WO2012156294A1 - Hydrotreating catalyst comprising a group viii and/or group vib metal silicide compound - Google Patents

Hydrotreating catalyst comprising a group viii and/or group vib metal silicide compound 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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French (fr)
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/en

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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

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 and hydrotreating catalyst comprising non-noble Group VIII and/or Group VIb metal silicide compounds.

Description

HYDROTREATING CATALYST COMPRISING A GROUP VIII AND/OR GROUP VIB METAL
SILICIDE COMPOUND
Field of the Invention
The present invention concerns hydrotreating
processes, particularly hydrodesulphurisation processes, in which a sulphur containing hydrocarbon feed is
contacted with a hydrotreating catalyst.
Background of the Invention
In refinery processes, 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
catalytically active metals or metal compounds on a
refractory oxide carrier. 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
catalyst before operation or during start of the
operation. The metal compounds will remain in the form of a sulfide during operation as hydrotreating feeds contain sulphur containing hydrocarbons .
It is desirable to increase the activity of
hydrotreating catalysts. 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.
US-A-4 , 101 , 592 describes the use of commercially purchased MoSi2 for hydrogenation of butene .
The article "Synthesis and Catalytic Properties for
Phenylacetylene Hydrogenation of Silicide Modified Nickel Catalysts" by Xiao Chen et al . , J. Phys . Chem. C 2010, 114, 16525-16533 describes the use of silicide-modified nickel for selective hydrogenation of phenylacetylene to styrene and ethylbenzene . Neither of these publications describes or hints at the use of catalysts in
hydrotreating .
Summary of the Invention
We have now unexpectedly found that 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.
Furthermore, the high hydrotreating activity was observed for a long time which suggests that metal silicides can withstand sulfidation at hydrotreating operating conditions.
Therefore, 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
manufactured by contacting a composition comprising one or more non-noble Group VIII and/or Group VIb metals with a silane compound in the presence of hydrogen. Further, the invention relates to a hydrotreating process
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.
Detailed Description of the Invention
The term xhydrotreating' 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. Besides the conversion of sulphur containing compounds, 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. However, the focus or further objective of the hydrotreating process can be hydrodenitrogenation, hydrocracking and/or aromatics hydrogenation.
The hydrotreating processes of the present invention are especially preferred to be used for
hydrodesulphurization. In the art of refinery processing different terms may be used to refer to
hydrodesulphurization. The hydrodesulphurization
processes of the present invention are processes in which a sulfur containing feed is converted into a product have a substantially lower sulfur content. Preferably, the sulfur content of the product is at most 50 % by weight (%wt) of the sulfur content of the feed, more
specifically at most 30 %wt, more specifically at most 10
%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
distillation, cracking for example catalytic cracking, thermal cracking, or hydrocracking, or any other
hydroprocessing treatment.
Examples of 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,
optionally originating from tar sand, shale oils, residue upgrading processes and biomass.
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.
Additionally, 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
depending on the specific application foreseen.
Preferably, 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. Preferably, 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 ( xThe Rubber Handbook' ) , 63rd 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 . Preferably, the total amount of Group VIb and non-noble VIII metal silicides is of from of from 0.2 %wt to
25 %wt, preferably of from 0.5 %wt to 20 %wt, and, most preferably, of from 1 %wt to 15 %wt . The above-referenced 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
compounds .
The metal compounds, more specifically the metal silicide particles, preferably are distributed
homogeneously over the catalyst surface.
It is preferred that 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. Besides the small particles, larger particles can be present. However, large particles offer less surface for catalytic activity and are less preferred from an efficiency point of view. Preferably, 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. Where the catalyst composition of the present invention is exposed first to the feed, then 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. Generally, 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 (at the reactor outlet) 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 .
The composition is contacted with the silane
compound at a temperature of from 100 to 700 °C, more specifically of from 200 to 600 °C. Preferably, the silane compound is diluted with 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.
Generally, the time period will be of from 0.5 to 10 hours, more specifically of from 1 to 8 hours.
After contact with the silane compound, the catalyst is cooled preferably while in contact with inert gas optionally containing silane compound.
Subsequently, 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. Or, another method includes the co-precipitation of
refractory oxide carrier and metal or metal compound to form a co-precipitated mixture. Or, in a preferred method, the refractory oxide carrier is impregnated with a metal component using any of the known impregnation methods such as incipient wetness or pore volume
impregnation to incorporate the metal component into the support material.
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. To form the shaped particle, 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 . After drying, 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 N2, ASTM test method D 3037) that is in the range of from 50 m2/g to 450 m2/g, preferably from 75 m2/g to 400 m2/g, and, most preferably, from 100 m2/g to 350 m2/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. Preferably, 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 %.
The 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. The measurement of the pore size distribution of the calcined shaped
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 .
In a preferred embodiment of the invention, the calcined shaped particle is impregnated in one or more impregnation steps with a metal component using one or more aqueous solutions. For the non-noble Group VIII metals, 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,
hydroxides, carbonates, and mixtures thereof. The
preferred non-noble Group VIII metal components are metal nitrates. For the Group VIb metals, 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. Typically, 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 . Preferably, 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 .
Preferably, 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 following Examples illustrate the present invention .
EXAMPLES
In these Examples the following test methods
Preparation of catalysts Example 1 (C0/AI2O3 preparation)
2.2 g of C0CO3 were suspended in 8.4 ml of water. After the addition of 3.6 g of citric acid (19 mmol) , C02 gas evolved and the mixture was refluxed for 10 minutes. Subsequently, the solution was cooled to room temperature and 3 ml of aqueous ammonia (30%wt) was added. A dark violet solution was obtained. 10 g of γ-Α1203 carrier with a pore volume of 0.84 cm3/g was dried at 300°C and pore impregnated with the cobalt solution, and then dried and subsequently calcined in a ventilated furnace
(heating in 1 h to 120°C, maintain for 1 h at 120°C, and subsequently heating in 2 h to 450°C, maintain for 2 h at 450°C) .
The catalyst obtained is hereinafter referred to as
Example 2 (Ni/Al203 preparation)
2.4 g of NiC03 (20 mmol), 3.9 g citric acid (20 mmol) and 15 ml of water were refluxed for 15 min.
Subsequently, the pale green solution was concentrated to a volume of 8.4 ml. 10 g of γ-Α1203 carrier was
impregnated, dried and calcined as above. The catalyst obtained is hereinafter referred to as Ni/Al203.
Example 3 (M0/AI2O3 preparation)
A solution was prepared comprising
[Mo2 (acetate) 2 (ethylenediamine) 4] · (acetate) 2 -ethylenediami ne in ethylenediamine which preparation is described in detail in the article by B.W. Eichhorn, M.C. Kerby, R.C. Haushalter, K.P.C. Vollhardt, Inorg. Chem. 1990, 29(4), pages 723-728 and involved dissolving 0.4 g Mo2 (acetate) 4 (0.87 mmol) in 9 ml of ethylenediamine (0.13 mol) .
Subsequently, 10.5 g of γ-Α1203 was pore impregnated to obtain 1.6 %wt molybdenum on alumina. Afterwards the composite was dried under vacuum at room temperature overnight . The catalyst obtained is hereinafter referred to as
Example 4 (silylated Co/Al203)
500 mg of Co on γ-Α1203 catalyst as prepared in
Example 1 was loaded into a reactor tube and reduced by heating at 10°C/min to 400°C in a flow of H2/argon (23% H2/77% 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. Next, the catalyst was treated with a mixture of 18% by volume tetraethylsilane, 5% H2 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/Al203.
Example 5 (silylated Ni/A12Q3)
The silylation procedure of Example 4 was applied to the Ni on A1203 catalyst of Example 2.
The catalyst obtained is hereinafter referred to as silylated Ni/Al203.
Example 6 (silylated Mo/Al2Q3)
The silylation procedure of Example 4 was applied to the Mo on A1203 catalyst of Example 3 with the following differences: reduction in H2/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/Al203.
Example 7 (Performance test)
Dibenzothiophene hydrodesulphurisation experiments were carried out in trickle flow, in a nanoflow reactor setup with six reactors. Each reactor was loaded with 385 mg of crushed and sieved catalyst particles (30-80 mesh) , diluted with inert material to ensure proper hydrodynamic behaviour. Prior to testing, the catalysts were in situ presulfided with a mixture of hexadecane and 5.4 %wt of ditertiononylpentasulfide fed at 0.75 ml/min, in trickle flow with H2 at a flow rate of 250 ml/g feed, heated at 20°C/h to 280°C then maintaining it for 5 h, next heating at 20°C/h to 340°C and maintaining it for 2 h. The test feed was a mixture of 5 %wt
dibenzothiophene (DBT) , 1.75 %wt dodecane and the
remainder hexadecane, fed at 0.75 ml/min, in trickle flow with H2 at a flow rate of 250 ml/g feed.
Results are summarized in the following Table 1.
The reaction constant for DBT conversion (kDBT) was calculated assuming first order reaction kinetics in DBT conversion .
The transmission electron microscopy (TEM) image and energy-dispersive X-ray spectroscopy (EDX) image of the silylated Ni/Al203 show that nickel silicide is present, that both the nickel and the silicon are distributed evenly and that no particles are discernible which means that their size must be well below 5 nm.
Table 1
kDBT silylated/
Catalyst DBT conversion (%) ■k-DBT (g.min/ml)
kDBT non-silylated
300°C 325°C 350°C 300°C 325°C 350°C 300°C 325°C 350°C
Co/Al203 15.4 35.3 68.5 0.23 0.61 1.62
Silylated
Co/Al203 22.6 47.3 84.1 0.36 0.90 2.57 1.5 1.5 1.6
Ni/Al203 11.2 24.3 51.4 0.17 0.39 1.01
Silylated
Ni/Al203 58.4 94.0 99.6 1.23 3.94 7.73 7.4 10.1 7.7
Mo/Al203 9.7 21.7 44.9 0.14 0.34 0.83
Silylated
Mo/Al203 31.7 51.9 78.5 0.53 1.02 2.15 3.7 3.0 2.6

Claims

C L A I M S
1. 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.
2. Hydrotreating process as claimed in claim 1, in which the temperature is in the range of from 200 to 500°C, the total reactor pressure is in the range of from 1.0 to 20 MPa and the hydrogen partial pressure at the reactor outlet is in the range of from 1.0 to 20 MPa.
3. Hydrotreating process as claimed in claim 1 or 2, in which the catalyst comprises non-noble Group VIII and/or Group VIb metal silicide compounds of which the metal is chosen from the group consisting of nickel, cobalt, molybdenum and tungsten.
4. Hydrotreating process as claimed in any one of claims 1 to 3, in which the catalyst further comprises a refractory oxide carrier.
5. Hydrotreating process as claimed in claim 4, in which the refractory oxide carrier is alumina.
6. Hydrotreating process as claimed in any one of claims 1 to 5 in which the hydrotreating catalyst is manufactured by contacting a composition comprising one or more non-noble Group VIII and/or Group VIb metals with a silane compound in the presence of hydrogen.
7. Hydrotreating process as claimed in claim 6, in which the silane compound is a compound comprising silicon and hydrogen and/or alkyl groups.
8. Hydrotreating process as claimed in claim 7, in which the silane compound is silane or an alkylsilane comprising of from 1 to 4 alkyl groups containing of from 1 to 3 carbon atoms .
9. Hydrotreating process as claimed in any one of claims 6 to 8, which process comprises calcining the catalyst at a temperature of from 150 to 600 °C after contact with the silane compound.
10. Hydrotreating catalyst comprising non-noble Group VIII and/or Group VIb metal silicide compounds.
11. Process for manufacture of a hydrotreating catalyst according to claim 10, which process comprises contacting a composition comprising one or more non-noble Group VIII and/or Group VIb metals with a silane compound in the presence of hydrogen.
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