WO2012156294A1 - Catalyseur d'hydrotraitement comprenant un composé de siliciure d'un métal du groupe viii et/ou du groupe vib - Google Patents

Catalyseur d'hydrotraitement comprenant un composé de siliciure d'un métal du groupe viii et/ou du groupe vib Download PDF

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Publication number
WO2012156294A1
WO2012156294A1 PCT/EP2012/058741 EP2012058741W WO2012156294A1 WO 2012156294 A1 WO2012156294 A1 WO 2012156294A1 EP 2012058741 W EP2012058741 W EP 2012058741W WO 2012156294 A1 WO2012156294 A1 WO 2012156294A1
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Prior art keywords
hydrotreating
catalyst
metal
group viii
group vib
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PCT/EP2012/058741
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English (en)
Inventor
Ali AZGHAY
Geert Marten Bakker
Jandirk Maarten DORTMUNDT
Van An DU
Marcello Stefano Rigutto
Ulrich Schubert
Arend Jan Van Welsenes
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Shell Internationale Research Maatschappij B.V.
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Publication of WO2012156294A1 publication Critical patent/WO2012156294A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Definitions

  • the present invention concerns hydrotreating
  • feeds such as crude oil, distillates and residual crude oil fractions generally contain contaminants which tend to deactivate catalyst for chemical conversion of the feeds.
  • Contaminants which are especially abundant are sulphur containing compounds, such as hydrogen sulfide and sulphur containing
  • hydrocarbons and nitrogen containing compounds.
  • Hydrotreating processes can remove such contaminants and generally involve contacting the hydrocarbon feed with a catalyst containing one or more non-noble Group VIII and/or Group VIb metals. Besides contaminants removal, further conversions can take place such as hydrocracking and aromatics hydrogenation .
  • Hydrotreating catalysts generally contain
  • the metal compounds tend to be present as metal sulfide.
  • the metal can be incorporated into the carrier in the form of the sulfide but generally is converted into sulfide either by sulfiding the
  • the metal compounds will remain in the form of a sulfide during operation as hydrotreating feeds contain sulphur containing hydrocarbons .
  • Zerovalent catalytically active metals tend to have a higher initial actitivity. However, such activity is observed to rapidly decrease which is thought to be due to sulfidation of the catalytically active metal compounds.
  • catalysts comprising Group VIB and/or non-noble Group VIII metal silicides have a higher hydrotreating activity, more specifically a higher hydrodesulphurization activity, than catalysts which contain metal sulfides.
  • the present invention relates to a hydrotreating process comprising contacting a sulphur containing hydrocarbon feed with a hydrotreating catalyst comprising non-noble Group VIII and/or Group VIb metal silicide compounds at elevated temperature and pressure.
  • the invention furthermore relates to hydrotreating catalysts comprising non-noble Group VIII and/or Group VIb metal silicide compounds, especially those
  • the invention relates to a hydrotreating process
  • hydrotreating catalyst comprising contacting hydrotreating catalyst according to the invention or prepared according to the invention with a sulphur containing hydrocarbon feed at temperature in the range of from 200 to 500°C, a total reactor pressure in the range of from 1.0 to 20 MPa and a hydrogen partial pressure at the reactor outlet in the range of from 1.0 to 20 MPa.
  • x hydrotreating' is used herein to cover a range of processes in which a sulfur containing
  • hydrocarbon feed is contacted with a catalyst in the presence of hydrogen, more specifically in order to attain chemical conversion.
  • further reactions can take place such as hydrodenitrogenation, hydrocracking and aromatics hydrogenation .
  • the hydrotreating process of the present invention will involve hydrodesulphurization to a certain extent due to the presence of sulphur in the feed.
  • the focus or further objective of the hydrotreating process can be hydrodenitrogenation, hydrocracking and/or aromatics hydrogenation.
  • hydrotreating processes of the present invention are especially preferred to be used for
  • processes of the present invention are processes in which a sulfur containing feed is converted into a product have a substantially lower sulfur content.
  • the sulfur content of the product is at most 50 % by weight (%wt) of the sulfur content of the feed, more
  • %wt most specifically at most 5 %wt .
  • the amounts are based on the amounts of elemental sulfur in each feed and product .
  • Hydrocarbon feeds that contain sulfur include any crude or petroleum oil or fraction thereof which have a measureable sulfur content.
  • the feeds may be previously untreated or have already undergone such treatment as fractionation, for example atmospheric or vacuum
  • cracking for example catalytic cracking, thermal cracking, or hydrocracking, or any other
  • suitable hydrocarbon feeds include catalytically cracked light and heavy gas oils,
  • hydrotreated gas oil light flash distillate, light cycle oil, vacuum gas oil, light gas oil, straight run gas oil, coker gas oil, synthetic gas oil, and mixtures of any two or more thereof.
  • Other possible feeds include deasphalted oils, waxes obtained from a Fischer-Tropsch synthesis process, long and short residues, and syncrudes,
  • the feed may have a sulfur content of up to 6 %wt, based on elemental sulfur. Typically, sulfur contents are in the range of from 0.0001 to 5 %wt, more specifically at least 0.001 %wt, more specifically at least 0.01 %wt .
  • the sulfur compounds are usually in the form of hydrogen sulfide or complex organic sulfur compounds.
  • the feed may have a nitrogen content of up to 10,000 ppmw (parts per million by weight), more specifically up to 2,000 ppmw, based on elemental
  • nitrogen typically, nitrogen contents are in the range of from 5 to 5,000 ppmw, more specifically in the range of from 5 to 1500 or to 500, most specifically of from 5 to 200, ppmw.
  • the nitrogen compounds are usually in the form of complex organic nitrogen compounds.
  • the catalyst of this invention contains one or more metals chosen from the group consisting of Group VIb metals (especially molybdenum and tungsten) and non-noble Group VIII metals (especially nickel and cobalt) . It is especially preferred to choose one or more metals from the group consisting of nickel, cobalt, molybdenum and tungsten. Further metal compounds and further promoters to increase the catalytic activity can be present
  • the catalyst further comprises an inert refractory oxide carrier.
  • the refractory oxide can be any compound known to be suitable such as silica, alumina, magnesia, titania, zirconia, boria, zinc oxide, or mixtures thereof.
  • the carrier is alumina, more specifically gamma-alumina.
  • the catalyst preferably consists of a refractory oxide carrier and metal compounds of which the metal is chosen from the group consisting of Group VIb and non- noble Group VIII metals, more specifically nickel, cobalt, molybdenum and tungsten.
  • the Group VIb van Group VIII metal are as described in the Periodic Table of Elements which appears on the inside cover of the CRC Handbook of Chemistry and Physics ( x The Rubber Handbook' ) , 63 rd edition and using the CAS version notation.
  • the metal silicide present can contain a certain amount of impurities for example carbide or oxidation products such as metal silicate. Additionally, metal sulfides can be formed during operation.
  • the metal silicide can contain up to at most 70 %wt of metal compounds other than metal silicide, more specifically up to most 60 %wt .
  • the catalysts of the present invention preferably contain of from 0.2 %wt to 10 %wt, preferably of from 0.5 %wt to 8 %wt, and, most preferably, from 1 %wt to 6 %wt, of non-noble Group VIII metal silicide.
  • the Group VIb metal silicide preferably is present in an amount in the range of from 2 %wt to 25 %wt, preferably from 4 %wt to 20 %wt, and, most preferably, from 6 %wt to 15 %wt .
  • the total amount of Group VIb and non-noble VIII metal silicides is of from of from 0.2 %wt to
  • weight percents for the metal components are based on the dry support material and the weight amount of silicide metals. Additionally, further metal can be present in the zerovalent form or in the form of different metal
  • the metal compounds more specifically the metal silicide particles, preferably are distributed
  • a substantial amount of the metal silicide is present in the form of relatively small particles such as at most 10 nm, more specifically at most 5 nm.
  • the size is the length of the particle as visible on a transmission electron microscopy (TEM) image.
  • TEM transmission electron microscopy
  • larger particles can be present.
  • large particles offer less surface for catalytic activity and are less preferred from an efficiency point of view.
  • at least 40 %wt of the metal silicides is present in the form of the above mentioned small particles, more specifically at least 50 %wt, most specifically at least 70 %wt .
  • the catalysts may be applied in any reactor type but are most suited for use in a fixed bed reactor. If necessary two or more reactors containing the catalyst may be used in series.
  • the catalyst compositions may be applied in single bed or stacked bed configuration.
  • the latter has the compositions according to the present invention loaded together with layers of other hydrotreating catalyst into one or a series of reactors.
  • Such other catalyst may be for example a hydroprocessing catalyst or a hydrocracking catalyst.
  • a second catalyst can be more susceptible to poisoning sulfur and optionally nitrogen.
  • the hydrotreating process of the invention may be run with the hydrogen gas flow being either co-current or counter-current to the feed flow.
  • the process of the invention is operated under the conditions of elevated temperature and pressure which are conventional for the relevant hydrotreating reaction intended.
  • the reaction temperature lies in the range of from 200 to 500°C, preferably from 200 to 450°C, and especially from 300 to 400°C.
  • Suitable total reactor pressures lie in the range of from 1.0 to 20 MPa.
  • Typical hydrogen partial pressures are in the range of from 1.0 to 20 MPa (10 to 200 bar), and preferably from 5.0 to 15.0 MPa (50 to 150 bar) at which pressure compositions of and for use in the present invention have been found to have a particularly improved activity compared with conventional catalysts.
  • the hydrogen gas flow rate in the reactor is most suitably in the range of from 10 to 2,000 Nl/kg liquid feed, for example 100 to 1000 Nl/kg, more suitably 150 to 500 Nl/kg.
  • a typical liquid hourly space velocity is in the range of from 0.05 to 10 kg feed per liter catalyst per hour (kg/l/h) , suitably from 0.1 to 10, preferably to 5, more preferably from 0.5 to 5, kg/l/h.
  • the catalyst compositions for use in the present invention can be sulfided before use. Such sulfidation procedures are well known to the skilled person.
  • the hydrotreating catalysts of the present invention can be manufactured in any way known to be suitable by someone skilled in the art.
  • a process which has been found to give especially preferred catalysts comprises contacting a composition comprising one or more metals or metal compounds in which the metal is chosen from the group consisting of Group VIb and non-noble Group VIII metals with a silane compound in the presence of hydrogen at a temperature of at least 100 °C, preferably at least 150 °C, more preferably of from 200 to 750 °C, more specifically of from 200 to 700 °C, more specifically of from 200 to 650 °C.
  • the silane compound for use in this manufacturing process preferably is a compound comprising silicon and hydrogen and/or alkyl groups, more specifically silane or an alkylsilane comprising of from 1 to 4 alkyl groups each of which alkyl groups has of from 1 to 5, more specifically of from 1 to 3 carbon atoms.
  • the metal containing composition can be reduced before contact with the silane compound.
  • the reduction can be carried out by contacting the composition with a hydrogen containing gas at a temperature of from 100 to 700 °C, more specifically of from 200 to 600 °C. It is preferred that the metal and/or metal compound containing composition is not reduced before contact with the silane compound .
  • composition is contacted with the silane
  • the silane compound at a temperature of from 100 to 700 °C, more specifically of from 200 to 600 °C.
  • the silane compound is diluted with a gas, more specifically an inert gas.
  • a gas more specifically an inert gas. The exact time period required to convert a sufficient amount of the metal into metal silicides depends on the circumstances such as temperature and dilution of the silane compound, the metal compound present and the amount of metal silicides desired.
  • the time period will be of from 0.5 to 10 hours, more specifically of from 1 to 8 hours.
  • the catalyst After contact with the silane compound, the catalyst is cooled preferably while in contact with inert gas optionally containing silane compound.
  • the catalyst preferably is sulfided before actual use.
  • the metal may be incorporated into the composition by any suitable method or means.
  • One method includes, for example, co-mulling refractory oxide carrier with a metal or metal compound to yield a co-mulled mixture.
  • another method includes the co-precipitation of
  • the refractory oxide carrier is impregnated with a metal component using any of the known impregnation methods such as incipient wetness or pore volume
  • the refractory oxide carrier When using the impregnation method, it is preferred for the refractory oxide carrier to be formed into a shaped particle and thereafter load it with metal, preferably, by impregnation with an aqueous solution of a metal salt.
  • the refractory oxide carrier which preferably is in powder form, is mixed with water and, if desired or needed, a peptizing agent and/or a binder to form a mixture that can be shaped into an agglomerate. It is desirable for the mixture to be in the form of an extrudable paste suitable for extrusion into extrudate particles, which may be of various shapes such as cylinders and trilobes.
  • the shaped particle is then dried under standard drying conditions that can include a drying temperature in the range of from 50 °C to 200 °C and, most preferably, from 90 °C to 150 °C .
  • the shaped particle preferably is calcined under standard calcination conditions that can include a calcination temperature in the range of from 250 °C to 900 °C, preferably, from 300 °C to 800 °C, and, most preferably, from 350 °C to 600 °C .
  • the calcined Group VIb and/or non-noble Group VIII metal or metal compounds comprising composition can have a surface area (determined by the BET method employing N 2 , ASTM test method D 3037) that is in the range of from 50 m 2 /g to 450 m 2 /g, preferably from 75 m 2 /g to 400 m 2 /g, and, most preferably, from 100 m 2 /g to 350 m 2 /g.
  • the mean pore diameter in angstroms (A) of the calcined shaped particle preferably is in the range of from 50 to 200, more preferably, from 70 to 150, and, most preferably, from 75 to 125.
  • the pore volume of the calcined shaped particle preferably is in the range of from 0.5 cc/g to 1.1 cc/g, preferably, from 0.6 cc/g to 1.0 cc/g, and, most preferably, from 0.7 to 0.9 cc/g.
  • less than ten percent (10%) of the total pore volume of the calcined shaped particle is contained in the pores having a pore diameter greater than 350 A, preferably, less than 7.5% of the total pore volume of the calcined shaped particle is contained in the pores having a pore diameter greater than 350 A, and, most preferably, less than 5 %.
  • references herein to the pore size distribution and pore volume of the calcined shaped particle are to those properties as determined by mercury intrusion porosimetry, ASTM test method D 4284.
  • particle is by any suitable measurement instrument using a contact angle of 140° with a mercury surface tension of 474 dyne/cm at 25 °C .
  • the calcined shaped particle is impregnated in one or more impregnation steps with a metal component using one or more aqueous solutions.
  • the metal components include metal acetates, formates, citrates, oxides, hydroxides, carbonates, nitrates, sulfates, and mixtures thereof.
  • Preferred components are non-noble Group VIII metal oxides,
  • preferred non-noble Group VIII metal components are metal nitrates.
  • the metal components include metal oxides and sulfides.
  • Preferred Group VIb metal components are oxides such as molybdenum oxide and salts containing the Group VIb metal and ammonium ion, such as ammonium heptamolybdate and ammonium dimolybdate.
  • the concentration of the metal compounds in the impregnation solution is selected so as to provide the desired metal content in the final composition of the invention taking into consideration the pore volume of the support material into which the aqueous solution is to be impregnated and the amount of hydrocarbon oil to be incorporated into the support material that is loaded with a metal component.
  • the concentration of metal compound in the impregnation solution is in the range of from 0.01 to 100 moles per liter.
  • the metal content may depend upon the application for which the catalyst is to be used, but, generally, for hydrotreating applications, the non-noble Group VIII metal component can be present in the composition in an amount in the range of from 0.5 %wt to 20 %wt, preferably of from 1 %wt to 15 %wt, and, most preferably, from 2 %wt to 12 %wt .
  • the Group VIb metal can be present in the composition in an amount in the range of from 5 %wt to 50 %wt, preferably from 8 %wt to 40 %wt, and, most preferably, from 12 %wt to 30 %wt .
  • the total amount of Group VIb and non-noble Group VIII metals is of from of from 0.5 %wt to 50 %wt, preferably of from 1 %wt to 40 %wt, and, most preferably, of from 2 %wt to 30 %wt .
  • the above-referenced weight percents for the metal components are based on dry support material before silylation of the composition and the metal component as the element regardless of the actual form of the metal component .
  • the catalysts according to the present invention comprise one metal chosen from the group consisting of nickel and cobalt and one metal chosen from the group consisting of tungsten and molybdenum.
  • the catalyst obtained is hereinafter referred to as
  • the catalyst obtained is hereinafter referred to as Ni/Al 2 0 3 .
  • a solution was prepared comprising
  • Example 1 was loaded into a reactor tube and reduced by heating at 10°C/min to 400°C in a flow of H 2 /argon (23% H 2 /77% argon, 50 ml/min) , maintaining the temperature at 400°C for 3 hours, and cooling to 40°C room temperature in a flow of argon.
  • the catalyst was treated with a mixture of 18% by volume tetraethylsilane, 5% H 2 and 77% argon at 41 ml/min, and heated in this flow to 400°C at a rate of 10°C/min. The temperature was kept at 400°C for 5.5 hours while maintaining the flow, after which the silylated catalyst was cooled to 40°C in a flow of argon.
  • the catalyst obtained is hereinafter referred to as silylated Co/Al 2 0 3 .
  • Example 4 The silylation procedure of Example 4 was applied to the Ni on A1 2 0 3 catalyst of Example 2.
  • the catalyst obtained is hereinafter referred to as silylated Ni/Al 2 0 3 .
  • Example 4 The silylation procedure of Example 4 was applied to the Mo on A1 2 0 3 catalyst of Example 3 with the following differences: reduction in H 2 /argon was carried out by heating to 600°C with 10°C/min, and maintaining that temperature for 4 minutes.
  • the catalyst obtained is hereinafter referred to as silylated Mo/Al 2 0 3 .
  • DBT dibenzothiophene
  • reaction constant for DBT conversion (k DB T) was calculated assuming first order reaction kinetics in DBT conversion .
  • TEM transmission electron microscopy
  • EDX energy-dispersive X-ray spectroscopy

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Abstract

L'invention concerne un procédé d'hydrotraitement comprenant la mise en contact d'une alimentation hydrocarbonée contenant du soufre avec un catalyseur d'hydrotraitement comprenant des composés de siliciure d'un métal non noble du groupe VIII et/ou du groupe VIb à température et pression élevées, et un catalyseur d'hydrotraitement comprenant des composés de siliciure d'un métal non noble du groupe VIII et/ou du groupe VIb.
PCT/EP2012/058741 2011-05-13 2012-05-11 Catalyseur d'hydrotraitement comprenant un composé de siliciure d'un métal du groupe viii et/ou du groupe vib WO2012156294A1 (fr)

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WO2016183195A1 (fr) * 2015-05-12 2016-11-17 Ergon, Inc. Huile de procédé à haute performance
KR20180006938A (ko) * 2015-05-12 2018-01-19 에르곤,인크 증류된 방향족 추출물에 기반한 고성능 공정 오일

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Publication number Priority date Publication date Assignee Title
WO2016183195A1 (fr) * 2015-05-12 2016-11-17 Ergon, Inc. Huile de procédé à haute performance
KR20180006937A (ko) * 2015-05-12 2018-01-19 에르곤,인크 고성능 공정 오일
KR20180006938A (ko) * 2015-05-12 2018-01-19 에르곤,인크 증류된 방향족 추출물에 기반한 고성능 공정 오일
CN107636123A (zh) * 2015-05-12 2018-01-26 埃尔根公司 基于蒸馏的芳族提取物的高性能加工油
CN107636120A (zh) * 2015-05-12 2018-01-26 埃尔根公司 高性能加工油
RU2726612C2 (ru) * 2015-05-12 2020-07-15 Эргон, Инк. Технологическое масло с высокими эксплуатационными характеристиками
US11332679B2 (en) 2015-05-12 2022-05-17 Ergon, Inc. High performance process oil
CN107636123B (zh) * 2015-05-12 2022-08-05 埃尔根公司 基于蒸馏的芳族提取物的高性能加工油
US11560521B2 (en) 2015-05-12 2023-01-24 Ergon, Inc. High performance process oil
US11566187B2 (en) 2015-05-12 2023-01-31 Ergon, Inc. High performance process oil based on distilled aromatic extracts
KR102608627B1 (ko) * 2015-05-12 2023-12-04 에르곤,인크 고성능 공정 오일
KR102608532B1 (ko) * 2015-05-12 2023-12-04 에르곤,인크 증류된 방향족 추출물에 기반한 고성능 공정 오일

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