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
  • 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
  • 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
  • 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
  • B01J23/74—Iron group metals
  • B01J23/755—Nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; 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
  • B01J35/635—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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0207—Pretreatment of the support
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
  • C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
• • 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
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/15—X-ray diffraction
• • 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
  • 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
• • 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
• • 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
  • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/30—Particle morphology extending in three dimensions
  • C01P2004/32—Spheres
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/14—Pore volume
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/16—Pore diameter
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/205—Metal content

Definitions

• the present invention relates to the catalytic hydrotreating of heavy hydrocarbon oils containing metals.
• the present invention relates to a catalyst support, a method of preparing the catalyst support, catalyst compositions prepared using the support and a process of reducing sulfur and metals content of heavy hydrocarbon oils and resids using the aforementioned catalyst compositions.
• Catalysts used in hydrotreating processes generally comprise catalytically active metals from Groups 6, 9 and 10 of The Periodic Table and are typically supported on alumina which may be combined with other inorganic refractory materials such as silica, magnesia, titania, zirconia and the like. Secondary promoters or additives such as halogens, phosphorous and boron, have also been used to enhance catalytic properties . To achieve the maximum effect from hydrotreating processes, it is necessary to optimize catalyst activity and selectivity to a desired hydrotreating reaction. Catalyst activity and selectivity is determined and affected by such factors as the nature and properties of the catalyst support, the catalytic agents, activity and selectivity of promoters as well as the preparation and activation method used .
• Hydrotreated hydrocarbon feedstocks having a low Conradson carbon residue are also highly desirable in the refining industry.
• Carbon residue is a measurement of the tendency of a hydrocarbon to form coke. Expressed in weight percent, carbon residue may be measured as microcarbon residue (MCR) .
• MCR microcarbon residue
• the MCR content in a hydrotreated residual feedstock is an important parameter since the hydrotreated residue usually acts as feed to a coker or a fluid catalytic cracking (FCC) unit. Decreasing the MCR content in a hydrotreated residue decreases the amount of low value coke generated in the coker and increases the amount of gasoline generated in the FCC unit .
• the present invention provides alumina base compositions which are useful to prepare catalyst supports having a pore volume distribution especially suited for the preparation of demetallation and desulfurization hydroconversion catalysts .
• the alumina compositions are prepared by a co-precipitation process wherein at least two cycles of pH changes are applied by subsequent addition of an acid solution followed by a base solution.
• Catalyst compositions of the invention exhibit an increased catalytic activity and stability to remove metals while simultaneously reducing the content of sulfur and microcarbon residue (MCR) of a heavy hydrocarbon fraction during a hydrotreating process.
• MCR microcarbon residue
• alumina compositions comprise spherical or substantially spherical shaped particles having a crystalline size X-ray Diffraction Ratio (020:120) of less than 1.0.
• Alumina compositions of the invention typically have a total nitrogen pore volume greater than 0.9 cc/g, and a BET surface area in the range of about 250 to about 500 m 2 /g .
• a low temperature pH swing process useful to prepare alumina compositions from which catalyst supports and supported catalysts having increased catalytic activity and stability to remove metals and reduce the content of sulfur and microcarbon residue (MCR) in a heavy hydrocarbon fraction during a hydrotreating process.
• the pH swing process of the invention comprises performing at least two cycles of pH changes at a temperature of about 15°C to about 72°C by the addition of an acid solution followed by addition of a base solution to provide a co-precipitated alumina in accordance with the invention.
• alumina based catalyst supports having a distinct pore structure are provided.
• Alumina supports of the invention are prepared using inventive alumina compositions of the invention and possess a pore volume distribution such that a large proportion of its pore volume is in pores having a diameter in the range of about 200A to about 500A.
• Catalysts in accordance with the present invention are prepared by impregnating catalytically active Group 6, 9 and 10 metals or precursor metal compounds, and optionally, phosphorous compounds, on a catalyst support in accordance with the invention.
• Still another embodiment of the present invention provides improved hydrotreating catalysts which have the ability to reduce the content of metals while simultaneously reducing the content of sulfur and microcarbon residue (MCR) in a hydrotreated heavy hydrocarbon fraction.
• MCR microcarbon residue
• Figure 1 is a graphic representation of temperature, pH and reactant flow versus time for a pH swing process in accordance with the present invention.
• the present invention provides inventive alumina compositions prepared by a low temperature pH swing process .
• pH swing refers to a method wherein the pH of an aqueous slurry is changed or cycled from a low, acidic pH to a high, alkaline pH by the addition of one or more acidic compounds to lower the pH in a first step followed by the addition to the slurry of one or more alkaline compounds in order to raise the pH in a second step.
• alumina compositions of the invention comprise are in the form of powders, i.e., particles having an average particle size ranging from about 5 micron to about 80 micron.
• Particles comprising the alumina compositions of the invention are generally spherical or substantially spherical in shape.
• spherical is used herein to designate an oblate or spheroid shape.
• substantially spherical is used herein to indicate greater than 90% of the particles have an oblate or spheroid shape.
• the alumina compositions of the invention possess a nitrogen total pore volume of about 0.9 cc/g or greater. In a preferred embodiment of the invention, alumina compositions of the invention have a nitrogen total pore volume in the range of about 0.9 cc/g to about 1.5 cc/g.
• Surface area as defined herein is determined by BET surface area analysis. The BET method of measuring surface area has been described in detail by Brunauer, Emmett and Teller in J. Am. Chem. Soc. 60 (1938) 309-319, which is incorporated herein in its entirety by reference.
• alumina compositions of the present invention have a BET surface area of at least about 80 m 2 /g. In a preferred embodiment, the alumina compositions of the present invention have a BET surface area ranging from about 80 m 2 /g to about 180 m 2 /g.
• particles comprising the alumina compositions of the invention have a crystalline structure with a maximum crystalline dimension of up to about 60 A as measured using X-ray Diffraction (XRD) techniques.
• the particles of the inventive alumina compositions have a crystalline structure having a first dimension as measured along a 120 XRD plane and a second dimension as measured along a 020 XRD plane, wherein the ratio of the second dimension as measured along a 020 XRD plane, and the first dimension as measured along a 120 XRD plane (020:120) is less than 1.
• the XRD ratio (020:120) ranges from about 0.6 to about 0.9.
• the process used for preparing the alumina compositions of the invention generally comprises a low temperature pH swing process wherein in a first step, at least one acidic compound is added to heated water in an amount sufficient to provide an initial aqueous slurry having a pH of less than 5.
• the acidic compound is added in an amount sufficient to provide a pH ranging from about 2 to about 4.5 in the initial slurry.
• the acidic compound is added in an amount sufficient to provide a pH ranging from about 2.5 to about 4.0 in the initial slurry.
• the process comprises adding an amount of at least one alkaline compound to the initial slurry in an amount sufficient to increase the pH of the resulting slurry to a value greater than 7 and precipitate seed alumina.
• the alkaline compound is added to the initial slurry in an amount sufficient to increase the pH of the slurry within a range of about 7.5 to about 10.0.
• the alkaline compound is added in an amount sufficient to increase the pH of the resulting slurry within a range of from about 8.0 to about 9.5.
• the two-step precipitation process completes a first cycle or swing.
• an acidic compound is again added to the slurry in an amount sufficient to lower its pH to within the range of about 2.0 to about 5.0, preferably from about 2.0 to about 4.5, most preferably, from about 2.5 to about 4.0.
• This step is followed by the addition of at least one alkaline compound in an amount sufficient to increase the pH of the slurry to a value above 7.0, preferably within the range from about 7.5 to about 10, most preferably from about 8.0 to about 9.5, which completes a second pH swing or cycle.
• the number of swings prior to a final pH swing may vary depending upon the desired properties in the final precipitated alumina.
• at least two pH swings are conducted prior to the final pH swing.
• the sequence of pH swings before the final pH swing is two or more.
• the sequence of pH swings before the final pH swing ranges from about 3 to about 7 swings or cycles.
• a final pH swing is conducted wherein the acidic compound is again introduced to lower the pH of the slurry to within the range as described herein above, while the alkaline compound is added in an amount sufficient to increase the pH of the final slurry to at least about 9.
• the alkaline compound is added in an amount sufficient to increase the pH of the final slurry to within a range of about 9 to about 9.5.
• Acidic compounds useful in the pH swing process of the invention include, but are not limited to, compounds selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum chlorohydrate , and combinations thereof.
• the acidic compound is aluminum sulfate.
• Alkaline compounds useful in the pH swing process of the invention include, but are not limited to, a compound selected from the group consisting of sodium hydroxide, sodium aluminate, aluminum hydroxide, ammonium hydroxide, or combinations thereof.
• the alkaline compound is sodium aluminate.
• the temperature conditions at which the pH swing process is conducted can affect the properties of final alumina particles .
• a low temperature during the entire process is preferred.
• the temperature of the mixing and reaction steps of each of the pH swings should be in the range of about 72 °C or less. Suitable temperatures include about 15°C to about 72°C and individual temperatures and temperature ranges between and including these endpoints, for example: about 20°C to about 70°C, about 25°C to about 65°C, about 20°C to about 72°C, about 30°C to about 60°C; and, as stated, individual temperatures between 15°C and 72°C, such as 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, . . .
• the temperature of each of the pH swings should be in the range of about 48°C to about 72°C. In a more preferred embodiment of the invention, the temperature of each pH swing ranges from about 52°C to about 66°C.
• the period of time elapsed between the two addition steps of a pH swing or cycle should be a period of time sufficient to provide for adequate mixing of slurry components.
• the time between the two additions steps is a period of time sufficient to provide a homogeneous or substantially homogeneous slurry.
• the time period between the two additions steps in a cycle ranges from about 1 minute to about 10 minutes.
• the alumina precipitate resulting from the final swing may be recovered from the slurry.
• Any suitable method known to those skilled in the art for separating the precipitate solids from the final slurry may be used to recover the precipitated solid.
• Such methods include gravity separation, pressure separation, and vacuum separation and can include the use of equipment such as, for example, belt filters, plate-and-frame filters and rotary vacuum filters.
• the filtered precipitated alumina, or filter cake may be washed with water to remove impurities such as sodium and sulfate salts .
• One or more washing steps may be used to wash the filtered precipitate alumina.
• the washed precipitate is thereafter dried using any conventional drying method known to those skilled in the art to provide a dried precipitated alumina having a moisture content of about 22 to about 38 weight percent as determined by loss of ignition at 955°C (1750°F) .
• the dried alumina has a moisture content of about 25 to about 36 weight percent based on the total weight of the alumina.
• the precipitated alumina of the invention comprises a strongly aggregated system of spherical or substantially spherical alumina particles which form high viscosity aqueous acidic slurries, i.e. a slurry having an alumina content of greater than 20%, a pH below 5, and a viscosity greater than 500cps.
• the precipitated alumina of the invention are particularly useful to prepare support materials from which a supported hydrotreating catalyst may be manufactured.
• an aqueous slurry of the dried alumina is treated with a peptizing agent to peptize the alumina.
• Suitable peptizing agents include but are not limited to, strong monobasic acids such as nitric acid or hydrochloric acid, organic acids such as formic acid, acetic acid or propionic acid and aqueous bases such as ammonium hydroxide.
• the peptized alumina is extruded and dried at a temperature ranging from about 100°C to about 150°C for about 10 minutes to about 2 hours.
• the dried extrudate is thereafter calcined at a high temperature ranging from about 800°C to about 1100°C for about 1 hour to about 3 hours to obtain a final catalyst support.
• the dried extrudate is calcined at a temperature ranging from about 900°C to about 1040°C to obtain a final catalyst support material.
• Supports of the invention have a distinct pore volume distribution such that a large portion of its pore volume is in pores having a diameter in the range of about 200A to about 500A.
• alumina catalyst supports in accordance with the present invention have the following pore volume distribution: a total pore volume in the range from about 0.8 cc/g to about 1.2 cc/g, with greater than 8% of the volume of pores, preferably from about O.lcc/g to about 0.4 cc/g, having a diameter greater than 350A, and 40% or greater of the volume of pores, preferably from about 0.4cc/g to about 0.8 cc/g, having a diameter in the range of about 200A to about 500A and at least 5% of the volume of pores, preferably from about 0.04cc/g to about 0.2 cc/g, having a diameter above 1500A.
• about 50% to about 80% of the total pore volume of the supports have pores with a diameter in the range of about 200 A to about 500A.
• about 5% to about 20% of the total pore volume of the supports have pores with a diameter above 1,500A.
• greater than about 15% of the total pore volume of the support has pores with a diameter above 350A.
• the BET surface area of alumina supports in accordance with the present invention ranges from about 80 m 2 /g to about 180 m 2 /g. In a preferred embodiment of the invention, the BET surface area of the alumina supports ranges from about 100 m 2 /g to about 150 m 2 /g.
• Extruded supports in accordance with the invention may have various geometric forms, such as cylinders, rings, and symmetric and/or asymmetric polylobes, for instance, trior quadrulobes .
• Nominal sizes of the extrudates may vary.
• the diameter usually ranges from about 1 to about 10 mm, and the length ranges from about 1 to about 30 mm. In one embodiment of the invention, the diameter ranges from about 1 to about 3 mm and the length ranges from about 2 mm to about 10 mm.
• catalyst particles produced from the supports will have a similar size and shape as the support.
• hydrotreating catalyst compositions which compositions are comprised of catalytically active metals or precursor metal compounds of metals of Groups 6, 9 and 10 of The Periodic Table, and optionally phosphorous compounds, supported on alumina catalyst supports of the invention .
• Catalysts in accordance with the invention are prepared by contacting the alumina supports with an aqueous solution of at least one catalytically active metal or precursor metal compound to uniformly distribute the desired metal on the support. Preferably, the metal is distributed uniformly throughout the pores of the support.
• the catalysts are prepared by impregnation of the catalyst supports to incipient wetness with an aqueous solution of the desired catalytically active metal or precursor compound.
• Catalytically active metal and/or precursor metals compounds useful to prepare catalyst compositions of the invention include, but are not limited to metals or compounds of metals selected from the group consisting of Group 6 of The Periodic Table, Group 9 of The Periodic Table, Group 10 of The Periodic Table and combinations thereof.
• Preferred Group 6 metals include, but are not limited to, molybdenum and tungsten.
• Preferred Groups 9 and 10 metals include, but are not limited to, cobalt and nickel.
• the Periodic Table is used herein to mean "The Periodic Table of Elements”.
• Concentrations of Group 6 metals and/or metal compounds useful to prepared catalyst compositions of the present invention typically is an amount sufficient to provide from about 1.0 wt% to about 10 wt% of the desired Group 6 metal, preferably from about 2.0 wt% to about 5.0 wt%, in the total catalyst composition.
• Concentrations of Group 9 metals and/or metal compounds useful to prepare the catalyst compositions of the present invention typically is an amount sufficient to provide from about 0 wt% to about 5.0 wt% of the desired Group 9 metal, preferably from about 0.5 wt% to about 2.0 wt%, in the total catalyst composition.
• Concentrations of Group 10 metals and/or metal compounds useful to prepare the catalyst compositions of the present invention typically is an amount sufficient to provide from about 0 wt% to about 5.0 wt% of the desired Group 10 metal, preferably from about 0.5 wt% to about 2.0 wt%, in the total catalyst composition.
• the combinations of nickel and molybdenum catalytic agents are preferred.
• the resulting catalyst comprises Mo concentrations in the range of about 3 to about 10 wt% and Ni concentrations in the range of about 0.1 to about 4 wt%, said wt% being based on the total catalyst composition.
• Suitable precursor metal compounds of Groups 9 and 10 metals include, but are not limited to, metallic salts such as nitrates, acetates and the like.
• Suitable precursor metal compounds of Group 6 metals include, but are not limited to, ammonium molybdate, molybdic acid, molybdenum trioxide, and the like.
• Catalytically active metals contemplated for use with the supports of the present invention are preferably used in the form of oxides and/or sulfides of the metals.
• the catalytically active metals are used in the form of oxides.
• Catalyst compositions of the invention may also comprise a phosphorus component.
• the impregnating solution may also contain a phosphorus compound, e.g. phosphoric acid, phosphates, and the like, in addition to the desired catalytically active metals or precursor metal compounds .
• Concentrations in the range of about 0.1 to about 2.0 wt% of phosphorous based on the total catalyst composition are suitable for use in the catalyst compositions of the invention.
• the catalyst are optionally dried at a temperature in the range of about 100°C to about 200°C for about 10 minutes to about 2 hours.
• the dried catalyst is thereafter calcined at a temperature and for a time sufficient to convert at least part, preferably all, of the metal components or precursors to the oxide form.
• the catalyst is calcined at a temperature in the range of about 300°C to about 600°C for about 1 hour to about 3 hours .
• impregnating method used to support the catalytic active metals on the catalyst supports. It is possible to apply a plurality of impregnating steps. It is within the scope of the invention that the impregnating solutions may contain one or more of the component or precursors to be deposited, or a portion thereof. Instead of impregnating techniques, other conventional methods of applying the active metals on the support, e.g. dipping, spraying, and the like, can be used. In the case of multiple or mixed (impregnation and dipping) applications steps, drying and/or calcining may be carried out as between steps.
• Catalyst compositions according to the invention exhibit an increased catalytic activity and stability for demetallation of a heavy hydrocarbon feedstock containing metals during a hydrotreating process.
• the heavy hydrocarbon feedstock useful in the present invention can be obtained from any suitable source of hydrocarbons, including, for example, petroleum crude oils and tar sand hydrocarbons, such as, the heavy oils extracted from tar sand.
• the heavy hydrocarbon feedstock can be a vacuum resid or atmospheric resid component of a petroleum crude oil or a tar sand hydrocarbon.
• the heavy hydrocarbon feedstock may also include light and heavy gas oils, as well as petroleum crude oil, atmospheric residues and vacuum residues blended with gas oils, particularly vacuum gas oils, crudes, shale oils, and tar sand oils.
• the heavy hydrocarbon feedstock generally will include a mixture of hydrocarbons derived from a crude oil or tar sand hydrocarbon material or other source of heavy hydrocarbons. A portion, preferably a major portion, of the heavy hydrocarbons of the mixture has a boiling temperature exceeding about 343°C (650°F).
• the heavy hydrocarbon feedstock is thus defined as having a boiling range, as determined by ASTM test procedure D-1160, such that at least about 20 wt% of the heavy hydrocarbon feedstock boils at a temperature exceeding 524°C (975°F).
• the preferred heavy hydrocarbon feedstock has a boiling range such that at least 30 wt% boils at a temperature exceeding 524°C (975°F), and, most preferably, at least 40 wt% of the heavy hydrocarbon feedstock boils at a temperature exceeding 524°C (975°F).
• the API gravity of the heavy hydrocarbon feedstock can range from about 3 to about 20, but, more specifically, the API gravity is in the range of from 4 to 15, and, more specifically, from 4 to 11.
• the heavy hydrocarbon feedstock can have a Conradson carbon residue content, as determined by ASTM testing method D-189, exceeding 5 weight percent and, more specifically, the Conradson carbon residue content is in the range of from 8 weight percent to 30 weight percent.
• the metals contained in the heavy hydrocarbon feedstock can include nickel or vanadium, or both.
• the nickel concentration in the heavy hydrocarbon feedstock can exceed 10 parts per million by weight (ppmw) or it can exceed 30 ppmw. More specifically, the nickel concentration in the heavy hydrocarbon feedstock can be in the range of from 40 ppmw to 500 ppmw.
• the vanadium concentration in the heavy hydrocarbon feedstock can exceed 50 ppmw or it can exceed 100 ppmw. More specifically, the vanadium concentration in the heavy hydrocarbon feedstock can be in the range of from 150 ppmw to 1500 ppmw.
• Catalysts of the invention are also useful to decrease the content of sulfur simultaneously with demetallation during a hydrotreating process where the hydrocarbon feedstock being treated contains both sulfur and metals.
• the sulfur content of the feed is generally above 0.1 wt% and will frequently be more than 1 wt%.
• the nitrogen content is generally above 500 ppm and will frequently be in the range of from 500 ppm to 4000 ppm.
• catalysts in accordance with the present invention provide an increased micro carbon residue (MCR) conversion during a hydrotreating process. Consequently, the hydrotreated hydrocarbon fraction obtained exhibits a reduced MCR content as compared to the MCR content of the starting heavy hydrocarbon feedstock.
• MCR micro carbon residue
• a hydrotreating process employing the catalyst compositions of this invention may be carried out under hydrotreating process conditions in an apparatus whereby an intimate contact of the catalyst composition with said metal containing feedstock and a free hydrogen containing gas is achieved, to produce a hydrocarbon-containing product having a reduced level of metals, e.g. nickel and vanadium, and, optionally sulfur.
• the hydrotreating process can be carried out using a fixed catalyst bed.
• the hydrotreating process can be carried out as a batch process or, as a continuous process containing one or more fixed catalyst beds or in a plurality of fixed bed reactors in parallel or in series .
• Typical hydrotreating process conditions useful in the invention include, but are not limited to, temperatures between 300° and 450°C, hydrogen pressures between 25 and 200 bar, H 2 :oil ratios between 150 and 1500 Nl/1, and space velocities (hr- 1 ) between 0.1 and 5.
• the operating conditions for metal containing hydrocarbon feedstock desulfurization process include a reaction zone temperature of 350°C to 400°C, a pressure of 100 to 200 bar, and a hydrogen feed rate of 300 to about 1000 normal liters per liter of oil feed.
• any range of numbers recited in the specification or claims, such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited.
• R L lower limit
• Ro upper limit
• any number R falling within the range is specifically disclosed.
• R R L + k(R D -R L ), where k is a variable ranging from 1% to 100% with a 1% increment, e.g., k is 1%, 2%, 3%, 4%, 5%. ...
• any numerical range represented by any two values of R is also specifically disclosed.
• a range of values represented by two endpoints will be understood to include the endpoint values unless the context of the disclosure clearly suggests otherwise.
• aqueous aluminum sulfate was added to decrease the pH to 3.6.
• aqueous sodium aluminate was added to increase the pH to about 9.2.
• the precipitated alumina mix was then filtered to provide a filter cake.
• the filter cake was water washed on a belt filter to remove the residual sodium sulfate, and thereafter was dried at a temperature of about 120 °C.
• the dried alumina powder was used for catalyst support preparation.
• the dried alumina powder was peptized by mixing with an aqueous solution of nitric acid in a batch mixer. The wet mix was extruded through buttons with nominal hole diameter of 1.3 mm. The extruded support particles were dried at 120°C, and then calcined at 980°C.
• Metals solution was prepared by diluting phosphoric acid with water under agitation. This diluted solution was heated to 90°C before molybdenum trioxide was slowly added. After all the molybdenum was added the resulting solution was allowed to cook at 90°C for 1 hour. The solution was diluted with extra water and allowed to cool below 65°C. Then 13% nickel nitrate solution was added resulting in the final metals solution.
• Catalyst A had a nominal active metal content of 5 wt% Mo and 0.25 wt% Ni .
• the catalyst had a total pore volume measured by Hg intrusion of 0.89 cc/g, mesopore volume measured by N 2 desorption of 0.68 cc/g and surface area measured by N 2 adsorption of 139 m 2 /g.
• Alumina was prepared by coprecipitation by mixing an aqueous stream of aluminum sulfate with an aqueous stream of sodium aluminate . After an initial pH stabilization period, the addition rates of the two streams were adjusted to maintain the pH of the slurry between 7 and 8. At the end of the precipitation process the pH was increased above 9. The precipitated alumina mix was then filtered and water washed on a belt filter to remove the residual sodium sulfate. Filter cake was dried. Dried alumina powder was used for catalyst base preparation.
• the dried alumina powder was peptized by mixing with an aqueous solution of nitric acid in a batch mixer.
• the wet mix was extruded through buttons with nominal hole diameter of 1.3 mm to provided spherical particles.
• the extruded base particles were dried at 120°C, and then calcined at 1040°C to provide an alumina support.
• Metals solution was prepared by diluting phosphoric acid with water under agitation. This diluted solution was heated to 90°C before molybdenum trioxide was slowly added. After all the molybdenum was added the resulting solution was allowed to cook at 90°C for 1 hour. The solution was diluted with extra water and allowed to cool below 65°C. Then 13% nickel nitrate solution was added resulting in the final metals solution.
• Catalyst B had a nominal active metal content of 5 wt% Mo and 0.25 wt% Ni .
• the catalyst had a total pore volume measured by Hg intrusion of 0.76 cc/g, mesopore volume measured by N 2 desorption of 0.52 cc/g and surface area measured by N 2 adsorption of 107 m 2 /g.
• Catalyst A prepared using the low temperature, pH-swing alumina of the invention, exhibited enhanced catalytic activity for demetallation and desulfurization as compared to the performance of Catalyst B.
• Catalyst A also showed increased MCR conversion as compared to Catalyst B.
• a catalyst composition having improved activity and stability in the hydrodemetallation of heavy hydrocarbons comprising: (a) a support which comprises precipitated alumina comprising spherical or substantially spherical shaped particles; and
• the support has a total pore volume in the range of from about 0.8 cc/g to about 1.2 cc/g, with greater than 8% of the total pore volume having a diameter greater than 350A, and 40% or greater of the total pore volume having a diameter in the range of about 200A to about 500A and at least 5% of the total pore volume having a diameter above 1500A.
• step (d) adding an acidic compound to the alumina- containing slurry of step (c) in an amount sufficient to provide an alumina slurry having a pH of less than 5;
• step (e) adding an alkaline compound to the alumina slurry of step (d) in an amount sufficient to provide a final alumina slurry having a pH of at least about 9;
• steps (a) - (e) wherein the temperature during steps (a) - (e) is maintained at a temperature of about 15°C to about 72°C.
• particles comprising the precipitated alumina have a crystalline structure having a first dimension as measured along a 120 XRD plane and a second dimension as measured along a 020 XRD plane, wherein the ratio of the second dimension to the first dimension is less than 1.0.
• step (g) drying the precipitated alumina of step (f) ;
• the catalyst of paragraph 6 wherein the alkaline compound is selected from the group consisting of sodium aluminate, aluminum hydroxide, sodium hydroxide, ammonium hydroxide and combinations thereof.
• a process for hydrotreating a metal-containing heavy hydrocarbon fraction to remove metals comprises contacting a heavy hydrocarbon fraction containing metals and optionally sulfur with a catalyst of paragraph 1 under hydrotreating process conditions and reducing the content of metals in the heavy hydrocarbon fraction.
• a process of reducing the microcarbon residue (MCR) content of a heavy hydrocarbon feed comprising contacting a heavy hydrocarbon feed having a MCR content with the catalyst of paragraph 1 under hydrotreating process conditions and providing a hydrotreated hydrocarbon fraction having a reduced MCR content as compared to the MCR content of the heavy hydrocarbon feed.
• MCR microcarbon residue
• An alumina support for a hydroconversion catalyst having improved activity and stability in the hydrodemetallation of heavy hydrocarbons comprising spherical or substantially spherical particles having a total pore volume in the range from about 0.9 cc/g to about 1.2 cc/g, a surface area from about 250 m 2 /g to about 500 m 2 /g and a crystalline structure having a first dimension as measured along a 120 XRD plane and a second dimension as measured along a 020 XRD plane, wherein the ratio of the second dimension to the first dimension is less than 1.0.
• step (d) adding an acidic compound to the alumina- containing slurry of step (c) in an amount sufficient to provide an alumina slurry having a pH of less than 5;
• step (e) adding an alkaline compound to the alumina slurry of step (d) in an amount sufficient to provide a final alumina slurry having a pH of at least about 9;
• steps (a) - (e) wherein the temperature during steps (a) - (e) is maintained at a temperature of about 15°C to about 72°C.
• a catalyst support comprising the alumina of paragraph 29, wherein the support has a total pore volume in the range of from about 0.8 cc/g to about 1.2 cc/g, with greater than 8% of the total pore volume having a diameter greater than 350A, and 40% or greater of the total pore volume having a diameter in the range of about 200A to about 500A and at least 5% of the total pore volume having a diameter above 1500A.
• a catalyst support comprising the alumina of paragraph 30, wherein the support has a total pore volume in the range of from about 0.8 cc/g to about 1.2 cc/g, with greater than 8% of the total pore volume having a diameter greater than 350A, and 40% or greater of the total pore volume having a diameter in the range of about 200A to about 500A and at least 5% of the total pore volume having a diameter above 1500A.
• a process of preparing a precipitated alumina composition comprising:
• step (d) adding an acidic compound to the alumina- containing slurry of step (c) in an amount sufficient to provide an alumina slurry having a pH of less than 5; (e) adding an alkaline compound to the alumina slurry of step (d) in an amount sufficient to provide a final alumina slurry having a pH of at least about 9; and
• steps (a) - (e) wherein the temperature during steps (a) - (e) is maintained at a temperature of about 15°C to about 72°C.
• alkaline compound is selected from the group consisting of sodium aluminate, aluminum hydroxide, sodium hydroxide, ammonium hydroxide and combinations thereof.
• a catalyst composition having improved activity and stability in the hydrodemetallation of heavy hydrocarbons comprising:
• At least one catalytic agent selected from the group consisting of a metal of Group 6 of The Periodic Table, a metal of Group 9 of The Periodic Table, a metal of Group 10 of The Periodic Table, phosphorous and combinations thereof;
• the support has a total pore volume in the range of from about 0.8 cc/g to about 1.2 cc/g, with greater than 8% of the total pore volume having a diameter greater than 350A, and 40% or greater of the total pore volume having a diameter in the range of about 200A to about 500A and at least 5% of the total pore volume having a diameter above 1500A.
• the catalyst of claim 51 wherein the pore size distribution is selected from the group consisting of from about 0.04 cc/g to about 0.2 cc/g of the total pore volume of the support in pores having a diameter greater than 350A; from about 0.4 cc/g to about 0.8 cc/g of the total pore volume of the support in pores having a diameter in the range of about 200A to about 500A; from about 0.04 cc/g to about 0.2 cc/g of the total pore volume of the support in pores having a diameter above 1500A; and combinations thereof.
• the precipitated alumina has nitrogen total pore volume of greater than 0.9 cc/g and a BET surface area of about 80 to about 180 m /g; or (ii) particles comprising the precipitated alumina have a crystalline structure having a first dimension as measured along a 120 XRD plane and a second dimension as measured along a 020 XRD plane, wherein the ratio of the second dimension to the first dimension is less than 1.0; or (iii) both (i) and (ii).
• step (d) adding an acidic compound to the alumina- containing slurry of step (c) in an amount sufficient to provide an alumina slurry having a pH of less than 5;
• step (e) adding an alkaline compound to the alumina slurry of step (d) in an amount sufficient to provide a final alumina slurry having a pH of at least about 9;
• steps (a) - (e) wherein the temperature during steps (a) - (e) is maintained at a temperature of about 15°C to about 72°C.
• step (g) drying the precipitated alumina of step (f);
• the initial slurry pH ranges from about 2.0 to about 4.5;
• the second slurry pH ranges from about 7.5 to about 10;
• step (c) the alumina-containing slurry pH of step (c) ranges from about 7.5 to about 10;
• step (d) the alumina slurry pH of step (d) ranges from about 2.0 to about 4.5;
• step (e) the final alumina slurry pH of step (e) ranges from about 9 to about 9.5.
• a process for hydrotreating a heavy hydrocarbon fraction containing a component selected from the group consisting of metals, sulfur, microcarbon residue and mixtures thereof which process comprises contacting the heavy hydrocarbon fraction with a catalyst of claim 1 under hydrotreating process conditions and reducing the content of a component selected from the group consisting of metals, sulfur and microcarbon residue in the heavy hydrocarbon fraction compared to the level originally present.
• An alumina support for a hydroconversion catalyst having improved activity and stability in the hydrodemetallation of heavy hydrocarbons comprising spherical or substantially spherical particles having a total pore volume in the range from about 0.9 cc/g to about 1.2 cc/g, a surface area from about 250 m /g to about 500 m 2 /g and a crystalline structure having a first dimension as measured along a 120 XRD plane and a second dimension as measured along a 020 XRD plane, wherein the ratio of the second dimension to the first dimension is less than 1.0.
• the catalyst support of claim 60 comprising a total pore volume in the range of from about 0.8 cc/g to about 1.2 cc/g, with greater than 8% of the total pore volume having a diameter greater than 350A, and 40% or greater of the total pore volume having a diameter in the range of about 200A to about 500A and at least 5% of the total pore volume having a diameter above 1500A.
• a process of preparing a precipitated alumina composition suitable for use as the catalyst support of claim 51 or claim 60 comprising:
• step (d) adding an acidic compound to the alumina- containing slurry of step (c) in an amount sufficient to provide an alumina slurry having a pH of less than 5;
• step (e) adding an alkaline compound to the alumina slurry of step (d) in an amount sufficient to provide a final alumina slurry having a pH of at least about 9;
• step (f) recovering the precipitated alumina from the final alumina slurry; wherein the temperature during steps (a) - (e) is maintained at a temperature of about 15°C to about 72°C.
• the initial slurry pH ranges from about 2.0 to about 4.5;
• the second slurry pH ranges from about 7.5 to about 10;
• step (d) the alumina slurry pH of step (d) ranges from about 2.0 to about 4.5;
• step (e) the final alumina slurry pH of step (e) ranges from about 9 to about 9.5.
• step (g) drying the precipitated alumina of step (f);

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