EP2424659A2 - Catalyseur multi-métallique d'hydroconversion et son procédé de fabrication - Google Patents

Catalyseur multi-métallique d'hydroconversion et son procédé de fabrication

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Publication number
EP2424659A2
EP2424659A2 EP10770341A EP10770341A EP2424659A2 EP 2424659 A2 EP2424659 A2 EP 2424659A2 EP 10770341 A EP10770341 A EP 10770341A EP 10770341 A EP10770341 A EP 10770341A EP 2424659 A2 EP2424659 A2 EP 2424659A2
Authority
EP
European Patent Office
Prior art keywords
catalyst precursor
catalyst
acid
group
precursor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10770341A
Other languages
German (de)
English (en)
Other versions
EP2424659A4 (fr
Inventor
Theodorus Maesen
Alexander E. Kuperman
Dennis Dykstra
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron USA Inc
Original Assignee
Chevron USA Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/432,723 external-priority patent/US7931799B2/en
Priority claimed from US12/432,728 external-priority patent/US7964526B2/en
Priority claimed from US12/432,730 external-priority patent/US8080492B2/en
Application filed by Chevron USA Inc filed Critical Chevron USA Inc
Publication of EP2424659A2 publication Critical patent/EP2424659A2/fr
Publication of EP2424659A4 publication Critical patent/EP2424659A4/fr
Withdrawn legal-status Critical Current

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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • 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
    • 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
    • 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
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also 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
    • 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
    • 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
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—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
    • 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)
    • 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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B01J35/32—Bulk density
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/34—Mechanical properties
    • B01J35/37—Crush or impact strength
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/34—Mechanical properties
    • B01J35/38—Abrasion or attrition resistance

Definitions

  • the invention relates generally to a hydroprocessing catalyst precursor, processes for preparing the catalyst precursor, multi-metallic catalysts prepared using the catalyst precursor, and hydroconversion processes employing the multi-metallic catalysts.
  • TECHNICAL FIELD The petroleum industry is increasingly turning to heavy crudes, resids, coals and tar sands, i.e., lower grade hydrocarbon ("heavy oil"), as sources for feedstocks.
  • the upgrading or refining of these feedstocks is accomplished by treating the feedstocks with hydrogen in the presence of catalysts to effect conversion of at least a portion of the feeds to lower molecular weight hydrocarbons, or to effect the removal of unwanted components, or compounds, or their conversion to innocuous or less undesirable compounds.
  • the pore structure of catalysts is usually formed in the crystallization stage or in subsequent treatment. Depending on their predominant pore size, the solid materials are classified according to size into three categories; micropores (dimension smaller than 3.5 nm), mesopores (dimension ranging from 3.5 - 500 nm) and macropores (dimension larger than 500 nm).
  • micropores dimension smaller than 3.5 nm
  • mesopores dimension ranging from 3.5 - 500 nm
  • macropores dimension larger than 500 nm.
  • the use of macroporous solids as adsorbents and catalysts is relatively limited due to their low surface area and large non-uniform pores. Microporous and mesoporous solids, however, are widely used in adsorption, separation technology and catalysis.
  • a catalyst that is highly porous does not necessarily mean that the catalyst has a lot of surface area.
  • the catalyst may be too porous, having very little in terms of surface area and correspondingly, low catalytic activity in terms of reactive sites.
  • the invention relates to a stable bulk multi-metallic catalyst formed from a catalyst precursor having a Type IV isotherms with a H3-type hysteresis loop.
  • the mesopores are characterized as being tunable.
  • the catalyst precursor is characterized as having a poorly crystalline structure with disordered stacking layers, i.e., the stacking of the layers is highly random.
  • the invention relates to a method for making a stable bulk multi-metallic catalyst formed from a catalyst precursor having a Type IV isotherm with a H3-type hysteresis loop.
  • the manufacturing method comprises: a) forming a precipitate comprising at least a promoter metal precursor, at least a Group VIB metal precursor, optionally a ligating agent, and optionally at least a diluent, wherein the promoter metal precursor is selected from Group VIII, Group HB, Group HA, Group IVA and combinations thereof; b) removing at least 50% of liquid from the precipitate forming a filter cake; c) adding to the filter cake at least one of a shaping aid agent, a pore forming agent, a peptizing agent, a diluent, and combinations thereof, forming a batch mixture; d) shaping the batch mixture into a shaped catalyst precursor via any of pelletizing, extrusion, tableting, molding, tumbling, pressing, spraying and spray drying; and b) sulfiding the shaped catalyst precursor forming a bulk multi-metallic catalyst.
  • the amount of ligating agent is controlled to vary or tune the mesopores of the catalyst precursor.
  • the additives to the shaping step are varied and controlled to tune the mesopores of the catalyst precursor.
  • Figure 1 is block diagram showing an embodiment of a process for making a multi-metallic catalyst from a mesoporous catalyst precursor having a Type IV isotherm with a H3-type hysteresis loop.
  • Figure 2 is a graph illustrating the N2 adsorption (- ⁇ - ) and desorption (- ⁇ -) isotherms of one embodiment of the catalyst precursor.
  • Figure 3 is a graph illustrating the N2 adsorption (- ⁇ - ) and desorption (- ⁇ -) isotherms of the catalyst precursor of Figure 2 in the relative pressure range of 0.35 to 1.00.
  • Figure 4 is a graph illustrating the N2 adsorption (- ⁇ - ) and desorption (- ⁇ -) isotherms of another embodiment of the catalyst precursor, showing a broad type H3 desorption hysteresis loop.
  • Figure 5 is a graph illustrating the N2 adsorption (- ⁇ - ) and desorption (- ⁇ -) isotherms of the catalyst precursor of Figure 4 in the relative pressure range of 0.35 to 1.00.
  • Figure 6 is a graph illustrating the N2 adsorption (- ⁇ - ) of a catalyst precursor that does not have a type IV isotherms.
  • SCF / BBL (or scf / bbl, or scfb or SCFB) refers to a unit of standard cubic foot of gas (N 2 , H 2 , etc.) per barrel of hydrocarbon feed.
  • LHSV means liquid hourly space velocity.
  • the Periodic Table referred to herein is the Table approved by IUPAC and the U.S. National Bureau of Standards, an example is the Periodic Table of the Elements by Los Alamos National Laboratory's Chemistry Division of October 2001.
  • the term “bulk catalyst” may be used interchangeably with “unsupported catalyst,” meaning that the catalyst composition is NOT of the conventional catalyst form which has a preformed, shaped catalyst support which is then loaded with metals via impregnation or deposition catalyst.
  • the bulk catalyst is formed through precipitation.
  • the bulk catalyst has a binder incorporated into the catalyst composition.
  • the bulk catalyst is formed from metal compounds and without any binder.
  • the phrases "one or more of or "at least one of when used to preface several elements or classes of elements such as X, Y and Z or Xi-X n , Y 1 - Y n and Zi-Z n is intended to refer to a single element selected from X or Y or Z, a combination of elements selected from the same common class (such as Xi and X 2 ), as well as a combination of elements selected from different classes (such as X 1 , Y 2 and Zn).
  • hydroconversion or “hydroprocessing” is meant any process that is carried out in the presence of hydrogen, including, but not limited to, methanation, water gas shift reactions, hydrogenation, hydrotreating, hydrodesulphurization, hydrodenitrogenation, hydrodemetallation, hydrodearomatization, hydroisomerization, hydrodewaxing and hydrocracking including selective hydrocracking.
  • the products of hydroprocessing can show improved viscosities, viscosity indices, saturates content, low temperature properties, volatilities and depolarization, etc.
  • 700°F+ conversion rate refers to the conversion of an oil feedstock having a boiling point of greater than 700°F+ to less than 700° F (371. 0 C) boiling point materials in a hydroconversion process, computed as (100% * (wt. % boiling above 700 0 F materials in feed - wt. % boiling above 700 0 F materials in products) / wt. % boiling above 700 0 F materials in feed)).
  • LD50 is the amount of a material, given all at once, causes the death of 50% (one half) of a group of test animals. LD-50 measures the short- term poisoning potential (acute toxicity) of a material with the testing being done with smaller animals such as rats and mice (in mg/Kg).
  • shaped catalyst precursor means catalyst precursor formed (or shaped) by spray drying, pelleting, pilling, granulating, beading, tablet pressing, bricketting, using compression method via extrusion or other means known in the art or by the agglomeration of wet mixtures.
  • the shaped catalyst precursor can be in any form or shape, including but not limited to pellets, cylinders, straight or rifled (twisted) trilobes, multiholed cylinders, tablets, rings, cubes, honeycombs, stars, tri-lobes, quadra-lobes, pills, granules, etc.
  • Pore porosity and pore size distribution in one embodiment can be measured using mercury intrusion porosimetry, designed as ASTM standard method D 4284. In another embodiment, pore porosity and size distribution are measured via the nitrogen adsorption method.
  • Layered or textural porosity is the porosity that can be attributed to voids between layers or platters of catalyst precursors.
  • TEM transmission electron spectroscopy
  • adsorption can distinguish and evaluate the layered porosity by the specific adsorption behavior of the catalyst precursor.
  • One way to detect and assess layered or textural mesoporosity is evidenced by the presence of a type IV adsorption-desorption isotherm exhibiting we 11- defined hysteresis loop in the region of relative pressure P/P o > 0.40 (Sing et al., Pure Appl Chem., vol. 57, 603-619 (1985)).
  • the bulk catalyst of the present invention is made from a randomly stacking layered or textural mesoporous catalyst precursor, i.e., a poorly crystalline structured catalyst precursor exhibiting type IV isotherms.
  • the catalyst precursor for forming the bulk catalyst is characterized as having a H3-type hysteresis loop.
  • Catalyst Product The catalyst precursor with a type IV adsorption- desorption isotherm is converted into a catalyst (becoming catalytically active) upon sulfidation, for subsequent use in hydrodesulfurization (HDS), hydrodearomatization (HDA), and hydrodenitrification (HDN) processes.
  • the catalyst precursor can be a hydroxide or oxide material, prepared from at least a Promoter metal precursor and at least a Group VIB metal precursor.
  • the catalyst precursor in the form of a bulk multi- metallic oxide comprising of at least one Group VIII non-noble material and at least two Group VIB metals.
  • the ratio of Group VIB metal to Group VIII non-noble metal ranges from about 10:1 to about 1 :10.
  • the oxide catalyst precursor further comprises one or more ligating agents L.
  • ligand may be used interchangeably with “ligating agent,” “chelating agent” or “complexing agent” (or chelator, or chelant), referring to an additive that combines with metal ions, e.g., Group VIB and / or Promoter metals, forming a larger complex, e.g., a catalyst precursor, and facilitating the tuning or adjustment of the porosity of the mesopores.
  • the catalyst precursor is in the form of a hydroxide comprising of at least one Group VIII non-noble material and at least two Group VIB metals.
  • the hydroxide compound is of the general formula A V [(M P ) (OH) x (L) n y ] z (M VIB C> 4 ), wherein A is one or more monovalent cationic species, M refers to at least a metal in their elemental or compound form, and L refers to one or more ligating agents.
  • the catalyst precursor is prepared from a process with the inclusion of at least a diluent, for the precursor to have the formula A r [(M IIA ) s (M VIII ) t (Al) u (OH) V (L) w ] x (Si(i_y)Al y ⁇ 2)z (M VIB ⁇ 4), wherein A is one or more monovalent cationic species, M IIA is one or more group HA metals, M WI is one or more Group VIII metals, Al is aluminum, L is one or more ligating agents, (Si (1-y) Al y O 2 ) is a silica-alumina moiety, M VIB is one or more Group VIB metals with the atomic ratio of M vi ⁇ : M VIB between 100: 1 and 1 : 100.
  • A is at least one of an alkali metal cation, an ammonium, an organic ammonium and a phosphonium cation. In one embodiment, A is selected from monovalent cations such as NH4+, other quaternary ammonium ions, organic phosphonium cations, alkali metal cations, and combinations thereof.
  • L is one or more optional ligating agents.
  • L is a non-toxic organic oxygen containing ligating agent with an LD50 rate (as single oral dose to rats) of greater than 500 mg/Kg.
  • LD50 rate as single oral dose to rats
  • Examples include but are not limited to polydentate as well as monodentate, e.g., NH3 as well as alkyl and aryl amines; carboxylates, carboxylic acids, aldehydes, ketones, the enolate forms of aldehydes, the enolate forms of ketones and hemiacetals; organic acid addition salts such as formic acid, acetic acid, propionic acid, maleic acid, malic acid, cluconic acid, fumaric acid, succinic acid, tartaric acid, citric acid, oxalic acid, glyoxylic acid, aspartic acid, alkane sulfonic acids, aryl sulfonic acids; arylcarboxylic acids; carboxylate containing compounds; and combinations thereof.
  • organic acid addition salts such as formic acid, acetic acid, propionic acid, maleic acid, malic acid, cluconic acid, fumaric acid, succinic acid, tartaric acid,
  • M p is at least a promoter metal. In one embodiment, M p has an oxidation state of either +2 or +4 depending on the Promoter metal(s) being employed. M p is selected from Group VIII, Group HB, Group HA, Group IVA and combinations thereof. In one embodiment, M p is at least a Group VIII metal and M p has an oxidation state P of +2. In another embodiment, M p is selected from Group HB, Group IVA and combinations thereof.
  • the Promoter metal M p is a mixture of two Group VIII metals such as Ni and Co.
  • M p is a combination of three metals such as Ni, Co and Fe.
  • the catalyst precursor is of the formula A v [(Zn a Cd a' ) (OH )x (L) y ] z (M VIB O 4 )
  • M p is a combination of three metals such as Zn, Cd and Hg
  • the catalyst precursor is of the formula A v [(Zn a Cd a ⁇ g a") (OH) x (L) n y ] z (M ⁇ 8 O 4 '
  • the Promoter metal M p is selected from the group of IIB and VIA metals such as zinc, cadmium, mercury, germanium, tin or lead, and combinations thereof, in their elemental, compound, or ionic form.
  • the Promoter metal M p further comprises at least one of Ni, Co, Fe and combinations thereof, in their elemental, compound, or ionic form.
  • the Promoter metal is a Group HA metal compound, selected from the group of magnesium, calcium, strontium and barium compounds which are at least partly in the solid state, e.g., a water-insoluble compound such as a carbonate, hydroxide, fumarate, phosphate, phosphite, sulphide, molybdate, tungstate, oxide, or mixtures thereof.
  • a water-insoluble compound such as a carbonate, hydroxide, fumarate, phosphate, phosphite, sulphide, molybdate, tungstate, oxide, or mixtures thereof.
  • M VIB is at least a Group VIB metal having an oxidation state of +6.
  • M VIB is molybdenum.
  • M VIB is a mixture of at least two Group VIB metals, e.g., molybdenum and tungsten.
  • FIG. 1 is a block diagram schematically illustrating an embodiment of a general process for making the bulk catalyst out of a catalyst precursor exhibiting type IV adsorption isotherms.
  • Forming a Precipitate or Cogel The first step 10 in the process is a precipitation or cogellation step, which involves reacting in a mixture of the metal precursors 11, e.g., Promoter metal component(s) and the Group VIB metal component to obtain a precipitate or cogel.
  • the term "cogel” refers to a co-precipitate (or precipitate) of at least two metal compounds.
  • the metal precursors can be added to the reaction mixture as a solid, in solution, suspension, or a combination thereof. If soluble salts are added as such, they will dissolve in the reaction mixture and subsequently be precipitated or cogelled, or forming a suspension.
  • the solution can be heated optionally under vacuum to effect precipitation and evaporation of the liquid.
  • the precipitation is carried out at a temperature and pH under which the Promoter metal compound and the Group VIB metal compound precipitate or form a cogel.
  • the temperature at which the cogel is formed is between 25 - 35O 0 C.
  • the catalyst precursor is formed at a pressure between 0 to 3000 psig. In a second embodiment, between 10 to 1000 psig. In a third embodiment, between 30 to 100 psig.
  • the pH of the mixture can be changed to increase or decrease the rate of precipitation or cogelation depending on the desired characteristics of the product. In one embodiment, the mixture is left at its natural pH during the reaction step(s). In another embodiment, the pH is maintained in the range of 0 - 12.
  • the pH is maintained in the range of 7 - 10.
  • Changing the pH can be done by adding base or acid 12 to the reaction mixture, or adding compounds, which decompose upon temperature increase into hydroxide ions or H + ions that respectively increase or decrease the pH.
  • adding compounds which participate in the hydrolysis reaction [039]
  • at least a ligating agent L can be optionally added as one of the reagents forming the precipitate (prior to the precipitation or cogelation of the promoter metal compounds and / or Group VIB metal compounds).
  • the litigating agent L is added after the precipitate is formed (as shown in step 25 of Figure 1).
  • the ligating agent L added after the precipitation step is different from the ligating agent added prior to the precipitation step.
  • the mesoporosity of the catalyst precursor can be controlled or tuned with the selection of the ligating agent and / or the amount added. In one embodiment, it is observed that the incorporation of the ligating agent L significantly increases the porosity of the catalyst precursor. [041] In one embodiment, instead of or in addition to the ligating agent L, diluent amounts from 5-95 wt. % of the total composition of the catalyst precursor can also be added to this step, depending on the envisaged catalytic application. These materials can be applied before or after the precipitation or cogelation of the metal precursors.
  • titania examples include but are not limited to zinc oxide; zinc sulfide; niobia; tetraethyl orthosilicate; silicic acid; titania; silicon components such as sodium silicate, potassium silicate, silica gels, silica sols, silica gels, hydronium- or ammonium-stabilized silica sols, and combinations thereof; aluminum components useful in the process of the present invention include, but are not limited to, sodium aluminate, potassium aluminate, aluminum sulfate, aluminum nitrate, and combinations thereof; magnesium components such as magnesium aluminosilicate clay, magnesium metal, magnesium hydroxide, magnesium halides, magnesium sulfate, and magnesium nitrate; zirconia; cationic clays or anionic clays such as saponite, bentonite, kaoline, sepiolite or hydrotalcite, or mixtures thereof.
  • titania is used as a diluent in an amount
  • liquid is removed from the precipitate (or suspension) via separation processes known in the art, e.g., filtering, decanting, centrifuging, etc.
  • liquid in the precipitate is removed via filtration with vacuum techniques or equipment known in the art, giving a wet filter cake.
  • a wet filter cake is generally defined as filter cake having approximately 10 to 50 wt. % liquid, thus being generally free of water or other solvent such as methanol and the like.
  • optional drying of the filter cake is performed under atmospheric conditions or under an inert atmosphere such as nitrogen, argon, or vacuum, and at a temperature sufficient to remove water but not removal of organic compounds.
  • the drying is performed at about 50 to 120 0 C until a constant weight of the catalyst precursor is reached.
  • the drying is done at a temperature between 5O 0 C to 200 0 C for a period ranging from Vi hour to 6 hours. Drying can be done via thermal drying techniques known in the art, e.g., flash drying, belt drying, oven drying, etc.
  • the filter cake is mixed together with water and other optional materials including but not limited to shaping aids 32, peptizing agents, pore forming agents, and diluent materials 13.
  • rework material in the form of filter cake material, extrudable dough and / or dry particles / pieces of precursor materials from previous runs can be optionally included the materials to form a new batch of catalyst precursor mix.
  • the amount of water and / or the amount of/ type of optional materials is varied to control and / or tune the mesoporosity of the catalyst precursor formed.
  • the addition of water helps increase the surface area of the catalyst precursor.
  • the precursor batch mixture is mixed for a sufficient period of time to obtain a mixture that is substantially uniform or homogeneous.
  • the mixing time depends on the type and efficiency of the mixing technique, e.g., milling, kneading, slurry mixing, dry or wet mixing, or combinations thereof and the mixing apparatus used, e.g., a pug mill, a blender, a double-arm kneading mixer, a rotor stator mixer, or a mix muller.
  • the mixing time ranges from 0.1 to 10 hours.
  • a shaping aid agent is added in a ratio of between 100:1 and 10:1 (wt. % catalyst precursor to wt. % shaping aid).
  • shaping aid agents include but are not limited to organic binders of the cellulose ether type and / or derivatives, polyakylene glycols, saturated or unsaturated fatty acid (such as politic acid, satiric acid or oleic acid) or a salt thereof, a polysaccharide derived acid or a salt thereof, graphite, starch, alkali stearate, ammonium stearate, stearic acid, mineral oils, and combinations thereof.
  • organic binders of the cellulose ether type and / or derivatives polyakylene glycols, saturated or unsaturated fatty acid (such as politic acid, satiric acid or oleic acid) or a salt thereof, a polysaccharide derived acid or a salt thereof, graphite, starch, alkali stearate, ammonium stearate, stearic acid, mineral oils, and combinations thereof.
  • a peptizing agent may be added to the mixture.
  • the peptizing agent may be an alkali or an acid, e.g., ammonia, formic acid, citric acid, nitric acid, maleic acid, carboxylic acid, etc.
  • a pore forming agent is also added to the mixture along with the rework. Examples of pore forming agents include but are not limited to mineral oils, steric acid, polyethylene glycol polymers, carbohydrate polymers, methacrylates, cellulose polymers, and carboxylates which decompose upon being heated.
  • diluent materials can be added. The diluent materials added in this step can be the same as or different from any diluent materials that may have been added to the step of forming the precipitate from metal precursors above.
  • a sufficient amount of water is added to the mixing batch to adjust the batch viscosity to a convenient level for plasticizing and shaping, i.e., a mixture of dough consistency.
  • a sufficient amount of water is added for the mixture to have between 50 to 90 % solids (LOI). In another embodiment, between 60 to 70 % solids (LOI).
  • the catalyst precursor mix is shaped into formed particles, such as spheroids, pills, tablets, cylinders, irregular extrusions, merely loosely bound aggregates or clusters, etc., using any of the methods known in the art including pelletizing, extrusion, tableting, molding, tumbling, pressing, spraying and spray drying.
  • a shaped catalyst precursor is formed via extrusion, using extrusion equipment known in the art, e.g., single screw extruder, ram extruder, twin-screw extruder, etc.
  • the shaping is done via spray drying at an outlet temperature ranging from 100 0 C to 32O 0 C.
  • shaped catalyst precursor is extruded into extrudate having a diameter from about 1/16 to 1/6 of an inch. After extrusion the extrudate can be cut to suitable lengths, e.g., 1/16-inch to 5/16-inch, to produce cylindrical pellets.
  • the shaped catalyst precursor undergoes a thermal treatment step 50.
  • the catalyst precursor is air (or nitrogen) dried in a directly or indirectly heated oven, tray drier, or belt drier at about 50 0 C. to 325°C. for about 15 minutes to 24 hours, and wherein the temperature is room temperature to drying temperature at a rate of 1-50 0 C. per minute.
  • the temperature is ramped up at a slow rate of 1-2°C. per minute.
  • air drying is performed at a fast ramp up rate of at least 25°C. per minute.
  • the drying is at a temperature at or below 100 0 C.
  • the higher temperature of the heat treatment the higher the densities of the catalyst precursor and therefore, upon sulfidation, resulting in a catalyst that also has a low shrinkage rate.
  • low (less than 10%) volumetric shrinkage is obtained with the thermal treatment at a low temperature, e.g., less than 325 0 C, less than 200 0 C, and even at a temperature at or below 100 0 C.
  • the shaped catalyst can be optionally calcined at a temperature in the range of about 350 0 C. to 750 0 C in a suitable atmosphere, e.g., inerts such as nitrogen or argon, or steam.
  • a suitable atmosphere e.g., inerts such as nitrogen or argon, or steam.
  • the calcination is carried out at a temperature between 350 0 C. to 600 0 C.
  • the catalyst precursor gets converted into an oxide.
  • the catalyst precursor is nitrogen stable.
  • nitrogen stable means that the properties (after the catalyst precursor is sulfided to form a catalyst) are not affected by the drying agent, i.e., whether drying in a nitrogen or oxygen environment.
  • the shaped catalyst precursor (with optional rework materials) can be sulfided in a sulf ⁇ ding step 60 to form an active catalyst, with the use of at least a sulfiding agent 62 selected from the group of: elemental sulfur by itself; a sulfur-containing compound which under prevailing conditions, is decomposable into hydrogen sulphide; H 2 S by itself or H 2 S in any inert or reducing environment, e.g., H 2 .
  • a sulfiding agent 62 selected from the group of: elemental sulfur by itself; a sulfur-containing compound which under prevailing conditions, is decomposable into hydrogen sulphide; H 2 S by itself or H 2 S in any inert or reducing environment, e.g., H 2 .
  • sulfiding agents include ammonium sulfide, ammonium polysulf ⁇ de ([(NELt) 2 S x ), ammonium thiosulfate ((NH 4 ) 2 S 2 ⁇ 3), sodium thiosulfate (Na 2 S 2 Os), thiourea CSN 2 H 4 , carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), dibutyl polysulf ⁇ de (DBPS), mercaptanes, tertiarybutyl polysulf ⁇ de (PSTB), tertiarynonyl polysulf ⁇ de (PSTN), and the like.
  • hydrocarbon feedstock is used as a sulfur source for performing the sulf ⁇ dation of the catalyst precursor.
  • shaped catalyst precursor is converted into an active catalyst upon contact with the sulf ⁇ ding agent at a temperature ranging from 25 0 C. to 500 0 C, from 10 minutes to 15 days, and under a H 2 -containing gas pressure.
  • the total pressure during the sulf ⁇ dation step can range between atmospheric to about 10 bar (IMPa). If the sulf ⁇ dation temperature is below the boiling point of the sulf ⁇ ding agent, the process is generally carried out at atmospheric pressure. Above the boiling temperature of the sulf ⁇ ding agent / optional components (if any), the reaction is generally carried out at an increased pressure.
  • catalyst performance can be characterized by the properties of the catalyst precursors before sulf ⁇ dation.
  • the catalyst precursor for preparing the bulk catalyst is characterized as having a poorly crystalline structure with disordered stacking layers, with a type IV adsorption-desorption isotherms of nitrogen. The point at which the relative pressure P/P o of N 2 adsorption and desorption isotherms begins to diverse defines the adsorption capacity of the sulfided catalyst product.
  • the N 2 adsorption desorption isotherms of the catalyst precursor of the invention forms a close hysteresis cycle which enclosed area is proportional to the specific volume of the mesopores.
  • P 0 is the N 2 saturation pressure.
  • the catalyst precursor has a P/P o hysteresis starting point value of about 0.35.
  • the precursor is characterized as having a type H3 hysteresis loop.
  • the hysteresis loop is characterized as having a well developed plateau above P/P o of about 0.55.
  • the precursor is also characterized as having a mesoporous structure with an average pore size (width) ranging from 2 nm to 200 nm in one embodiment; from 5 to 150 nm in a second embodiment, from 10 nm to 125 nm in another embodiment, and from 15 nm to 100 nm in a fourth embodiment.
  • the pore volume in one embodiment is more than 0.01 cm 3 /g. In yet another embodiment, the pore volume ranges from 0.01 to 0.50 cm 3 /g. In a third embodiment ranging from 0.02 to 0.20 cm 3 /g, and in a fourth embodiment ranging from 0.05 to 0.15 cm 3 /g.
  • the surface area measured by the BET method, using nitrogen as adsorbate ranges from 25 to 400 m 2 /g in one embodiment; from 40 to 200 m 2 /g in a second embodiment; and from 60 to 150 m 2 /g in a third embodiment.
  • the bulk metallic catalyst in one embodiment is particularly suitable for hydrotreating heavy petroleum feeds having an atmospheric residue (AR) boiling point in the range of 343 0 C. (65O 0 F.) - to 454 0 C. (850 0 F.) and particularly above 371 0 C. (700 0 F.).
  • Heavy oil feeds having a boiling point greater than 343 0 C. (65O 0 F.) are commonly characterized as having relatively high specific gravity, low hydrogen-to-carbon ratios, and high carbon residue. They contain large amounts of asphaltenes, sulfur, nitrogen and metals, which increase hydrotreating difficulty with their large molecular diameter.
  • the bulk catalyst formed from the precursor with disordered stacking layers and a type IV adsorption-desorption isotherms is characterized as being very stable.
  • a catalyst's stability can be evaluated based on the residual geometric volume shrinkage of the catalyst precursor, measured as the change in the geometric volume of the shaped catalyst precursor before and after it is sulf ⁇ ded.
  • the volumetric shrinkage measured after the sulfidation step can be used as an indication of a catalyst's mechanical integrity under severe hydroprocessing conditions, as precursors are often sulf ⁇ ded in-situ in the same reactor as the hydroprocessing reactor.
  • the catalyst precursor with a type IV adsorption-desorption isotherms is characterized as having a residual geometric volume shrinkage of less than about 12% upon exposure to a temperature of at least 100 0 C. for at least 30 minutes in a sulf ⁇ ding step.
  • the volume shrinkage is less than about 10%.
  • the volume shrinkage is less than about 8%.
  • less than 5% is a value that is less than the volume shrinkage in a second embodiment.
  • the bulk catalyst is particularly suited for hydrotreating heavy petroleum feeds having an average molecular diameter ranging from 0.9 nm to 1.7 nm (9 to 17 angstrom), providing an HDN conversion level of > 99.99% (700°F+ conversion), lowering the sulfur level in fraction above 700 0 F. boiling point to less than 20 ppm in one embodiment, and less than 10 ppm in a second embodiment.
  • the bulk catalyst is particularly suited for hydrotreating a heavy petroleum feed having an average molecular diameter ranging from 0.9 nm to 1.7 nm.
  • the bulk catalyst is particularly suitable for treating a heavy oil feed having an average molecular weight Mn ranging from 300 to 400 g/mole.
  • the precursor for forming the catalyst also exhibits other desirable properties, including a compact bulk density (CBD) of at most 1.6 g/cc; a crush strength of at least about 4 lbs; and an attrition loss of less than 7 wt.%. Attrition loss is the loss to fine amount measured when tumbled one-half hour in a rotating drum. In another embodiment, the attrition loss is less than 5 wt. %.
  • the CBD is at most 1.4 g/cc.
  • the CBD is at most 1.2 g/cc.
  • the crush strength is at least 6 lbs.
  • the catalyst precursor has a particle density of equal or less 2.5 g/cc. In another embodiment, the particle density is equal or less than 2.2 g/cc.
  • the bulk multi-metallic catalyst can be used in virtually all hydroprocessing processes to treat a plurality of feeds under wide-ranging reaction conditions such as temperatures of from 200 to 45O 0 C, hydrogen pressures of from 15 to 300 bar, liquid hourly space velocities of from 0.05 to 10 h "1 and hydrogen treat gas rates of from 35.6 to 2670 m 3 / m 3 (200 to 15000 SCF/B - or "Standard Cubic Feet per Barrel" of hydrocarbon compound feed to the reactor).
  • the catalyst is also characterized by excellent catalytic activity, as giving an almost full HDN conversion rate (> 99.99%) in the hydrotreating of heavy oil feedstock such as VGO.
  • EXAMPLES The following illustrative examples are intended to be non- limiting.
  • the pore structure was characterized by measuring the N2 adsorption desorption isotherms using standard continuous sorption procedures. The specific surface area and the total pore volume can be calculated from the isotherms following IUPAC recommendations. The volume of pores corresponding to the textural mesopores can be evaluated from the upper inflection point of the low P/P o hysteresis loop.
  • Example 1 Ni-Mo-W-maleate catalyst precursor.
  • a catalyst precursor of the formula (NH 4 ) ⁇ [Ni 2 .6 (OH) 2 .o8 (C 4 H 2 0 4 2" )o.o6] (Mo 0 .35W 0 . 6 5O 4 ) 2 ⁇ was prepared as follows: 954.8g of ammonium heptamolybdate (NH 4 )eM ⁇ 7 ⁇ 24 ' 4H 2 O was dissolved in 4.8L of deionized water at room temperature. The pH of the resulting solution was within the range of 2-3.
  • the precipitate was mixed with 4 wt-% Methocel, and dried at 50 C until it exhibited a Loss On Ignition (LOI) of 45 wt-% and a carver of 1500 psi, and extruded in a Wolf screw extruder with NAQ dies.
  • LOI Loss On Ignition
  • the N2 adsorption desorption isotherm of the precursor is shown in Figures 2-3, composed of a well defined hysteresis loop corresponding to the presence of mesoporosity.
  • Pore size characteristics including desorption average pore width (4 V/ A by BET) of 31.9662 angstrom; BJH adsorption average pore width of 37.254 angstrom; and BJH desorption average pore width of 39.350 angstrom.
  • Example 2 Another embodiment of a Ni-Mo-W-maleate catalyst precursor.
  • a catalyst precursor of the formula (NH 4 ) ([Ni 2-6 (OH) 2 .o8 (C 4 H 2 O 4 2- )COO] (M ⁇ o.35Wo.65 ⁇ 4 ) 2 ⁇ was prepared as follows: 477.2g of ammonium heptamolybdate (NH 4 )eM ⁇ 7 ⁇ 24 ' 4H 2 O was dissolved in 2.9L of deionized water at room temperature. 666.6g of ammonium metatungstate (NH 4 ) 6 H 2 Wi 2 0 4 o ' 4.7H 2 O was dissolved in 0.67 L water.
  • the molybdate and tungstate solutions were added to 15.4 L deionized water.
  • a 7.0 wt-% NH 4 OH (ammonia) solution was added so as to reach a pH in the range of 9-10.
  • the temperature was increased to 76 C with constant stirring.
  • a second solution was prepared containing 1575g of Ni(NOs) 2 6H 2 O dissolved in 1.5 L deionized water.
  • the nickel solution was then added in 25 minutes to the molybdate/ tungstate solution while maintaining the temperature at 76 C.
  • the resulting mixture was kept at 76°C and stirred for half an hour.
  • N2 adsorption desorption isotherm of the precursor of Example 2 is shown in Figures 4-5, also composed of a well defined hysteresis loop corresponding to the presence of mesoporosity.
  • Pore size characteristics including desorption average pore width (4 V/A by BET) of 102.8301 angstrom; BJH adsorption average pore width of 103.635 angstrom; and BJH desorption average pore width of 99.889 angstrom.
  • Example 3 A third embodiment of a Ni-Mo-W-maleate catalyst precursor.
  • a catalyst precursor of the formula (NH 4 ) ⁇ [Ni 2 .6 (OH) 2 .os (C 4 H 2 O 4 2- )COO] (M ⁇ o .35 Wo .65 ⁇ 4 ) 2 ⁇ was prepared as follows: 954.4g of ammonium heptamolybdate (NH 4 )eM ⁇ 7 ⁇ 2 4 ' 4H 2 O was dissolved in 5.8L of deionized water at room temperature. 1333g of ammonium metatungstate (NHZt) 6 H 2 Wi 2 O 4 O ' 4.7H 2 O was dissolved in 1.3 L water.
  • the molybdate and tungstate solutions were added to 15.0 L deionized water.
  • 5.0 L of a 7.0 wt-% NH 4 OH (ammonia) solution was added until the pH reached 9.8.
  • a second solution was prepared containing 2835g of Ni(NOs) 2 6H 2 O dissolved in 6.38 L deionized water.
  • a third solution was prepared by dissolving 284.9 g Ni(SO 4 ) 6H 2 O in 2.0 L water, and by subsequently adjusting the pH to 1.0 with concentrated sulfuric acid. After combination of the two nickel solutions, 110.0 g maleic acid dissolved in 0.60 L water was added to the nickel solution.
  • the mixed molybdate/tungstate solution was combined with the nickel solution through an in-line, high-shear mixer which discharged the combined solution into 9.78 L deionized water.
  • the resulting suspension was continuously stirred and maintained at 77 C.
  • the pH of this suspension was raised to 6.5 through addition of an 7.0 wt-% NH40H solution, and aged for 90 minutes with continuous stirring at 77 C.
  • a blue-green precipitate was collected by filtration and dried at 115 C until Carver of 5000 psi. Subsequently the paste was wetted to a Carver of 1500 psi, 4 wt-% MethocelTM was added, and the paste was extruded in a Wolf screw extruder with NAQ dies.
  • Figure 6 is a graph showing the isotherms of catalyst precursor prepared in Example 3, which do not fall into the pattern of a type IV isotherms.

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Abstract

L'invention porte sur un catalyseur multi-métallique en vrac pour l'hydrotraitement de charges d'alimentation d'huile lourde et sur un procédé de préparation du catalyseur. Le catalyseur multi-métallique en vrac est préparé par sulfuration d'un précurseur de catalyseur ayant une structure de cristallinité médiocre avec des couches à empilement désordonné, avec des isothermes de type IV d'adsorption-désorption d'azote avec une valeur de point de départ d'hystérésis d'environ 0,35, pour un catalyseur sulfuré qui facilitera la diffusion du réactif et du produit dans des applications catalytiques. Dans un autre mode de réalisation, le précurseur est caractérisé comme ayant une boucle d'hystérésis de type H3. Dans un troisième mode de réalisation, la boucle d'hystérésis est caractérisée comme ayant un plateau bien développé au-dessus de P/P0 d'environ 0,55. Les mésopores du précurseur peuvent être ajustables ou accordables.
EP10770341.5A 2009-04-29 2010-04-29 Catalyseur multi-métallique d'hydroconversion et son procédé de fabrication Withdrawn EP2424659A4 (fr)

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US12/432,730 US8080492B2 (en) 2009-04-29 2009-04-29 Hydroconversion multi-metallic catalyst and method for making thereof
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US8173570B2 (en) * 2007-10-31 2012-05-08 Chevron U.S.A. Inc. Hydroconversion processes employing multi-metallic catalysts and method for making thereof

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AU2010242953A1 (en) 2011-11-03
CA2759044A1 (fr) 2010-11-04
SG175824A1 (en) 2011-12-29
EA022003B1 (ru) 2015-10-30
EP2424659A4 (fr) 2014-08-27
AU2010242953A2 (en) 2011-11-03
CN102413926B (zh) 2014-01-01
CN102413926A (zh) 2012-04-11
AU2010242953B2 (en) 2015-03-19
WO2010127130A3 (fr) 2011-02-24
WO2010127130A2 (fr) 2010-11-04
CA2759044C (fr) 2017-09-26
EA201171322A1 (ru) 2012-04-30
JP2012525255A (ja) 2012-10-22
JP5502192B2 (ja) 2014-05-28

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