Classifications

• • 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • 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
• • 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
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • 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
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  • 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
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
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  • 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
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
• • 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
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• • 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
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0063—Granulating
• • 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
  • B01J37/08—Heat treatment
  • B01J37/10—Heat treatment in the presence of water, e.g. steam
• • 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
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/638—Pore volume more than 1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/651—50-500 nm
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/66—Pore distribution

Definitions

• the present invention concerns a catalyst for hydrotreating and/or hydroconverting heavy metal-containing hydrocarbon feeds, said catalyst comprising a support in the form of mainly irregular and non-spherical alumina-based agglomerates the specific shape of which results from a crushing step, and comprising at least one catalytic metal or a compound of a catalytic metal from group VIB (group 6 in the new periodic table notation) and/or group VIII (groups 8, 9 and 10 of the new periodic table notation), optionally at least one doping element selected from the group constituted by phosphorus, boron and silicon (or silica which does not form part of that which may be contained in the selected support) and halogens, said catalyst essentially being constituted by a plurality of juxtaposed agglomerates each formed by a plurality of acicular platelets, the platelets of each agglomerate generally being oriented radially with respect to each other and with respect to the centre of the agglomerate.
• the specific shape of the catalyst
• the accumulation of solid deposits in the pores of a catalyst may continue until some of the pores controlling access of reagents to a fraction of the interconnected pore network is plugged so that that fraction becomes inactive even though the pores of that fraction are only slightly obscured or even intact. That phenomenon may thus cause premature and major deactivation of the catalyst. This is particularly the case with hydrodemetallization reactions carried out in the presence of a supported heterogeneous catalyst.
• heterogeneous means not soluble in the hydrocarbon feed. In this case, it can be shown that the pores of the periphery become blocked more quickly that the central pores. Similarly, the pore mouths become blocked more quickly than their other parts.
• Pore obstruction goes hand in hand with a gradual reduction in their diameter, which increasingly limits diffusion of molecules and accentuates the concentration gradient and thus the heterogeneity of the deposit from the periphery to the interior of the porous particles, to the point that total obstruction of the pores mouth to the exterior occurs very rapidly: access to the almost intact internal porosity of the particles is thus impossible for the reagents and the catalyst is prematurely deactivated.
• a catalyst for hydrotreating heavy metal-containing hydrocarbon cuts must thus be composed of a support having a pore profile, a pore structure and a shape (geometry) which is particularly suited to the intragranular diffusional constraints specific to hydrotreatments to avoid problems with plugging mentioned above.
• the catalysts are in the form of beads or extrudates and are composed of an alumina-based support having a particular porosity and an active phase based on mixed sulphides constituted both by a sulphide of a group VIB metal (preferably molybdenum) and a sulphide of a group VIII metal (preferably Ni or Co).
• the metals are deposited in the oxide state and are sulphided to be active for hydrotreatment.
• the atomic ratio between the group VIII element and the group VIB element which is usually considered to be optimal, group VIII atom/group VIB atom, is in the range 0.4 to 0.6.
• European document EP-A1-1 364 707 FR-A-2 839 902
• a ratio of less than 0.4 can limit catalyst deactivation and thus prolong the service life of the catalysts.
• alumina-based support for catalysts for hydrorefining and/or hydroconverting heavy metal-containing hydrocarbon feeds. These supports are broadly distinguished by their pore distribution profiles.
• Catalysts with a bimodal porosity profile are highly active, but have a poorer retention capacity than catalysts with a polymodal porosity profile.
• the polymodal porosity profile corresponds to a graph of the cumulative distribution of the pore volume as a function of the pore diameter obtained by the mercury intrusion method which is neither monomodal nor bimodal, in the sense that distinct categories of pores appear with pore diameters which are centred on well defined mean values do not appear, but a relatively continuous pore distribution is seen between two extreme diameter values. Between those extreme values, there is no horizontal stage in the pore distribution curve.
• Said polymodal distribution is linked to a “thorny chestnut husk” or “sea-urchins” pore structure obtained with alumina agglomerates prepared by the rapid dehydration of hydrargillite then agglomerating the flash alumina powder obtained in accordance with one of the Applicant's patents (U.S. Pat. No. 4,552,650-IFP).
• the prepared alumina agglomerates may be in the form of beads or in the form of extrudates, as shown in FR-A-2 764 213 and U.S. Pat. No. 6,043,187.
• the thorny chestnut husk or sea-urchins structure is constituted by a plurality of juxtaposed agglomerates each formed by a plurality of acicular platelets, the platelets of each agglomerate generally being radially orientated with respect to each other and with respect to the centre of the agglomerate.
• At least 50% of the acicular platelets have a dimension along their longer axis of between 0.05 and 5 micrometers and preferably between 0.1 and 2 micrometers, a ratio of this dimension to their average width of between 2 and 20, preferably between 5 and 15, and a ratio of this dimension to their average thickness of between 1 and 5000, preferably between 10 and 200.
• At least 50% of the agglomerates of acicular platelets constitutes a collection of pseudo-spherical particles with a mean size of between 1 and 20 micrometers, preferably between 2 and 10 micrometers.
• a highly suitable image which can be used to help to represent such a structure is a pile of thorny chestnut-husks or of a pile of sea-urchins, hence the pore structure denominations “thorny chestnut husk” or “sea-urchins” which is used by the skilled person.
• the majority of the pores is constituted by the free spaces located between the radiating acicular platelets. These pores, which are by nature “wedge-shaped”, have a continuously variable diameter of between 100 and 1000 ⁇ .
• the network of interconnected macropores results from the space which is left free between the juxtaposed agglomerates.
• These catalysts with a polymodal pore profile have a pore distribution (determined by mercury porosimetry) which is preferably characterized as follows:
• the specific surface area of these catalysts is in the range 50 to 250 m 2 /g.
• the “thorny chestnut husk” or “sea-urchins” pore structure associated with the pore distribution characteristics described above can produce hydrorefining and/or hydroconversion catalysts with very high retention powers while keeping the hydrodemetallization activity high, which performances cannot be achieved with bimodal catalysts.
• the reasons are that the “wedge-shaped” shape of the mesopores in the thorny chestnut husk or sea-urchins structure compensate for or cut out the concentration gradients of the reagents which would normally be established in a cylindrical pore, which phenomenon forms a highly favorable geometry which can counter pore mouth plugging.
• each mesopore or practically each pore has access independently of others to the interstitial macroporosity favoring homogeneous accumulation of deposits without premature deactivating plugging.
• the catalyst is used in the form of beads or extrudates.
• the “bead” form means that bed fluidization is more homogeneous and its abrasion resistance properties are improved over the “extrudate” form.
• the beads move more homogeneously and the homogeneity of the solids in the bed means that a good metal retention level is achieved while avoiding the phenomena of segregation due to gravity.
• the bead size is also adjustable as a function of the desired chemical activity to minimize problems linked to diffusion of molecules into the pores of the catalyst. Metal capture is considerably enhanced in an ebullated bed compared with a fixed bed.
• the catalyst with a thorny chestnut husk or sea-urchins pore structure has a poorer performance (compared with bimodal catalysts) as regards the initial performance in the HDAC7, HDM, HDCCR functions, although they have a high retaining power which is necessary to process hydrocarbon feeds with a high metals content (Ni+V of more than 40 ppm, for example).
• a high metals content Ni+V of more than 40 ppm, for example.
• FR-A-2 534 828 describes the preparation of catalysts containing one or more metals from groups V, VI and/or VIII and an alumina, silica or silica-alumina type support, said support being crushed but when an autoclaving step is carried out in the process, the crushing operation is systematically carried out after that autoclaving step.
• polymodal catalysts with a thorny chestnut husk structure in the form of alumina-based agglomerates which are mainly irregular and non-spherical, may be obtained with an improved strength compared with those obtained by the process of FR-A-2 534 828 by modifying the position of the crushing step in the steps of the preparation process.
• This important advantage allows the catalyst to be used in an ebullated bed reactor, whereas this would have been impossible with the catalyst obtained by the process of FR-A-2 534 828.
• the catalysts obtained in accordance with the invention can produce optimum performances as regards HDAC7, HDM activity, stability and retention capacity for hydroconverting heavy metal-containing hydrocarbon feeds.
• the invention concerns a catalyst which can be used in fixed or ebullated bed hydrorefining (hydrotreatment) and/or hydroconversion of heavy metal-containing hydrocarbon feeds having both an improved activity, a high retention power, a high stability of performance and a high strength.
• Said catalyst comprises a porous alumina-based support having a thorny chestnut husk or sea-urchins pore structure and is characterized by the irregular and non-spherical shape of said support. This is mainly in the form of fragments obtained by crushing alumina beads using a process as defined below.
• the invention concerns a catalyst comprising an alumina-based support, at least one catalytic metal or compound of a catalytic metal from group VIB and/or VIII, the pore structure of which is composed of a plurality of juxtaposed agglomerates each formed by a plurality of acicular platelets, the platelets of each agglomerate being generally oriented radially with respect to the others and with respect to the centre of the agglomerate, said support having an irregular and non-spherical shape and being mainly in the form of fragments obtained by crushing alumina beads, and prepared using a process including the following steps:
• the granulometry of the support obtained at the end of the process is such that the diameter of the sphere which circumscribes at least 80% by weight of said fragments after crushing is in the range 0.05 to 3 mm.
• said diameter is preferably between 0.1 and 2 mm and, highly preferably, between 0.3 and 1.5 mm.
• said diameter is preferably between 1.0 and 2.0 mm.
• the active phase of said catalyst contains at least one catalytic metal or a compound of a catalytic metal from group VIB (group 6 in the new periodic table notation), preferably molybdenum or tungsten, and/or optionally at least one catalytic metal or a compound of a catalytic metal from group VIII (groups 8, 9 and 10 in the new periodic table notation), preferably nickel or cobalt.
• the catalyst may further comprise at least one doping element selected from phosphorus, boron, silicon and halogens (group VIIA or group 17 of the new periodic table notation), preferably phosphorus.
• group VIIA or group 17 of the new periodic table notation preferably phosphorus.
• the catalyst contains at least one group VIB metal (preferably molybdenum) and optionally at least one non noble group VIII metal, preferably nickel.
• group VIB metal preferably molybdenum
• non noble group VIII metal preferably nickel.
• a preferred catalyst of this type is Ni Mo P.
• the improved properties of the catalyst of the present invention are due to improved diffusion of species into the interior of the catalyst grain and by association, the small size of the grains or fragments, their specific form resulting in a higher external surface area/grain volume ratio and to a thorny chestnut husk or sea-urchins porosity.
• the “wedge-shaped” shape of mesopores of the thorny chestnut husk or sea-urchins structure compensates or cuts out the reagent concentration gradients which would normally occur in a cylindrical pore.
• the small grain size of the support and their specific irregular non-spherical shape encourages homogeneous ingress of reagents into the macroporosity and at each facet, without plugging the pore mouths.
• the mean free path or effective diameter inside a grain or fragment is always less than the diameter of the sphere circumscribing said fragment, while it is strictly identical to the diameter in the case of beads.
• the very irregular shape of the grains or fragments it is possible, however, to circumscribe a sphere in each of them and the fragment size is defined by the diameter of the sphere circumscribing said fragment.
• HDM hydrodemetallization
• HDAC7 hydroconversion functions of asphaltenes which are insoluble in n-heptane
• the quantity of group VIB metal expressed as a % by weight of oxide with respect to the weight of the final catalyst, is in the range 1% to 20%, preferably in the range 5% to 15%.
• the quantity of non-noble group VIII metal may be in the range 0 to 10%, preferably in the range 1% to 4%.
• the quantity of phosphorus expressed as a % by weight of oxide with respect to the final catalyst weight, may be in the range 0.3% to 10%, preferably in the range 1% to 5%, and more preferably in the range 1.2% to 4%.
• the quantity of boron expressed as a % by weight of oxide with respect to the weight of the final catalyst, is less than 6%, preferably less than 2%.
• the atomic ratio between the elemental phosphorus and the group VIB element is advantageously in the range 0.3 to 0.75.
• the silicon content is in the range 0.1% to 10% by weight of oxide with respect to the final catalyst weight.
• the halogen content is less than 5% by weight with respect to the final catalyst weight.
• the alumina-based support has a pore structure which is composed of a plurality of juxtaposed agglomerates each formed by a plurality of acicular platelets, the platelets of each agglomerate generally being oriented radially with respect to the others and with respect to the centre of the agglomerate, said support having an irregular and non-spherical shape and being mainly in the form of fragments obtained by crushing alumina beads, and prepared using a process including the following steps:
• the granulometry of the support obtained at the end of the process is such that the diameter of the sphere circumscribing at least 80% by weight of said fragments after crushing is in the range 0.05 to 3 mm.
• said diameter is preferably between 0.1 and 2 mm and, highly preferably, between 0.3 and 1.5 mm.
• said diameter is preferably between 1.0 and 2.0 mm.
• the active alumina support obtained in accordance with the invention mainly with an irregular and non-spherical shape, generally has the following characteristics: the loss on ignition, measured by calcining at 1000° C., is in the range from about 1% to about 15% by weight, the specific surface area is in the range from about 80 to about 300 m 2 /g, their total pore volume is in the range from about 0.45 to about 1.5 cm 3 /g.
• the process cited above for preparing an alumina support can modify the pore volume distribution depending on the pore size of the untreated agglomerates. It can increase the proportion of pores in the range 100 to 1000 ⁇ , reduce the proportion of pores of less than 100 ⁇ and reduce the proportion of pores of over 5000 ⁇ by modifying the proportion of pores in the range 1000 to 5000 ⁇ less.
• the alumina agglomerates obtained may have been thermally stabilized by rare earths, silica or alkaline-earth metals, as is well known to the skilled person. In particular, they may be stabilized using the process described in United States patent U.S. Pat. No. 4,061,594.
• the deposit obtained at the end of step g) is impregnated with at least one solution of at least one catalytic metal and optionally with at least one dopant.
• the deposit of active phase in the oxide state and the doping element or elements onto the crushed alumina agglomerates is preferably carried out by the “dry” impregnation method which is known to the skilled person. Impregnation is highly preferably carried out in a single step using a solution containing all of the constituent elements of the final catalyst (co impregnation). Other impregnation sequences may be carried out to obtain the catalyst of the present invention.
• Sources of elements from group VIB which may be used are well known to the skilled person.
• sources of molybdenum and tungsten which may advantageously be used are oxides, hydroxides, molybdic and tungstic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic and phosphotungstic acids and their salts, acetylacetonates, xanthates, fluorides, chlorides, bromides, iodides, oxyfluorides, oxychlorides, oxybromides, oxyiodides, carbonyl complexes, thiomolybdates and carboxylates.
• oxides and ammonium salts are used, such as ammonium molybdate, ammonium heptamolybdate or ammonium tungstate.
• Sources of group VIII elements which may be used are known; examples are nitrates, sulphates, phosphates, halides, carboxylates such as acetates or carbonates, hydroxides and oxides.
• the preferred phosphorus source is orthophosphoric acid, however salts and esters such as alkaline phosphates, ammonium phosphates, gallium phosphates or alkyl phosphates are also suitable.
• Phosphorous acids for example hypophosphorous acid, phosphomolybdic acid and its salts, phosphotungstic acid and its salts may also advantageously be used.
• the phosphorus may, for example, be introduced in the form of a mixture of phosphoric acid and a basic nitrogen-containing organic compound such as ammonia, primary and secondary amines, cyclic amines, compounds from the pyridine family and quinolines and compounds from the pyrrole family.
• the boron source may be boric acid, preferably orthoboric acid H 3 BO 4 , ammonium diborate or pentaborate, boron oxide or boric esters.
• the boron may, for example be introduced using a solution of boric acid in a water/alcohol mixture or in a water/ethanolamine mixture.
• a number of silicon sources may be employed.
• ethyl orthosilicate Si(OEt) 4 siloxanes, silicones, halogen silicates such as ammonium fluorosilicate (NH 4 ) 2 SiF 6 or sodium fluorosilicate Na 2 SiF 6 .
• Silicomolybdic acid and its salts or silicotungstic acid and its salts may also advantageously be employed.
• the silicon may, for example, be added by impregnating with ethyl silicate in solution in a water/alcohol mixture.
• Sources of the group VIIA element (halogens) which may be used are well known to the skilled person.
• fluoride anions which may be introduced in the form of hydrofluoric acid or its salts.
• Said salts are formed with alkali metals, ammonium or an organic compound.
• the salt is advantageously formed in the reaction mixture by reaction between the organic compound and hydrofluoric acid.
• hydrolyzable compounds which may liberate fluoride anions in water, such as ammonium fluorosilicate (NH 4 ) 2 SiF 6 , silicon tetrafluoride SiF 4 or sodium fluorosilicate Na 2 SiF 6 .
• the fluorine may, for example, be introduced by impregnating with an aqueous solution of hydrofluoric acid or ammonium fluoride.
• the process for preparing the catalyst of the present invention comprises the following steps:
• Calcining is not necessary in the case in which the impregnation solutions are examples of compounds containing elemental nitrogen.
• the pore distribution of the catalyst determined by mercury porosity, is as follows:
• the total pore volume of the catalysts of the invention is in the range 0.4 to 1.8 g/cm 3 .
• the settled packing density of the catalysts of the invention is in the range 0.35 to 0.80 g/cm 3 .
• the diameter of the pores at VHg/2 is in the range 300 to 700 ⁇ , i.e. the mean pore diameter wherein the volume on the pore distribution graph corresponds to half the total pore volume is in the range 300 to 700 ⁇ , i.e. 30 to 70 nm.
• the catalysts of the invention have a specific surface area, measured by the BET method, in the range 50 to 250 m 2 /g.
• the mechanical strength of the catalyst is a determining factor and is measured by determining the percentage of fines (particles passing through a 850 ⁇ m sieve) produced when the catalyst is rotated for a given period in a cylinder provided with baffles. At the end of the test, the solid obtained is sieved and the fines are weighed. The loss on attrition is quantified using the ASTM D4058-96 standard.
• % loss on attrition 100(1-weight of catalyst with a size of more than 850 ⁇ m after test/weight of catalyst with size more than 850 ⁇ m loaded into cylinder).
• the loss on attrition quantified using the ASTM D4058-96 standard is less than 5% by weight, and preferably 2% or less.
• the mechanical strength is determined by measuring the crush strength using the Shell (ESH) method which consists of crushing a certain quantity of particles and recovering the fines which are generated.
• the crush strength corresponds to the force exerted to obtain a percentage of fines (fines being the particles passing through a 425 ⁇ m sieve) representing 0.5% of the mass of particles which undergo the test.
• the method usually used known as the Shell Method, has the reference “Shell Method Series SMS1471-74” and is carried out in a bed crushing apparatus sold by Vinci Technologie under the reference “Bulk crush strength-Shell-SMS Method”.
• a catalyst can be used in fixed bed mode if its Shell crush strength is over 1.0 MPa.
• the crush strength measured using the Shell method is over 1.0 MPa and preferably 1.5 MPa or more.
• the invention also concerns the process for preparing the catalyst including the support preparation process followed by impregnating the support using at least one solution of at least one catalytic metal and an optional dopant.
• the catalysts of the invention may be employed in an ebullated bed reactor alone or partially in the form of fragments and partially in the form of beads, as described in U.S. Pat. No. 4,552,650, or in the form of cylindrical extrudates.
• the feeds may, for example, be atmospheric residues or vacuum residues from straight through distillation, deasphalted oils, residues from conversion processes such as those derived from coking, or from fixed bed, ebullated bed or moving bed hydroconversion. These feeds may be used as is or diluted with a hydrocarbon fraction of a mixture of hydrocarbon fractions which may, for example, be selected from products from the FCC process, a light cycle oil (LCO), a heavy cycle oil (HCO), a decanted oil (DO), a slurry, or they may be derived from distillation, gas oil fractions, in particular those obtained by vacuum distillation denoted VGO (vacuum gas oil).
• the heavy feeds may thus include cuts derived from coal liquefaction, aromatic extracts or any other hydrocarbon cut.
• the heavy feeds generally have initial boiling points of more than 300° C., more than 1% by weight of molecules having a boiling point of more than 500° C., a Ni+V metals content of more than 1 ppm by weight, and an asphaltenes content, precipitated in heptane, of more than 0.05%.
• part of the converted effluents may be recycled upstream of the unit operating the hydroconversion/hydrotreatment process.
• the heavy feeds may be mixed with powdered coal; this mixture is generally termed a slurry. These feeds may be by-products from the conversion of coal and re-mixed with fresh coal.
• the coal content in the heavy feed generally and preferably represents 0.25 by weight (coal/feed) and may vary between 0.1 and 1.
• the coal may contain lignite, it may be a sub-bituminous coal or it may be bituminous. Any type of coal may be used in the invention, both in the first reactor and in all of the ebullated bed reactors.
• the catalyst is generally used at a temperature in the range 320° C. to 470° C., preferably 400° C. to 450° C., at a partial pressure of hydrogen of about 3 MPa to about 30 MPa, preferably 10 to 20 MPa, at a space velocity of about 0.1 to 10 volumes of feed per volume of catalyst per hour, and with a ratio of gaseous hydrogen to liquid hydrocarbon feed in the range 100 to 3000 normal cubic metres per cubic metre, preferably 200 to 1200 normal cubic metres per cubic metre.
• a particular application of the catalyst of the invention is the use of the catalyst in the presence of coal mixed with the heavy feed to be converted.
• the powdered coal is mixed with a hydrocarbon feed which is richer in hydrogen for conversion in the presence of hydrogen and a supported catalyst.
• This operation is generally carried out in one or more reactors in series operating in ebullated bed mode.
• Using the catalyst of the invention could improve the hydrodynamic behaviour of the system and the continuous catalyst withdrawal unit.
• the conversion of coal in a liquid is carried out by the first reactor and then the HDM, the impurities are captured at the same time and then a finishing step may be carried out using other catalysts.
• the catalysts of the present invention preferably undergo a sulphurization treatment to transform at least part of the metallic species into the sulphide before bringing them into contact with the feed to be treated.
• This sulphurization activation treatment is well known to the skilled person and may be carried out using any method which has been described in the literature.
• One conventional sulphurization method which is well known to the skilled person consists of heating the mixture of solids in a stream of a mixture of hydrogen and hydrogen sulphide or in a stream of a mixture of hydrogen and hydrocarbons containing sulphur-containing molecules at a temperature in the range 150° C. to 800° C., preferably in the range 250° C. to 600° C., generally in a traversed bed reaction zone.
• the catalysts described above may also be used in a fixed bed reactor, alone or partly in the form of fragments and partly in the form of beads as described in U.S. Pat. No. 4,552,650 or in the form of cylindrical extrudates.
• the feeds may, for example, be atmospheric residues or vacuum residues from direct distillation, deasphalted oils, residues from conversion processes such as those from coking, fixed bed, ebullated bed or moving bed hydroconversion. These feeds may be used as is or be diluted with a hydrocarbon fraction or a mixture of hydrocarbon fractions which may, for example, be selected from products derived from the FCC process, a light cycle oil (LCO), a heavy cycle oil (HCO), a decanted oil (DO), a slurry, or they may be derived from distillation, gas oil fractions, in particular those obtained by vacuum distillation denoted VGO (vacuum gas oil).
• the heavy feeds may thus include cuts derived from coal liquefaction, aromatic extracts, or any other hydrocarbon cut.
• the heavy feeds generally have initial boiling points of more than 300° C., more than 1% by weight of molecules having a boiling point of more than 500° C., a Ni+V metals content of more than 1 ppm by weight, and an asphaltenes content, precipitated in heptane, of more than 0.05%.
• part of the converted effluents may be recycled upstream of the unit operating the hydroconversion/hydrotreatment process.
• the catalyst is generally used at a temperature in the range 320° C. to 450° C., preferably 350° C. to 410° C., at a partial pressure of hydrogen of about 3 MPa to about 30 MPa, preferably 10 to 20 MPa, at a space velocity of about 0.05 to 5 volumes of feed per volume of catalyst per hour, preferably 0.2 to 0.5 volumes of feed per volume of catalyst per hour, and with a ratio of gaseous hydrogen to liquid hydrocarbon feed in the range 200 to 5000 normal cubic metres per cubic metre, preferably 500 to 1500 normal cubic metres per cubic metre.
• the catalysts used in the present invention preferably undergo a sulphurization treatment to transform at least part of the metallic species into the sulphide form before bringing them into contact with the feed to be treated.
• This sulphurization activation treatment is well known to the skilled person and may be carried out using any method which has been described in the literature.
• One conventional sulphurization method which is well known to the skilled person consists of heating the mixture of solids in a stream of a mixture of hydrogen and hydrogen sulphide or in a stream of a mixture of hydrogen and hydrocarbons containing sulphur-containing molecules at a temperature in the range 150° C. to 800° C., preferably in the range 250° C. to 600° C., generally in a traversed bed reaction zone.
• the product obtained was constituted by a mixture of transition aluminas: (vic) and (rho) aluminas.
• the specific surface area of this product was 300 m 2 /g and the loss on ignition (LOI) was 5%.
• the alumina (after milling) was in the form of a powder the mean particle diameter of which was 7 micrometres.
• This alumina was mixed with wood flour as a pore-forming agent (15% by weight) then formed in a granulator or pelletizer for a period which was adapted to the desired granulometry.
• the agglomerates obtained underwent a maturation step by passing steam at 100° C. for 24 hours then drying. They were then sieved and crushed and finally calcined.
• beads were then dry impregnated with a solution containing, for example, a mixture of nitric acid and acetic acid in an aqueous phase in an impregnator drum. Once impregnated, they were introduced into an autoclave for about 2 hours, at a temperature of 210° C. and a pressure of 20.5 bars.
• crushed alumina agglomerates were obtained in accordance with the invention which were dried for 4 hours at 100° C. and calcined for 2 hours at 650° C.
• the agglomerate size was in the range 1 to 1.5 mm. Their pore volume was 0.95 cm 3 /g with a multimodal pore distribution. The specific surface area of the support was 130 m 2 /g.
• a catalyst was prepared in the form of beads using the procedure of Example 1 with the exception of the crushing step.
• Beads with a granulometry in the range 1.4 to 2.8 mm were selected.
• the support of this example was prepared as described in Example 1, but the granulation time and the sieving-crushing steps were modified to obtain agglomerates with a size in the range 1.4 to 2.8 mm.
• a catalyst was prepared in the form of beads using the procedure of Example 1 with the exception of the crushing step which was carried out after autoclaving.
• catalyst D could not be used in an ebullated bed as the amount of fines generated at the end of the attrition test was much higher than 5% by weight.
• the pilot reactor was loaded with 1 litre of catalyst.
• the unit was charged with a gas oil from vacuum distillation or VD with the characteristics shown in Table 3.
• the temperature was increased to 343° C. then the test feed, a Safaniya type vacuum distillation residue (VR) was injected.
• the reaction temperature was than raised to 410° C.
• the hydrogen flow rate was 600 l/l; the hourly space velocity was 0.3 l/l/h.
• the conditions of the test were isothermal, which allowed the deactivation of the catalyst to be measured by directly comparing the performances at different ages.
• the ages are expressed here in m 3 of feed/kg of catalyst (m 3 /kg), which represents the cumulative quantity of feed passed over the catalyst compared with the loaded weight of catalyst.
• HDM conversion performance
• HDM (wt %) ((ppm by wt of Ni+V) feed ⁇ (ppm by wt of Ni+V) test /(( ppm by wt of Ni+V) feed *100
• the feed was then changed to a Boscan atmospheric residue. This feed allowed the metal retention of the catalyst to be evaluated.
• the test aimed to maintain the % HDM in the range 80% to 60%. To this end, the reaction temperature was kept at 410° C. The test was stopped when the HDM fell below 60%. Conversion was maintained between 50% and 60% by weight to obtain good fuel stability. To evaluate the stability of the products formed, a measurement was carried out using the Shell P value method on the 350° C.+ fraction of the effluent recovered after the test.
• Table 4 compares the performance of catalysts A, B and C at the start of the test (0.56 m 3 /kg) and at the end of the test (1.44 m 3 /kg).
• Catalyst D could not be evaluated even in terms of initial activity as the production of fines at the end of the second day of the test (age ⁇ 0.17 m 3 /kg) caused operational problems (plugging, appearance of pressure gradients) and the unit was stopped.
• the HDM catalysts supported on crushed agglomerates of the invention had improved initial HDM properties and higher stability. Higher HDM performances were obtained with a smaller agglomerate size.
• Table 5 below shows the results obtained for fixed bed crushing measurements carried out using the method described for catalysts A, B, C, D.
• the Shell crush strength for catalyst D was not compatible with use in a fixed bed residue hydroconversion unit as this value was below 1 MPa.
• the tests were carried out in a hydrotreatment pilot unit comprising a fixed bed tubular reactor.
• the reactor was filled with 1 litre of catalyst.
• the fluid flow (residue+hydrogen) in the reactor was upwards.
• This type of pilot unit is representative of the operation of one of the reactors of a HYVAHL unit from IFP for fixed bed residue hydroconversion.
• the unit After a step for sulphurization by circulating a gas oil cut supplemented with dimethyldisulphide in a reactor at a final temperature of 350° C., the unit was operated for 300 hours with Arabian light atmospheric residue at 370° C., 150 bars of total pressure using a HSV of 0.5 l of feed/l of catalyst/h. The hydrogen flow rate was such that it had a ratio of 1000 l/l of feed.
• the test conditions using ALAR were isothermal, which allowed the initial deactivation of the catalyst to be measured by directly comparing the performances at different ages. The ages were expressed as hours of operation with Arabian light atmospheric residue, the zero time being taken as that when the test temperature (370° C.) was reached.
• the HDM, HDASC7 and HDCCR performances are defined as follows:
• HDM (wt %) ((ppm by wt of Ni+V) feed ⁇ (ppm by wt of Ni+V) test ((ppm by wt of Ni+V) feed *100
• HDCCR (wt %) ((wt % of CCR) feed ⁇ (wt % of CCR) test /((wt % of CCR) feed *100
• Table 7 compares the HDM, HDASC7and HDCCR performances of catalysts A, B and C at the start of the test (50 hours) and at the end of the test (300 hours).
• the feed was then changed to a Boscan atmospheric residue.
• the test conditions were aimed at maintaining a constant HDM ratio of about 80% by weight throughout the cycle. To this end, catalyst deactivation was compensated for by progressively increasing the reaction temperature. The test was stopped when the reaction temperature reached 420° C., a temperature which is considered to be representative of the temperature at the end of the cycle of an industrial residue hydrorefining unit.
• Table 8 compares the quantities of nickel+vanadium deriving from Boscan AR deposited on the 3 catalysts.
• HDM catalysts supported on agglomerates of the invention produced initial performances on ALAR and retention on BAR which were better than those for the catalyst supported on beads; the gains in performances and retention are better when the agglomerates are smaller.

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