WO2007084440A1 - Supports de silice - Google Patents

Supports de silice Download PDF

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Publication number
WO2007084440A1
WO2007084440A1 PCT/US2007/001003 US2007001003W WO2007084440A1 WO 2007084440 A1 WO2007084440 A1 WO 2007084440A1 US 2007001003 W US2007001003 W US 2007001003W WO 2007084440 A1 WO2007084440 A1 WO 2007084440A1
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WIPO (PCT)
Prior art keywords
carrier
silica
catalyst
carriers
angstroms
Prior art date
Application number
PCT/US2007/001003
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English (en)
Inventor
Jean W. Beeckman
Jason Wu
Theodore E. Datz
Ralph Dehaas
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Exxonmobil Research And Engineering Company
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Publication of WO2007084440A1 publication Critical patent/WO2007084440A1/fr

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    • 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
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/70—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
    • B01J23/76—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
    • B01J23/882—Molybdenum and 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
    • 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
    • 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)
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • 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
    • B01J35/613—10-100 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
    • B01J35/61—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
    • B01J35/635—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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm

Definitions

  • This invention relates to carriers, to methods of preparing said carriers, to catalyst compositions comprising said carriers and to catalytic conversion processes using catalyst compositions comprising said carriers.
  • Catalyst supports made of inorganic oxides are typically prepared by forming a mixture of one or several sources of the inorganic oxides and binders in a suitable vehicle, said vehicle typically being water, an organic solvent or mixtures thereof. The mixture is formed into bodies of various shapes, dried and calcined.
  • these bodies In order to be used as carriers, these bodies must have appropriate surface properties, sizes, shapes and porosities to support the desired amounts of active materials and to enable catalyst handling, especially during reactor loading and unloading.
  • the carriers must also be strong enough to sustain catalytic conditions, and they must also have appropriate porosities and shapes to avoid high pressure drops across the reactor and allow the desired catalytic reactions to take place.
  • catalyst carriers will depend on various factors, such as, for example, the type of catalytic material used, the required catalyst strength and the required diffusivity across catalyst particles.
  • silica carriers While silica carriers have been known for a long time and are commercially available in various forms, silica carriers having large pores are not easy to obtain on large commercial scale, for technical and economical reasons.
  • One of the technical problems in forming particulate inorganic material, such as silica resides in the difficulty of forming suitable plasticized mixtures that can be processed in conventional particle forming equipment, such as extruders, for example.
  • International Publication Number WO 2006/026067-A1 describes a method for the manufacture of a structured body, which process comprises (a) preparing a batch composition free of organic solvent comprising (i) at least one particulate inorganic material, (ii) at least one particulate silicone resin of average particle size 700 microns or less, and (iii) water, and (b) forming the batch composition into a structured body.
  • the invention relates to amorphous carriers having a silica content of at least about 85 wt%, preferably of at least about 90 wt%, more preferably of at least 95 wt%, a pore volume determined by mercury intrusion porosimetry of from 0.8 cm 3 /g to 1.0 cm 3 /g, preferably of from 0.8 crnVg to 0.95 cmVg and a median of about 180 Angstroms or greater, preferably in the range of from about 200 Angstroms to about 500 Angstroms, conveniently of about 220 Angstroms or greater, and more conveniently in the range of from about 220 Angstroms to about 450 Angstroms.
  • the carriers of the invention also have one or several of the following features:
  • the carrier further comprises up to 10 parts by weight, preferably up to 5 parts by weight, of a polymeric material per 100 parts by weight of carrier.
  • the invention also provides a method for making carriers having the any of aforementioned properties, wherein the method comprises the steps of a) shaping particles from a mixture obtained from at least one silica source, a liquid medium, and optionally at least one polymeric organic extrusion aid; b) drying the shaped particles obtained in step a), preferably at a temperature of 200 0 C or less; and c) heating the shaped particles to a temperature in the range of from about 500 0 C to about 800 0 C in the presence of steam.
  • At least one of the silica sources is an amorphous silica powder, and, preferably, the mixture used in step a) is obtained by a process comprising the step of combining the amorphous silica powder, a silica sol, more preferably, as silica sol having a pH below 7, and at least one polymeric organic extrusion aid.
  • step c) takes place under one or several of the following conditions:
  • the invention also provides a supported catalyst comprising the carrier of the invention and the use of such supported catalysts in hydrocarbon conversion processes, in particular, hydrocarbon hydrogenation processes.
  • the invention relates to carriers that are particularly suitable as catalyst components, in particular, as carriers for supported catalysts.
  • the carriers consist essentially of silica, that is, the silica content of the carrier is of at least 85 wt%, preferably at least 90 wt%, more preferably at least 95 wt%.
  • the carriers of the present invention are amorphous large pore materials, with a median pore size of about 180 Angstroms or greater, conveniently in the range of from about 200 Angstroms to about 500 Angstroms, and preferably of about 220 Angstroms or greater, conveniently in the range of from about 220 to about 450 Angstroms.
  • the carriers of the invention have a median pore size of 600 Angstroms or less, more preferably 500 Angstroms or less, conveniently 450 Angstroms or less.
  • median pore sizes are determined by mercury intrusion porosimetry, according to the ASTM D4284-03 method.
  • the pore size distribution may be monomodal, bimodal or plurimodal. However, monomodal pore size distributions are preferred.
  • the silica carriers of the invention are non-crystalline, amorphous solids. Their solid structure possesses substantially no short distance or long distance order, such as that found in zeolite or zeolite-type materials, or even mesoporous materials such as M-41 S-type materials.
  • the silica carriers of the invention may have various shapes and sizes, depending on their intended use.
  • suitable shapes include spheres, beads, cylinders, prisms with various prism base shapes, such as, for example, trilobe or quadrulobe prism base shapes, tubes or honeycombs.
  • the carrier conveniently has a size of from about 1 mm to about 20 mm.
  • the sphere, cylinder base or prism base shape conveniently has a size of from about 1 mm to about 3 mm, preferably from 1.1 mm to 2.5 mm.
  • the carriers of the invention typically have a pore volume of from 0.8 to 1.0 cm 3 /g, preferably of from 0.8 to 0.95 cm 3 /g, as determined by mercury intrusion porosimetry, according to the ASTM D4284-03 method.
  • the carriers of the invention have a surface area, determined by BET, in the range of from 50 to 150 m 2 /g, more preferably in the range of from 60 to 140 m 2 /g.
  • the silica carrier contains a very low level of alkaline metal ions.
  • Alkaline metal ions are often present in small amounts in silica carriers, due to their presence in the starting materials used to make the carriers. During calcination or catalytic use, traces of sodium or potassium can cause sintering and/or affect catalytic performance. To avoid these problems, the presence of sodium and potassium in the silica carriers must be kept as low as possible.
  • the alkaline ion levels in the silica carriers of the invention typically are less than 1 %, preferably less than 0.7 %, more preferably 0.6 % or less, and even more preferably 0.5 % or less of the weight of the carrier.
  • the carriers may also contain organic materials, for example up to 10 parts by weight, preferably up to 5 parts by weight of organic materials per 100 parts by weight of silica carrier.
  • the organic material is a polymeric material, for example an organic material selected from polyvinyl alcohols, cellulose, cellulose ethers, such as methylcellulose and hydroxypropyl methyl cellulose polymers, colloidal silica, floridin, carbon powder, graphite, polyoxyethylene, mixed walnut shell or a mixture thereof.
  • the organic material is a polyvinyl alcohol.
  • the carrier has a crush strength of at least 625 g/mm (35 lb/inch), preferably in the range of from 625 g/mm (35 lb/inch) to 2144 g/mm (120 lb/inch), when determined by the strain beam method with a 3.175 mm (1/8 inch) Anvil configuration, as described in the experimental section.
  • the silica carriers are conveniently prepared by a method comprising the steps of a) shaping particles from a mixture obtained from at least one silica source, a liquid medium and optionally at least one polymeric organic extrusion aid, b) drying the shaped particles obtained in step a), and c) heating the shaped particles to a temperature in the range from about 500 0 C to about 800 0 C in the presence of steam.
  • the silica source used to prepare the mixture of step a) is conveniently selected from readily available solid silica sources, silica sols or mixtures thereof.
  • the mixture that is shaped in step a) is obtained by combining at least one silica powder and at least one silica sol.
  • silica sols are stable colloidal dispersions of amorphous silica particles in an aqueous or organic liquid medium, preferably an aqueous medium.
  • Non-limiting examples of commercially available silica sols include those sold under the tradenames Nyacol (available from Nyacol Nano Technologies, Inc.
  • silica sols are prepared from sodium silicate that inevitably contain sodium. As mentioned previously, it is preferable to avoid the presence of alkali metals, such as sodium or portassium, in the carriers of the invention. Therefore, if silica sols containing sodium are used, a step of ion exchange will be required after formation of the particles in order to remove sodium. To avoid carrying out ion exchange steps, it is preferable to use silica sols that contain very little or, ideally, no detectable traces of sodium and have a pH value of less than 7.
  • the silica sol used in the process is slightly acidic.
  • preferred silica sols that contain no detectable traces of sodium include Nyacol 2034DI, Nalco 1034A, Ultra-Sol 7H or NexSil 2OA.
  • any silica powder can be used to form the solution used in step a), provided it forms with the other ingredients used in step a), a mixture that can be extruded.
  • Ultrasil VN3SP commercially available from Degussa
  • HiSiI 233 EP available from PPG Industries.
  • the mixture shaped in step a) also contains at least one polymeric organic extrusion aid.
  • suitable polymeric organic extrusion aids include polymeric materials selected from polyvinyl alcohols, cellulose, cellulose ethers, such as methylcellulose and hydroxypropyl methyl cellulose polymers, colloidal silica, floridin, carbon powder, graphite, polyoxyethylene, mixed walnut shell or mixtures thereof.
  • the organic material is a polyvinyl alcohol.
  • the mixture shaped in step a) contains a liquid medium, such as an organic or aqueous medium.
  • a liquid medium such as an organic or aqueous medium.
  • the liquid medium is water.
  • the amounts of ingredients can vary within wide limits, provided that the mixture used in step a) has the appropriate fluidity and cohesion to be converted into shaped particles.
  • the person skilled in the art will appreciate that the ratios of the mixture components will be different, depending on the physical and chemical properties of the ingredients used, as well as the shaping technique used.
  • the silica sol be used in an amount such that the silica sol contributes from about 5 wt. % to about 40 wt.%, preferably from about 10 wt. % to about 35 wt. %, and more preferably from about 12 wt.% to about 30 wt.
  • the amount of polymeric extrusion aid it should be kept as low as possible but should be sufficient to facilitate extrusion.
  • the polymeric extrusion aid can be used in amounts of about 0.5 to about 10 parts by weight, preferably of about 1 to about 7 parts by weight, more preferably of about 2 to about 5 parts by weight, per 100 parts by weight of silica in the mixture that is used in step a).
  • the mixture which is used in step a) is typically prepared by combining the ingredients together in a mixer, such as, for example, an Eirich mixer or a wheel mixer.
  • the mixture components may be added in different orders to the mixer.
  • the solid components can be placed first in the mixer, followed by the liquid components.
  • the components are typically mixed at room temperature during addition of the silica source(s), polymeric material and water. Mulling can also be applied if necessary, to break down solid particles to a suitable size for mixture cohesion and viscosity.
  • the amount of water can also be adjusted at any stage of the mixture preparation, to obtain a mixture with viscosity and cohesion suitable for the chosen particle shaping process.
  • Particle shaping can be performed by any method known in the art, such as extrusion, compression molding, spherudizing or other bead shaping techniques.
  • particle shaping is performed by extrusion.
  • Extrusion apparatuses suitable for making rod-, cylindrical or prism-shaped particles typically consist of a hopper for introduction of the mixture being shaped, a de- airing chamber, and either a screw-type or plunger-type transport barrel in which pressure is generated for passage of the mixture through a die of the desired geometry. The mixture is extruded onto a carrier belt and passed through driers to relax the strain remaining after extrusion.
  • the driers remove most of the water from the extruded product, but typically do not remove any organic material that may be present in the extrudates; drying is usually performed at a temperature of less than 200 0 C, such as between 100 0 C and 150 0 C, typically of from 120 0 C to 140 0 C for a period of at least 10 minutes, such as from 10 minutes to several hours.
  • the strands obtained after drying are broken up in smaller pieces to form cylinders or prisms.
  • the cylinders or prisms are then sieved and broken up further to the required size range.
  • the mixture used in step a) preferably has a solid contents of 35 to 55 wt%, preferably of 40 to 50 wt. %, most desirably of 40 to 45 wt.% and conveniently of about 43 wt.%.
  • Spherical shapes can be obtained using a spherudizer, such as a McNally-Wellman pelletizing disc or other similar equipment.
  • the spherudizer consists of a rotating disk operated on an angle. As it rotates, smaller spheres used as seed material are place in the bottom part of the disk and a spray of cohesive slurry is sprayed onto them. As the moisture in the slurry evaporates, the solids form a layer on the exterior of the spheres, increasing their diameter. As the spheres increase in size, they segregate into sections where the material of the desired size can be removed. Sphere or pellets can also be formed with pilling machines.
  • the shaped particles are usually referred to as "green" particles or green catalyst.
  • the green particles still contain any polymeric extrusion aid that may have been used and typically have crush strengths that are too low for use in catalytic processes.
  • Heat treatments are thus necessary to harden the particles, and remove any organic material that may be present in the catalyst and that could interfere during use of the carriers.
  • heat treatment is performed by steam calcination, i.e. by heating at temperatures ranging from about 500 0 C to about 800 0 C, preferably, from about 550 0 C to about 750 0 C, in the presence of steam.
  • calcination is performed in the presence of a mixture of steam and air.
  • the calcination atmosphere contains at least 10 vol. % steam, preferably at least 15 vol. % steam, and more preferably, at least 20 vol. % steam.
  • calcination atmosphere contains 10-20 vol. % steam and 90-80 vol. % air; in another particular embodiment, the calcination atmosphere contains 2-10 vol. % air and 98-90 vol. % steam.
  • Calcination conditions can be applied for variable amounts of time, depending on the calcination temperature and the composition of the calcination atmosphere. The duration should be sufficient to allow removal of any organic material present in the particles, and should also be sufficient to harden the particles to the desired level. However, calcination should not be carried out too long, so as to avoid carrier degradation. Typically, the desired results are achieved by applying the calcination conditions for a duration of from about 10 to about 120 minutes, preferably from about 15 to about 60 minutes.
  • the carriers of the invention are useful components of catalysts intended for use in catalytic processes, especially those that require rapid diffusion of reagents and products throughout the catalyst.
  • catalytic processes include reactions using hydrogen, such as hydrogenation, desulfurization, hydrof ⁇ ning, hydrofmishing or hydrocracking, or polymerization reactions, such as supported Ziegler-Natta or metallocene polymerization reactions.
  • the invention also relates to a catalyst comprising the carriers of the invention and an active material.
  • the catalyst comprises a carrier of the invention and one or several metals, more preferably one or several metal-based active materials.
  • the metal is selected from Group IVb, Via and Group VIII of the Periodic Table of Elements.
  • the catalyst comprises a silica carrier of the invention on which cobalt oxide and molybdenum oxide have been deposited.
  • the carriers can be impregnated by a solution of the catalyst or of a solution of a precursor of the catalyst, by methods well known in the art, such as, for example, incipient wetness.
  • incipient wetness a solution containing the catalyst or a precursor thereof is mixed with the carrier up to the point of incipient wetness.
  • the impregnated carrier is then heated and dried at a temperature typically in the range from about 50 0 C to about 200 0 C. Drying can take place under vacuum, or in air, or inert gas such as nitrogen.
  • Catalysts intended for use in hydrogenation often also undergo pretreatments before being used in the catalytic processes.
  • catalysts intended for use in hydrodesulfurization processes will typically undergo a sulf ⁇ dation or activation step before use.
  • the catalyst of the present invention comprises cobalt and molybdenum, and is used to selectively hydrodesulfurize naphtha streams, that is, hydrocarbon fractions that are major components of gasoline, and boiling in the range from about 10 0 C (i.e., starting from C 5 hydrocarbons) to about 232°C at atmospheric pressure, and preferably boiling in the range of from about 21 0 C to about 221 0 C at atmospheric pressure.
  • boiling in the range we mean that the hydrocarbon fractions have an initial and final boiling point within such range, but it does not necessarily mean that the initial and final boiling points necessarily have to be at the end points of the range.
  • the preferred naphtha streams have olefin contents of at least about 5 wt% to about 60 wt%, preferably of at least 5 wt% to about 40 wt%, based on the weight of the naphtha stream.
  • such streams have sulfur contents from about 300 ppm to about 7000 ppm, based on the weight of the naphtha stream, and/or preferably nitrogen contents of from 5 ppm to about 500 ppm, based on the weight of the naphtha stream.
  • Olefins include open chain olefins, cyclic olefins, dienes and cyclic unsaturated hydrocarbons.
  • the preferred catalyst for use to hydrodesulfurize such naphtha streams comprises a silica carrier of the invention and from about 2 wt% to about 8 wt %, preferably from about 3 wt% to about 6 wt% cobalt oxide, based on catalyst, and from about 8 wt% to about 30 wt%, preferably from about 10 wt% to about 25 wt% molybdenum oxide, based on catalyst.
  • the most preferred catalyst also contains an organic ligand used during the metal impregnation step, before the catalyst is used in the hydrodesulfurization process.
  • organic ligands include at least one of carboxylic acids, polyols, amino acids, amines, amino alcohols, ketones, esters and the like, for example, phenanthroline, quinolinol, salicylic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), cyclohexanediaminetetraacetic acid (CYDTA), alanine, arginine, triethanolamine (TEA), glycerol, histidine, acetylacetonate, guanidine, and nitrilotriacetic acid (NTA), citric acid and urea.
  • carboxylic acids for example, phenanthroline, quinolinol, salicylic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), cyclohexanediaminetetraacetic acid (CYDTA), alanine, arginine, triethanolamine (TEA), glycerol, histidine
  • the impregnated catalyst is preferably used in a dried, but not calcined, form.
  • the dried catalyst precursor is treated with hydrogen sulfide at preferred concentrations of from about 0.1 vol.% to about 10 vol.% based on total volume of gases present, for a period of time and at a temperature sufficient to convert metal oxide, metal salt or metal complex to the corresponding sulfide in order to form the HDS catalyst.
  • the hydrogen sulfide may be generated by a sulfiding agent incorporated in or on the catalyst precursor.
  • the sulfiding agent is combined with a diluent.
  • dimethyl disulfide can be combined with a naphtha diluent. Lesser amounts of hydrogen sulfide may be used, but this may extend the time required for activation.
  • An inert carrier may be present and activation may take place in either the liquid or gas phase. Examples of inert carriers include nitrogen and light hydrocarbons such as methane. When present, the inert gases are included as part of the total gas volume. Temperatures are preferably in the range from about 150 0 C to about 700 0 C, more preferably about 160 0 C to about 343°C. The temperature may be held constant or may be ramped up by starting at a lower temperature and increasing the temperature during activation.
  • Total pressure is preferably in the range up to about 5000 psig (34576 kPa), more preferably about 0 psig to about 5000 psig (101 to 34576 kPa), more preferably about 50 psig to about 2500 psig (446 to 17338 kPa).
  • the liquid hourly space velocity is from about 0.1 hr *1 to about 12 hr *1 , preferably about 0.1 hr "1 to about 5 hr '! .
  • the LHSV pertains to continuous mode. However, activation may also be done in batch mode.
  • Total gas rates may for example be from about 89 m 3 /m 3 to about 890 m 3 /m 3 (500 to 5000 scf/B).
  • Catalyst sulfiding may occur either in situ or ex situ. Sulfiding may occur by contacting the catalyst with a sulfiding agent, and can take place with either a liquid or gas phase sulfiding agent. Alternatively, the catalyst may be presulfurized such that H 2 S may be generated during sulfiding. In a liquid phase sulfiding agent, the catalyst to be sulfided is contacted with a carrier liquid containing sulfiding agent. The sulfiding agent may be added to the carrier liquid or the carrier liquid itself may be the sulfiding agent.
  • the carrier liquid is preferably a virgin hydrocarbon stream and may be the feedstock to be contacted with the hydroprocessing catalyst but may be any hydrocarbon stream such as a distillate derived from mineral (petroleum) or synthetic sources.
  • a sulfiding agent is added to the carrier liquid, the sulfiding agent itself may be a gas or liquid capable of generating hydrogen sulfide under activation conditions. Examples include hydrogen sulfide, carbonyl sulfide, carbon disulfide, sulfides such as dimethyl sulfide, disulfides such as dimethyl disulfide, and polysulfides such as di-t-nonylpolysulfide.
  • the sulfides present in certain feeds may act as sulfiding agent and include a wide variety of sulfur- containing species capable of generating hydrogen sulfide, including aliphatic, aromatic and heterocyclic compounds.
  • the catalyst may be contacted with naphtha under hydrodesulfurizing conditions.
  • Hydrodesulfurizing conditions include temperatures of from about 150 0 C to about 400 0 C, and/or pressures of from about 445 kPa to about 13890 kPa (50 to 2000 psig), and/or liquid hourly space velocities of from about 0.1 hr "1 to about 12 hr "1 and/or treat gas rates of from about 89 m 3 /m 3 to about 890 m 3 /m 3 (500 to 5000 scf/B).
  • the desulfurized naphtha can be conducted away for storage or further processing, such as stripping to remove hydrogen sulfide.
  • the desulfurized naphtha is useful for blending with other naphtha boiling-range hydrocarbons to make motor gasoline.
  • SA Surface area
  • the alumina content, sodium content and potassium content were determined by inductively coupled plasma (ICP) emission spectroscopy, using an IRIS instrument manufactured by Thermo . Electron Corporation.
  • ICP inductively coupled plasma
  • Crush strength was determined by averaging the crush strength of 100 or more particles, determined with a Vankel VK200 Tablet Hardness Tester, using a strain beam method with a 3.175 mm (1/8 inch) Anvil configuration. The principle of the method is that a force is applied by the beam to the particle; the crush strength is the amount of force applied by the beam that will cause particle fracture.
  • the instrument reports crush strength as lb/inches. A crush strength of 1 lb/inch can also be expressed as a crush strength of 17.87 g/mm.
  • Ultrasil VN3SP is a precipitated silica available from Degussa having a silica content of 98 wt%, a sodium content of about 0.4 wt%, an alumina content of about 0.1 wt% and a BET surface area of 155-195 m 2 /g.
  • Nyacol 2034DI (available from Nyacol Nano Technologies) is an aqueous colloidal silica sol having a silica content of 34 wt%, a pH of 3.0 and a viscosity of 7 cPs.
  • the polyvinyl alcohol (PVA) used in the experiments is a polyvinyl alcohol sold by Celanese under the tradename PVA 5 having an OH number of 78-82 mole%.
  • the Lancaster Muller is a mixing / mulling apparatus that consists of a rotating pan of approximately 40 liters (10 gallons) in size and is topped with a hydraulically operated stainless steel four inch wheel, scraping blade, and mixer. Pressure can be applied to the mulling wheel by use of regulated air pressure.
  • the purpose of the Lancaster Muller is to mix and push ingredients together. Additional ingredients can be added through a small door on top of the apparatus, or by stopping the rotation, raising the top half of unit and adding directly to the pan.
  • the Eirich Mixer is a mixing apparatus that consists of a variable speed rotating pan of approximately 28 liters (7 gallons) in size and is topped with a variable speed stainless steel four prong mixer, and scraping blade.
  • the purpose of the Eirich Muller is to mix and whip ingredients together. Additional ingredients can be added through a small door on top of the apparatus, or by stopping the rotation, raising the top half of unit and adding directly to the pan.
  • the Two Inch Bonnet Extruder is an extrusion apparatus that uses an electrical motor to drive a two inch diameter auger rotation. At one end of the auger is a feed hopper for supplying the catalyst mix. At the outlet of the auger tube, die plates for shaping the catalyst would be attached by means of bolting the plate to the face of the auger outlet tube. Die plate pressure can be monitored via a pressure transducer located at the outlet of the extruder. The shapes of the extrudate can be dictated by the individual die plate. Typically, either steel or plastic dies are used.
  • n.a. means not available ! below detection limit 3 based on vendor specification "bimodal
  • carrier IV of example 1 was contacted with steam at various temperatures.
  • the balance of the calcination atmosphere composition is air.
  • the balance of the calcination atmosphere composition is air.
  • an impregnation solution was prepared by dissolving ammonium heptamolybdate tetrahydrate and cobalt carbonate hydrate with citric acid (CA) as ligand.
  • the cobalt to molybdenum atomic ratio was 0.48.
  • the CoMo-CA solution was impregnated to silica support S, using the incipient wetness impregnation technique in a single step in an amount so that the dried solid would contain 5.2 wt.% CoO and 20.9 wt.% MoO 3 , based on the weight of the catalyst.
  • the impregnated solid was dried under vacuum at 60 0 C.
  • the silica supported CoMo catalyst was sulfided using 3% H 2 S in H 2 and virgin naphtha under sulfiding conditions. Feed for the catalyst evaluation was an FCC naphtha feed with an initial boiling point of 10 0 C and a final boiling point of 177 0 C containing 1408 ppm sulfur and 46.3 wt.% olefins, based on the weight of the feed.
  • the catalysts were evaluated in an MCFB-48 unit (Multi Channel Fixed Bed-48 Reactor) at 274°C (525°F) at 220 psig using H 2 .
  • Feed flow rate was adjusted to obtain a range of 2-methylthiophene desulfurization from 65 wt.% to 95 wt.%, based on the weight of the feed.
  • Product streams were analyzed using on-line GCs and SCDs.
  • C 5 Olefin content in the product was compared with C 5 olefin content in the feed on a weight basis to calculate the percentage of olefin saturation (% OSAT).
  • Results of the percentage of hydrodesulfurization (% HDS) and % OSAT were stable after about 30 hours of catalyst on stream, and were used to evaluate the olefin saturation (% OSAT) at various HDS conversions (% HDS). At 90% HDS conversion, there was about 8.7 wt.% olefin saturation for the CoMoZSiO 2 catalysts prepared using support S.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Silicon Compounds (AREA)

Abstract

La présente invention concerne des supports amorphes ayant une teneur en silice d’au moins environ 85 % en poids, un volume de pores déterminé par porosimétrie par intrusion de mercure allant de 0,8 cm3/g à 1,0 cm3/g et une taille de pores médiane supérieure ou égale à environ 180 Angströms, les procédés de préparation desdits supports, les compositions de catalyseur comprenant lesdits supports et les procédés catalytiques de conversion utilisant des compositions de catalyseur comprenant lesdits supports.
PCT/US2007/001003 2006-01-17 2007-01-12 Supports de silice WO2007084440A1 (fr)

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WO2011096991A1 (fr) 2010-02-05 2011-08-11 Exxonmobil Chemical Patents Inc. Procédé de déshydrogénation
WO2011096990A2 (fr) 2010-02-05 2011-08-11 Exxonmobil Chemical Patents Inc. Catalyseur et procédé de déshydrogénation
WO2012036819A1 (fr) 2010-09-14 2012-03-22 Exxonmobil Chemical Patents Inc. Procédé de déshydrogénation de cyclohexanone et compositions phénoliques
WO2012082409A1 (fr) 2010-12-17 2012-06-21 Exxonmobil Chemical Patents Inc. Procédé de production de cyclohexylbenzène
WO2012082407A1 (fr) 2010-12-17 2012-06-21 Exxonmobil Chemical Patents Inc. Catalyseur et procédé de déshydrogénation
WO2012115694A1 (fr) 2011-02-21 2012-08-30 Exxonmobil Chemical Patents Inc. Procédé de purification d'hydrogène
WO2012134552A1 (fr) 2011-03-28 2012-10-04 Exxonmobil Chemical Patents Inc. Procédé de déshydrogénation
WO2014085112A1 (fr) 2012-11-30 2014-06-05 Exxonmobil Chemical Patents Inc. Procédé de déshydrogénation
CN105772105A (zh) * 2014-12-16 2016-07-20 中国石油化工股份有限公司 一种改性加氢催化剂载体及其制备方法
US20190176131A1 (en) * 2017-12-11 2019-06-13 Exxonmobil Chemical Patents Inc. Methods of Making Supported Mixed Metal Dehydrogenation Catalysts

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EP2726578B1 (fr) * 2011-06-28 2020-04-29 Shell International Research Maatschappij B.V. Composition imprégnée d'additif d'éther-amine utile dans l'hydrotraitement catalytique d'hydrocarbures, procédé de fabrication d'une telle composition
RU2608740C2 (ru) * 2011-06-28 2017-01-23 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Композиция, имеющая активный металл или его предшественник, аминовый компонент и не содержащую амина полярную добавку, используемая в каталитической обработке водородом углеводородов, способ изготовления такого катализатора

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EP0067459A1 (fr) * 1981-04-13 1982-12-22 Shell Internationale Researchmaatschappij B.V. Particules en silice et procédé de production
EP0280342A2 (fr) * 1987-01-27 1988-08-31 Shell Internationale Researchmaatschappij B.V. Procédé pour la conversion catalytique d'huiles hydrocarbonées
EP0409353A1 (fr) * 1989-07-21 1991-01-23 Gastec N.V. Catalyseur et procédé pour l'oxydation sélective d'hydrogène sulfuré en soufre élémentaire
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Cited By (14)

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Publication number Priority date Publication date Assignee Title
WO2011096991A1 (fr) 2010-02-05 2011-08-11 Exxonmobil Chemical Patents Inc. Procédé de déshydrogénation
WO2011096990A2 (fr) 2010-02-05 2011-08-11 Exxonmobil Chemical Patents Inc. Catalyseur et procédé de déshydrogénation
WO2012036819A1 (fr) 2010-09-14 2012-03-22 Exxonmobil Chemical Patents Inc. Procédé de déshydrogénation de cyclohexanone et compositions phénoliques
US9365467B2 (en) 2010-12-17 2016-06-14 Exxonmobil Chemical Patents Inc. Process of producing cyclohexylbenzene
WO2012082407A1 (fr) 2010-12-17 2012-06-21 Exxonmobil Chemical Patents Inc. Catalyseur et procédé de déshydrogénation
WO2012082409A1 (fr) 2010-12-17 2012-06-21 Exxonmobil Chemical Patents Inc. Procédé de production de cyclohexylbenzène
US9579632B2 (en) 2010-12-17 2017-02-28 Exxonmobil Chemical Patents Inc. Dehydrogenation catalyst and process
US9580368B2 (en) 2010-12-17 2017-02-28 Exxonmobil Chemical Patents Inc. Dehydrogenation process
WO2012115694A1 (fr) 2011-02-21 2012-08-30 Exxonmobil Chemical Patents Inc. Procédé de purification d'hydrogène
US9017641B2 (en) 2011-02-21 2015-04-28 Exxonmobil Chemical Patents Inc. Hydrogen purification process
WO2012134552A1 (fr) 2011-03-28 2012-10-04 Exxonmobil Chemical Patents Inc. Procédé de déshydrogénation
WO2014085112A1 (fr) 2012-11-30 2014-06-05 Exxonmobil Chemical Patents Inc. Procédé de déshydrogénation
CN105772105A (zh) * 2014-12-16 2016-07-20 中国石油化工股份有限公司 一种改性加氢催化剂载体及其制备方法
US20190176131A1 (en) * 2017-12-11 2019-06-13 Exxonmobil Chemical Patents Inc. Methods of Making Supported Mixed Metal Dehydrogenation Catalysts

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RU2418037C2 (ru) 2011-05-10

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