) * 1996-04-01 2003-12-20 Закрытое акционерное общество "Грозненский нефтяной научно-исследовательский институт" Способ гидрогенизационной переработки остаточных нефтепродуктов
RU2146274C1 (ru) * 1998-12-18 2000-03-10 Скибицкая Наталья Александровна Способ переработки высокомолекулярного углеводородного сырья
RU2309974C1 (ru) * 2006-07-25 2007-11-10 Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" Способ переработки нефтяных остатков

Also Published As

Publication number Publication date
CA2095664A1 (en) 1994-01-03
JPH06100871A (ja) 1994-04-12

Similar Documents

Publication Publication Date Title
US5622616A (en) Hydroconversion process and catalyst
US5372705A (en) Hydroprocessing of heavy hydrocarbonaceous feeds
EP0546686B1 (en) Hydroconversion process
US5868923A (en) Hydroconversion process
US5474977A (en) Catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks
US5288681A (en) Catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks
US4134825A (en) Hydroconversion of heavy hydrocarbons
US3663431A (en) Two-phase hydrocarbon conversion system
US7431824B2 (en) Process for recycling an active slurry catalyst composition in heavy oil upgrading
US4687757A (en) Hydrofining catalyst composition and process for its preparation
US4626340A (en) Process for the conversion of heavy hydrocarbon feedstocks characterized by high molecular weight, low reactivity and high metal contents
US4734186A (en) Hydrofining process
US4340466A (en) Process for hydrotreating heavy oils containing metals
US4045331A (en) Demetallization and desulfurization of petroleum feed-stocks with manganese on alumina catalysts
US5051389A (en) Catalyst composition prepared by vapor depositing onto a carbon support
US4272357A (en) Desulfurization and demetalation of heavy charge stocks
US4954473A (en) Method of preparing a catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks
EP0577413A1 (en) Improved hydroconversion process
US3294678A (en) Process for deasphaltening heavy petroleum crude oil
EP0512778B1 (en) Hydroconversion process
EP0419123A1 (en) Thermal treatment of heavy petroleum stocks
US3948756A (en) Pentane insoluble asphaltene removal
US3753894A (en) Water injection between catalyst beds in hydrodesulfurization of residuum feed
DE2344251C3 (de) Verfahren zur katalytischen Hydrokrackung einer Schwefel, Asche und Asphaltene enthaltenden Kohlenwasserstoffbeschickung
US4298458A (en) Low pressure hydrotreating of residual fractions

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: A1

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19940607

17Q First examination report despatched

Effective date: 19960513

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19970701