WO2015171277A1 - Catalyseurs d'hydrotraitement et leur fabrication - Google Patents
Catalyseurs d'hydrotraitement et leur fabrication Download PDFInfo
- Publication number
- WO2015171277A1 WO2015171277A1 PCT/US2015/025863 US2015025863W WO2015171277A1 WO 2015171277 A1 WO2015171277 A1 WO 2015171277A1 US 2015025863 W US2015025863 W US 2015025863W WO 2015171277 A1 WO2015171277 A1 WO 2015171277A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- metal
- organic compound
- amide
- catalyst precursor
- Prior art date
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- XGSHEASGZHYHBU-UHFFFAOYSA-N tetradecane-1,1-diamine Chemical compound CCCCCCCCCCCCCC(N)N XGSHEASGZHYHBU-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
-
- 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
-
- B01J35/30—
-
- 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
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- 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
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- B01J35/393—
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- the invention relates to hydroprocessing catalysts and their production.
- BACKGROUND OF THE INVENTION [0002] As refineries are being forced to process crudes with larger amounts of sulfur and nitrogen, while at the same time environmental regulations are mandating lower levels of these heteroatoms in products, a need exists to synthesize catalysts that can do more efficient desulfurization and denitrogenation, particularly where existing units are limited in their pressure capability. In addition, more refractory feeds are desirable from a cost perspective.
- Alumina-supported Ni or Ni/Co-promoted molybdenum sulfides are the traditional catalysts used for hydrodenitrogenation (HDN) or hydrodesulfurization (HDS) at intermediate and relatively high pressures, and alumina-supported Co-promoted molybdenum sulfides are the traditional catalysts for HDS at relatively low pressures.
- Hydroprocessing catalysts usually comprise one or more sulfided Group 6 metals with one or more Group 8 to 10 metals as promoters on a refractory support, such as alumina. Bulk, unsupported catalysts are also known. Hydroprocessing catalysts that are particularly suitable for hydrodesulfurization, as well as hydrodenitrogenation, generally comprise molybdenum or tungsten sulfide promoted with a metal such as cobalt, nickel, iron, or a combination thereof. These sulfided catalysts generally have a layered or platelet morphology. [0004] The ability to modify the nanostructural morphology of hydroprocessing catalysts appears to provide a possible way to control their activity and selectivity.
- U.S. Published Patent Application No. 2007/0072765 discloses a method for preparing a catalyst composition, which method comprises: (a) impregnating an inorganic catalyst support with an aqueous solution containing (i) a salt of a Group VIII metal selected from Co and Ni, (ii) a salt of a Group VI metal selected from Mo and W, and (iii) an effective amount of an organic agent selected from amino alcohols and amino acids; (b) drying the impregnated catalyst support to remove substantially all water, thereby resulting in a metal-organic component on support catalyst precursor; (c) calcining the substantially dried catalyst precursor in the presence of an oxygen- containing atmosphere under conditions to oxidize at least 30%, but not all, of the organic agent and produce a partially oxidized catalyst precursor containing carbon; and (d
- the amine and the acid may be separately impregnated into the metal oxide component to form a catalyst precursor which can then be sulfided to form the active catalyst or, alternatively, the amine salt can be formed with the acid and then impregnated into the metal oxide component.
- Thermal treatment then follows to form the amide in situ and optionally to form additional unsaturation in the organic component.
- the organic when an oxide-organic hybrid phase is formed, the organic can take up“space” in the lattice of the hybrid phases, in some cases drastically reducing the density relative to the mixed metal oxide and/or further limiting the relative amount of inorganic constituents present in the phase.
- the organic component In most of the preparations described herein, the organic component is believed to be located in what were the empty pore spaces of the oxide phase, leaving the high density of the oxide phase substantially intact, and/or to be coordinated to the surface (-OH) groups of the oxide phase. Nonetheless the presence of the organic compound(s) can significantly impact the crystallite size of sulfides generated from the precursors seen by the reduction in the number of stacks.
- an additional or alternate advantage of the processes of the present invention can be that the promoter metals from Groups 8-10 (e.g., Ni) appear to situate very well in respect to the host Group 6 sulfide phase.
- the amide organic component of the catalyst precursors described in Application Serial No. 13/150,662 is formed in situ in the metal oxide component, we have now found that the amide may be preformed prior to impregnation with comparable results.
- one aspect of the present invention relates to a catalyst precursor composition
- a catalyst precursor composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, impregnated with an amide reaction product formed from (i) a first organic compound containing at least one amine group, and (ii) a second organic compound separate from the first organic compound and containing at least one carboxylic acid group.
- a thermal treatment is carried out following the impregnation of the amide into the metal oxide component in order to induce a controlled conversion of the amide into the final organic component of the catalyst precursor which contains additional unsaturation in excess of that in the impregnated amide and potentially additional oxygen when the treatment is carried out in an oxidizing atmosphere such as air.
- the thermal treatment may also be carried out under non-oxidizing conditions, e.g. in an inert gas such as nitrogen, is typically carried out at a temperature from about 195°C to about 250°C; although higher temperatures are possible e.g. up to about 280°C or even higher, the precautions described below to avoid gross decomposition of the organic are appropriate in all cases.
- a bulk mixed metal hydroprocessing catalyst can be produced from this bulk mixed metal oxide catalyst precursor by sulfiding it; the sulfidation should begin after impregnation into the metal oxide component and following the thermal treatment step in the presence of the amide or the oxidized form of the amide.
- Another aspect of the invention resides in a hydroprocessing process, in which a hydrocarbon feed is reacted with hydrogen in the presence of a sulfided form of the amide-containing catalyst precursor made by the steps outlined above.
- the hydroprocessing may typically be hydrodemetallation, hydrodewaxing, hydrotreating, hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, hydroisomerization, and/or hydrocracking.
- the amide-containing catalyst precursor composition is made by a process comprising: (a) impregnating the metal oxide component of the catalyst precursor comprising the metal(s) from Group 6 of the Periodic Table of the Elements, the metal(s) from Groups 8-10 of the Periodic Table of the Elements, with an amide formed from a first organic compound containing at least one amine group and a second organic compound separate from the first organic compound and containing at least one carboxylic acid group to form an organically treated precursor catalyst composition.
- This precursor composition is then (b) heated, typically at a temperature from about 150°C to about 275°C for a sufficient period of time.
- the product of this step is a thermally-treated catalyst precursor which may then be sulfided to form the active catalyst.
- the amide-containing catalyst precursor composition can, in one embodiment, consist essentially of the thermally treated amide reaction product, an oxide form of the metal(s) from Group 6, an oxide form of the metal(s) from Groups 8-10, and optionally about 20 wt% or less of a binder.
- the Group 6 metal component may suitably be Mo and/or W, and the Group 8-10 metal component can suitably be Co and/or Ni.
- the catalyst precursor can further comprise one or more metals from Group 5 of the Periodic Table of the Elements, for example V and/or Nb.
- the first organic compound can comprise at least 10 carbon atoms, for example, can comprise a primary monoamine having from 10 to 30 carbon atoms and/or the second organic compound can comprise at least 10 carbon atoms, for example, can comprise only one carboxylic acid group and can have from 10 to 30 carbon atoms.
- DRAWINGS [0019]
- Figure 1 shows an X-ray diffraction pattern of as-synthesized and dried hexagonal NiWO4 catalyst precursor, produced according to Comparative Example 1.
- Figure 2 shows an X-ray diffraction pattern of as-synthesized and dried NiWO 4 (1,2-diaminocyclohexane) 2 catalyst precursor, produced according to Example 1.
- Figure 3 shows an X-ray diffraction pattern of as-synthesized and dried NiWO 4 (ethylenediamine) 3 catalyst precursor, produced according to Example 2.
- Figure 4 shows X-ray diffraction patterns of the NiWO 4 catalyst precursor of Comparative Example 1 , the NiWO 4 (ethylenediamine) 3 catalyst precursor of Example 2, and the NiWO 4 /(en) 1 and NiWO 4 /(en) 1 /citric acid 0.33 catalyst precursors of Example 3.
- Figure 5 shows X-ray diffraction patterns of the sulfided NiWO 4 catalyst of Comparative Example 1 , as well as sulfided NiWO 4 /(en) 1 , sulfided NiWO 4 /(en) 1 /citric acid 0.33 , and sulfided NiWO 4 /citric acid 0.33 catalysts of Example 3, with and without prior N 2 treatment at about 320°C.
- Figure 6 shows X-ray diffraction patterns of the sulfided NiWO 4 /(en) 1 /citric acid 0.33 catalyst of Example 3 and sulfided NiWO 4 /citric acid 0.33 /(en) 1 and sulfided NiWO 4 /citric acid 0.33 plus (en) 1 catalysts of Example 4.
- Figure 7 shows X-ray diffraction patterns of sulfided catalysts prepared from the amine and organic acid impregnated NiWO 4 precursors of Example 5.
- Figure 8 compares X-ray diffraction patterns of the NiW 0.975 Nb 0.025 O 4 catalyst precursor produced according to Example 6 and the NiWO 4 catalyst precursor produced according to Comparative Example 1.
- Figure 9 compares X-ray diffraction patterns of the CoW 0.5 V 0.5 O 4 catalyst precursor produced according to Example 7 and the NiWO 4 catalyst precursor produced according to Comparative Example 1.
- Figure 10 represents a graph of relative hydrodenitrogenation activity against time on stream for certain Example 5 catalysts, compared to the activity of a reference catalyst.
- Figure 11 represents X-ray diffraction spectra of Catalysts A and C-F following sulfidation in H 2 S/H 2 .
- Figure 12 shows amide formation and decomposition in air and nitrogen for catalyst precursors treated in a similar manner to Catalysts E and F.
- Figure 13 shows X-ray diffraction spectra for a variety of cobalt-containing catalyst precursor oxides.
- Figure 14 shows X-ray diffraction spectra for NiW- and NiMoW- containing catalyst precursor oxides, with and without organic treatments.
- Figures 15A-B show infrared data characterizing bulk catalysts having undergone treatments using two organic compounds at various temperatures and under various conditions.
- a catalyst precursor composition is formed from a metal oxide component comprising at least one metal from Group 6 of the Periodic Table of the Elements and at least one metal from Groups 8-10 of the Periodic Table of the Elements.
- This metal oxide component is impregnated with an ex situ (preformed) amide reaction product of (i) a first organic compound containing at least one amine group, and (ii) a second organic compound containing at least one carboxylic acid group.
- the presence of the amide reaction product in any intermediate or final composition can be determined by known methods, e.g., by infrared spectroscopy (FTIR) or by gas chromatography-mass spectrometry (GC-MS) techniques.
- FTIR infrared spectroscopy
- GC-MS gas chromatography-mass spectrometry
- the thermal treatment which follows impregnation of the pre-formed amide into the metal oxide component may result in the formation of additional unsaturation(s) not present in the amine and the carboxylic acid used to make the amide, e.g., from the partial decomposition/dehydrogenation which takes place at the elevated temperatures used in the treatment.
- the presence of the additional unsaturation(s) in any intermediate or final composition can be determined by known methods, e.g., by FTIR.
- This catalyst precursor composition formed by the impregnation and thermal treatment can be a bulk metal catalyst precursor composition or a supported metal catalyst precursor composition.
- the term“bulk”, used in this specification when describing a mixed metal oxide catalyst composition, indicates that the catalyst composition is self-supporting in that it does not require a carrier or support.
- the bulk catalysts may have some minor amount of carrier or support material in their compositions (e.g., about 20 wt% or less, about 15 wt% or less, about 10 wt% or less, about 5 wt% or less, or substantially no carrier or support, based on the total weight of the catalyst composition); for instance, bulk hydroprocessing catalysts may contain a minor amount of a binder, e.g., to improve the physical and/or thermal properties of the catalyst.
- supported catalyst systems typically comprise a carrier or support onto which one or more catalytically active materials are deposited, often using an impregnation or coating technique.
- heterogeneous catalyst systems without a carrier or support or with a minor amount of carrier or support are generally referred to as bulk catalysts and are frequently formed by co-precipitation techniques.
- the thermal treatment of the amide-impregnated metal oxide component is carried out by heating the impregnated composition to a temperature from about 150°C to about 275°C for a time which does not result in gross decomposition of the amide, although additional unsaturation may arise from partial in situ decomposition; the temperature is typically from about 165°C to about 250°C but higher temperatures, e.g. in the range of 250 to 275°C, can be used in order to abbreviate the duration of the heating although due care is required to avoid the gross decomposition of the pre- formed amide, as discussed further below.
- the bulk mixed metal hydroprocessing catalyst can be produced from this precursor by sulfiding it with the sulfiding taking place with the amide present on the metal oxide component (i.e., when the thermally treated amide, is substantially present and/or preferably not significantly decomposed by the beginning of the sulfiding step).
- Additional unsaturation may be present in the organic component of the catalyst precursor resulting from a variety of mechanisms including partial decomposition, (e.g., via oxidative dehydrogenation in the presence of oxygen and/or via non-oxidative dehydrogenation in the absence of an appropriate concentration of oxygen), of typically-unfunctionalized organic portions of the amide and/or through conjugation/aromatization of unsaturations expanding upon an unsaturated portion the amide.
- the treated organic component may also contain additional oxygen in addition to the unsaturation when the treatment is carried out in an oxidizing atmosphere.
- Catalyst precursor compositions and hydroprocessing catalyst compositions of the present invention can advantageously comprise (or can have metal oxide components that consist essentially of) at least one oxide of a metal or metals from Group 6 of the Periodic Table of Elements and at least one oxide of a metal or metals from Groups 8-10 of the Periodic Table of Elements, and optionally at least one oxide of a metal or metals from Group 5 of the Periodic Table of Elements.
- these metals are present in their substantially fully oxidized form, which can typically take the form of simple metal oxides, but which may be present in a variety of other oxide forms, e.g., such as hydroxides, oxyhydroxides, oxycarbonates, carbonates, oxynitrates, oxysulfates, or some combination thereof.
- the Group 6 metal(s) can be Mo and/or W
- the Group 8-10 metal(s) can be Co and/or Ni.
- the atomic ratio of the Group 6 metal(s) to the metal(s) of Groups 8-10 can be from about 2:1 to about 1 :3, for example from about 5:4 to about 1:2, from about 5:4 to about 2:3, from about 5:4 to about 3:4, from about 10:9 to about 1 :2, from about 10:9 to about 2:3, from about 10:9 to about 3:4, from about 20:19 to about 2:3, or from about 20:19 to about 3:4.
- the composition further comprises at least one metal from Group 5, that at least one metal can suitably be V and/or Nb.
- the amount of Group 5 metal(s) can be such that the atomic ratio of the Group 6 metal(s) to the Group 5 metal(s) can be from about 99:1 to about 1:1 , for example from about 99:1 to about 5:1, from about 99:1 to about 10:1, or from about 99:1 to about 20:1.
- the atomic ratio of the sum of the Group 5 metal(s) plus the Group (6) metal(s) compared to the metal(s) of Groups 8-10 can be from about 2:1 to about 1:3, for example from about 5:4 to about 1:2, from about 5:4 to about 2:3, from about 5:4 to about 3:4, from about 10:9 to about 1:2, from about 10:9 to about 2:3, from about 10:9 to about 3:4, from about 20:19 to about 2:3, or from about 20:19 to about 3:4.
- the numbering scheme for the Periodic Table Groups is as disclosed in Chemical and Engineering News, 63(5), 27 (1985).
- the metals forming the metal oxide component in the catalyst precursor compositions and in the hydroprocessing catalyst compositions according to the invention can be present in any suitable form prior to sulfiding, but are typically and often present as metal oxides.
- the bulk oxide components of the catalyst precursor compositions and of the hydroprocessing catalysts can be prepared by any suitable method, but can generally be produced by forming a slurry, typically an aqueous slurry, comprising (1) (a) an oxyanion of the Group 6 metal(s), such as a tungstate and/or a molybdate, or (b) an insoluble (oxide, acid) form of the Group 6 metal(s), such as tungstic acid and/or molybdenum trioxide, (2) a salt of the Group 8-10 metal(s), such as nickel carbonate, and optionally, when present, (3) (a) a salt or oxyanion of a Group 5 metal, such as a vanadate and/or a niobat
- the slurry can be heated to a suitable temperature, such as from about 60°C to about 150°C, at a suitable pressure, e.g., at atmospheric or autogenous pressure, for an appropriate time, e.g., about 4 hours to about 24 hours.
- a suitable temperature such as from about 60°C to about 150°C
- a suitable pressure e.g., at atmospheric or autogenous pressure
- Non-limiting examples of suitable mixed metal oxide compositions can include, but are not limited to, nickel-tungsten oxides, cobalt-tungsten oxides, nickel- molybdenum oxides, cobalt-molybdenum oxides, nickel-molybdenum-tungsten oxides, cobalt-molybdenum-tungsten oxides, cobalt-nickel-tungsten oxides, cobalt-nickel- molybdenum oxides, cobalt-nickel-tungsten-molybdenum oxides, nickel-tungsten- niobium oxides, nickel-tungsten-vanadium oxides, cobalt-tungsten-vanadium oxides, cobalt-tungsten-niobium oxides, nickel-molybdenum-niobium oxides, nickel- molybdenum-vanadium oxides, nickel-molybdenum-tungsten-niobium oxides, nickel- molybdenum-vanadium oxides, nickel-molybdenum-tungsten-
- Suitable mixed metal oxide compositions can advantageously exhibit a specific surface area (as measured via the nitrogen BET method using a Quantachrome AutosorbTM apparatus) of at least about 20 m 2 /g, for example at least about 30 m 2 /g, at least about 40 m 2 /g, at least about 50 m 2 /g, at least about 60 m 2 /g, at least about 70 m 2 /g, or at least about 80 m 2 /g.
- the mixed metal oxide compositions can exhibit a specific surface area of not more than about 500 m 2 /g, for example not more than about 400 m 2 /g, not more than about 300 m 2 /g, not more than about 250 m 2 /g, not more than about 200 m 2 /g, not more than about 175 m 2 /g, not more than about 150 m 2 /g, not more than about 125 m 2 /g, or not more than about 100 m 2 /g.
- the mixed metal oxide (slurry) composition After separating and drying the mixed metal oxide (slurry) composition, it is treated, generally by impregnation, with the pre-formed amide derived from (i) the first organic compound containing at least one amine group, and (ii) the a second organic compound separate from the first organic compound and containing at least one carboxylic acid group.
- the amide is formed by a condensation reaction between the amine reactant and the carboxylic acid reactant; this reaction, carried out ex situ, is usually accomplished at temperatures between 50 and 250°C.
- the amine from which the amide is formed will preferably have at least 10 carbon atoms, for example from 10 to 20 carbon atoms or 10 to 30 carbon atoms and can comprise a primary monoamine having from 10 to 30 carbon atoms.
- the carboxylic acid used to form the amide can comprise at least 10 carbon atoms, for example can comprise from 10 to 20, e.g. 10 to 30, carbon atoms and may comprise only one carboxylic acid group. Additionally or alternatively, the total number of carbon atoms comprised by both the acid and amine reactants used to form the amide can be at least 15 carbon atoms, for example at least 20 carbon atoms, at least 25 carbon atoms, at least 30 carbon atoms, or at least 35 carbon atoms.
- the total number of carbon atoms comprised among both the first and second organic compounds can be 100 carbon atoms or less, for example 80 carbon atoms or less, 70 carbon atoms or less, 60 carbon atoms or less, or 50 carbon atoms or less.
- organic compounds containing amine groups can include, but are not limited to, primary and/or secondary, linear, branched, and/or cyclic amines, such as triacontanylamine, octacosanylamine, hexacosanylamine, tetracosanylamine, docosanylamine, erucylamine, eicosanylamine, octadecylamine, oleylamine, linoleylamine, hexadecylamine, sapienylamine, palmitoleylamine, tetradecylamine, myristoleylamine, dodecylamine, decylamine, nonylamine, cyclooctylamine, octylamine, cycloheptylamine, heptylamine, cyclohexylamine, n-hexylamine, isopentylamine, n-penty
- the molar ratio of the Group 6 metal(s) in the composition to the first organic compound during treatment can be from about 1 :1 to about 20:1.
- the amine functionality can include primary or secondary amines, as mentioned above, but generally does not include tertiary or quaternary amines, as tertiary and quaternary amines tend not to be able to form amides.
- the amine compound can contain other functional groups besides amine, whether or not they are capable of participating in forming an amide or other condensation reaction product the carboxylic acid compound.
- the first organic compound can comprise an aminoacid, which possesses an amine functional group and a carboxylic acid functional group simultaneously.
- the aminoacid would qualify as only one of the organic compounds, and not both; thus, in such an instance, either an additional amine-containing (first) organic compound would need to be present (in the circumstance where the aminoacid would be considered the second organic compound) or an additional carboxylic acid-containing (second) organic compound would need to be present (in the circumstance where the aminoacid would be considered the first organic compound).
- additional amine-containing (first) organic compound would need to be present (in the circumstance where the aminoacid would be considered the second organic compound)
- an additional carboxylic acid-containing (second) organic compound would need to be present (in the circumstance where the aminoacid would be considered the first organic compound).
- other examples of such secondary functional groups in amine-containing organic compounds can generally include, but are not limited to, hydroxyls, aldehydes, anhydrides, ethers, esters, imines, imides, ketones, thiols (mercaptans), thioesters, and the like, and combinations thereof.
- the amine portion of the first organic compound can be a part of a larger functional group in that compound, so long as the amine portion (notably the amine nitrogen and the constituents attached thereto) retains the capability of participating in forming an amide or other condensation reaction product with one or more of the functional groups from second organic compound.
- the first organic compound can comprise a urea, which functional group comprises an amine portion attached to the carbonyl portion of an amide group.
- the urea can be considered functionally as an“amine-containing” functional group for the purposes of the present invention herein, except in situations where such inclusion is specifically contradicted.
- other examples of such amine-containing functional groups that may be suitable for satisfying the at least one amine group in the first organic compound can generally include, but are not limited to, hydrazides, sulfonamides, and the like, and combinations thereof.
- organic compounds containing carboxylic acids can include, but are not limited to, primary and/or secondary, linear, branched, and/or cyclic acids, such as triacontanoic acid, octacosanoic acid, hexacosanoic acid, tetracosanoic acid, docosanoic acid, erucic acid, docosahexanoic acid, eicosanoic acid, eicosapentanoic acid, arachidonic acid, octadecanoic acid, oleic acid, elaidic acid, stearidonic acid, linoleic acid, alpha-linolenic acid, hexadecanoic acid, sapienic acid, palmitoleic acid, tetradecanoic acid, myristoleic acid, dodecanoic acid, decanoic acid, nonanoic acid, cyclooctanoic acids, such as tria
- the molar ratio of the Group 6 metal(s) in the composition to the second organic compound during treatment can be from about 3:1 to about 20:1.
- the acid reactant can contain other functional groups besides carboxylic acids, whether or not they are capable of participating in forming an amide or other condensation reaction product with one or more of the functional groups from first organic compound.
- the second organic compound can comprise an aminoacid, which possesses a carboxylic acid functional group and an amine functional group simultaneously.
- the aminoacid would qualify as only one of the organic compounds, and not both; thus, in such an instance, either an additional amine-containing (first) organic compound would need to be present (in the circumstance where the aminoacid would be considered the second organic compound) or an additional carboxylic acid-containing (second) organic compound would need to be present (in the circumstance where the aminoacid would be considered the first organic compound).
- additional amine-containing (first) organic compound would need to be present (in the circumstance where the aminoacid would be considered the second organic compound)
- an additional carboxylic acid-containing (second) organic compound would need to be present (in the circumstance where the aminoacid would be considered the first organic compound).
- carboxylic acid-containing organic compounds can generally include, but are not limited to, hydroxyls, aldehydes, anhydrides, ethers, esters, imines, imides, ketones, thiols (mercaptans), thioesters, and the like, and combinations thereof.
- the reactive portion of the second organic compound can be a part of a larger functional group in that compound and/or can be a derivative of a carboxylic acid that behaves similarly enough to a carboxylic acid in the presence of the amine functional group of the first organic compound, such that the reactive portion and/or derivative retains the capability of participating in forming an amide or other desired condensation reaction product with one or more of the functional groups from first organic compound.
- a carboxylic acid derivative can include an alkyl carboxylate ester, where the alkyl group does not substantially hinder (over a reasonable time scale) the condensation reaction between the amine and the carboxylate portion of the ester to form an amide.
- the amide is formed prior to impregnation into the metal oxide component of the catalyst precursor by reaction of the amine component and the carboxylic acid component. Reaction typically takes place readily at mildly elevated temperatures up to about 200°C with liberation of water as a by-product of the reaction at temperatures above 100°C and usually above 150°C.
- the reactants can usually be heated together to form a melt in which the reaction takes place; the amide can then be directly impregnated into the metal oxide component with heat assisting penetration into the structure of the metal oxide component.
- the reaction can also be carried out in the presence of a solvent if desired and the resulting solution used for the impregnation step.
- the amide and its heat treated derivative may not be located/incorporated within the crystal lattice of the mixed metal oxide precursor, e.g., may instead be located on the surface and/or within the pore volume of the precursor and/or be associated with (bound to) one or more metals or oxides of metals in a manner that does not significantly affect the crystalline lattice of the mixed metal oxide precursor composition, as observed through XRD and/or other crystallographic spectra.
- a sulfided version of the mixed metal oxide precursor composition can still have its sulfided form affected by the organic compound(s)/additive(s) and/or the reaction product(s), even though the oxide lattice is not significantly affected.
- the ratio of the reactive amine and carboxylic acid groups in the two reactants may vary, respectively, from about 1:4 to about 4:1 , for example from about 1 :3 to about 3:1 or from about 1:2 to about 2:1. It has been observed that catalysts made with amides from equimolar quantities of the amine and carboxylic acid reactants compounds show performance improvements in hydroprocessing certain feeds and for this reason, amides made with an equimolar ratio are preferred.
- the pre-formed amide is suitably impregnated into the metal oxide precursor by incipient wetness impregnation with the amount determined according to the pore volume of the metal oxide component. Following impregnation, a heat treatment is carried out which first removes any residual water and/or solvent but also creates a reaction product containing additional unsaturation sites and possibly additional oxygen. The amide-impregnated metal oxide component is then heated at a temperature sufficient and for a time sufficient to form a product containing the additional unsaturation which is characteristic of the desired organic component; this treatment with the pre-formed amide is typically from about 150°C to about 275°C, for example from about 200°C to about 250°C).
- the heating step should not be conducted for so long that the amide becomes substantially decomposed but is continued for a sufficiently long time to form additional unsaturation(s), which may result from at least partial decomposition (e.g., oxidative and/or non-oxidative dehydrogenation, oxidative cleavage of unsaturated carbon-carbon bonds, and/or aromatization) of some (typically-unfunctionalized organic) portions of the organic compounds.
- the heating should not be conducted for so long that the decomposition substantially results in gross decomposition of the amide or any condensation product.
- the impregnated catalyst precursor composition can be heated to a temperature high enough to form the unsaturated reaction product and typically high enough to enable any byproducts such as water to be removed.
- the temperature to which the impregnated precursor composition is heated should, however, be maintained low enough so as to substantially retain the amide reaction product with the additional unsaturations and any oxygen, and so as not to significantly decompose the functionalized reaction product, and/or so as not to significantly volatilize more than about 70 % by weight, preferably not more than 60% by weight and in most cases, not more than 50% by weight of the amide.
- the specific lower and upper temperature limits based on the above considerations can be dependent upon a variety of factors that can include, but are not limited to, the atmosphere under which the heating is conducted, the chemical and/or physical properties of the amide, the amide reaction product, and/or any functionalized reaction byproduct as well as the desired duration of the heating with higher temperatures, e.g. over the optimal temperature range up to 275°C, enabling shorter heating durations to be utilized.
- the minimum heating temperature can, for example, suitably be at least about 120°C, for example at least about 150°C, at least about 165°C, at least about 175°C, at least about 185°C, at least about 195°C, at least about 200°C, at least about 210°C, at least about 220°C, at least about 230°C, at least about 240°C, or at least about 250°C.
- the maximum heating temperature should not be greater than about 400°C, for example, not greater than about 375°C, not greater than about 350°C, not greater than about 325°C, not greater than about 300°C, not greater than about 275°C, not greater than about 250°C, not greater than about 240°C, not greater than about 230°C, not greater than about 220°C, not greater than about 210°C, or not greater than about 200°C.
- the temperature to be used should therefore be selected on an empirical basis depending on the nature of the amide used in the impregnation, the partial pressure of oxygen in the heating atmosphere, the equipment used to effect the heating and the time that the impregnated oxide is heat treated.
- the progress of the heating can be monitored according to the properties of the treated product, including analysis by GC-MS and by its infrared spectrum as described below.
- the heating can be conducted in a low- or non- oxidizing atmosphere (and conveniently in an inert atmosphere, such as nitrogen). Alternatively, the heating can be conducted in a moderately- or highly- oxidizing environment. Heating in air is a convenient and preferred procedure which has been found to result in the incorporation of additional oxygen into the reaction product when the treatment is carried out in air or another oxidizing atmosphere.
- the heating can be carried out in a multi-step procedure in which one or more heating steps can be conducted in the low- or non- oxidizing atmosphere, in which one or more heating steps can be conducted in the moderately- or highly- oxidizing environment, or both.
- the period of time for the heating in the environment can be from about 5 minutes to about 168 hours, for example from about 10 minutes to about 96 hours, from about 10 minutes to about 48 hours, from about 10 minutes to about 24 hours, from about 10 minutes to about 18 hours, from about 10 minutes to about 12 hours, from about 10 minutes to about 8 hours, from about 10 minutes to about 6 hours, from about 10 minutes to about 4 hours, from about 20 minutes to about 96 hours, from about 20 minutes to about 48 hours, from about 20 minutes to about 24 hours, from about 20 minutes to about 18 hours, from about 20 minutes to about 12 hours, from about 20 minutes to about 8 hours, from about 20 minutes to about 6 hours, from about 20 minutes to about 4 hours, from about 30 minutes to about 96 hours, from about 30 minutes to about 96 hours, from
- the catalyst precursor composition can be stated to consist essentially of the thermally treated amide reaction product, an oxide form of the metal(s) from Group 6, an oxide form of the metal(s) from Groups 8-10, and optionally about 20 wt% or less of a binder (e.g., about 10 wt% or less).
- the organic-containing thermally treated catalyst precursor composition containing the reaction product can typically contain from about 4 wt% to about 20 wt%, for example from about 5 wt% to about 15 wt%, carbon resulting from the amide and/or its reaction product, based on the total weight of the relevant composition.
- the thermally treated organic catalyst precursor characteristically exhibits a ratio of unsaturated carbon atoms to aromatic carbon atoms, as measured according to peak area ratios using transmission infrared spectroscopic techniques, of a deconvoluted peak centered from about 1700 cm –1 to about 1730 cm –1 (e.g., at about 1715 cm –1 ), compared to a deconvoluted peak centered from about 1380 cm –1 to about 1450 cm –1 (e.g., from about 1395 cm –1 to about 1415 cm –1 ), of at least 0.9.
- This ratio may be higher, for example at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.7, at least 2.0, at least 2.2, at least 2.5, at least 2.7, or at least 3.0.
- Much higher ratios up to 15 may be observed, for example up to 10, up to 8.0, up to 7.0, up to 6.0, up to 5.0, up to 4.5, up to 4.0, up to 3.5, or up to 3.0.
- an oxidizing atmosphere e.g. air
- very specific band forms in the 1710 to 1730 cm -1 range, e.g. at 1710 cm -1 which is not present in the initial amide but appears in the treated, active catalyst precursor.
- the pre- formed amide and/or additional unsaturation(s) present when the catalyst precursor is sulfided to form the final active sulfided (hydroprocessing) catalyst assist somehow in controlling one or more of the following: the size of sulfided crystallites; the coordination of one or more of the metals during sulfidation, such that a higher proportion of the one or more types of metals is are in appropriate sites for promoting desired hydroprocessing reactions (such as hydrotreating, hydrodenitrogenation, hydrodesulfurization, hydrodeoxygenation, hydrodemetallation, hydrocracking including selective hydrocracking, hydroisomerization, hydrodewaxing), and the like, and combinations thereof, and/or for reducing/minimizing undesired hydroprocessing reactions, such as aromatic saturation, hydrogenation of double bonds, and the like,
- desired hydroprocessing reactions such as hydrotreating, hydrodenitrogenation, hydrodesulfurization, hydrodeoxygenation, hydrodemetallation, hydrocracking including selective hydrocracking,
- Coordination/catalysis involving one or more of the metals after sulfidation is believed to proceed with a higher proportion of the form(s) in which the metals are present or that they are present in a form which is more efficient at promoting the desired hydroprocessing reactions (e.g., because the higher proportion of metal sites can catalyze more hydrodesulfurization reactions of the same type in a given timescale and/or because they higher proportion of the metal sites can catalyze more difficult hydrodesulfurization reactions in a similar timescale).
- the active sulfided hydroprocessing catalyst composition is produced by sulfiding the catalyst precursor composition.
- Sulfiding is generally carried out by contacting the catalyst precursor composition containing the amide and/or its oxidized reaction product with a sulfur-containing compound (e.g., elemental sulfur, hydrogen sulfide, polysulfides, , which may originate from a fossil/mineral oil stream, from a biocomponent-based oil stream, from a combination thereof, or from a sulfur-containing stream separate from the aforementioned oil stream(s)) at a temperature and for a time sufficient to substantially sulfide the composition and/or sufficient to render the sulfided composition active as a hydroprocessing catalyst.
- a sulfur-containing compound e.g., elemental sulfur, hydrogen sulfide, polysulfides, , which may originate from a fossil/mineral oil stream, from a biocomponent-based oil stream, from a combination thereof, or from a sulfur-containing stream separate from the aforementioned oil stream(s)
- the sulfidation can be carried out at a temperature from about 300°C to about 400°C, e.g., from about 310°C to about 350°C, for a period of time from about 30 minutes to about 96 hours, e.g., from about 1 hour to about 48 hours or from about 4 hours to about 24 hours.
- the sulfiding can generally be conducted before or after combining the metal (oxide) containing composition with a binder, if desired, and before or after forming the composition into a shaped catalyst.
- the sulfiding can additionally or alternately be conducted in situ in a hydroprocessing reactor.
- the initial or primary stage of the sulfiding step should be carried out with the amide with its additional unsaturation and added oxygen present.
- the oxide should be quantitatively converted to the sulfide during the sulfiding process although a small amount of residual oxide may remain.
- the sulfided catalyst composition preferably exhibits a layered structure comprising a plurality of stacked YS 2 layers, where Y is the Group 6 metal(s), such that the average number of stacks (typically for bulk organically treated catalysts) can be from about 1.5 to about 3.5, for example from about 1.5 to about 3.0, from about 2.0 to about 3.3, from about 2.0 to about 3.0, or from about 2.1 to about 2.8. The average number of stacks will be dependent on actual sulfiding conditions.
- the treatment of the metal (oxide) containing precursor composition according to the invention can afford a decrease in the average number of stacks of the treated precursor of at least about 0.8, for example at least about 1.0, at least about 1.2, at least about 1.3, at least about 1.4, or at least about 1.5, as compared to an untreated metal (oxide) containing precursor composition.
- the number of stacks can be considerably less than that obtained with an equivalent sulfided mixed metal (oxide) containing precursor composition produced without the amide and the heat treatment.
- the reduction in the average number of stacks can be evidenced, e.g., via X-ray diffraction spectra of relevant sulfided compositions, in which the (002) peak appears significantly broader (as determined by the same width at the half-height of the peak) than the corresponding peak in the spectrum of the sulfided mixed metal (oxide) containing precursor composition produced without the present organic treatment .
- TEM transmission electron microscopy
- the sulfided catalyst composition described above can be used as a hydroprocessing catalyst, either alone or in combination with a binder.
- the binder is a significant portion of the catalyst composition, e.g., at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, or at least about 70 wt%; additionally or alternately for heterogeneous/supported catalysts, the binder can comprise up to about 95 wt% of the catalyst composition, e.g., up to about 90 wt%, up to about 85 wt%, up to about 80 wt%, up to about 75 wt%, or up to about 70 wt%.
- Non- limiting examples of suitable binder materials can include, but are not limited to, silica, silica-alumina (e.g., conventional silica-alumina, silica-coated alumina, alumina-coated silica, or the like, or a combination thereof), alumina (e.g., boehmite, pseudo-boehmite, gibbsite, or the like, or a combination thereof), titania, zirconia, cationic clays or anionic clays (e.g., saponite, bentonite, kaoline, sepiolite, hydrotalcite, or the like, or a combination thereof), and mixtures thereof.
- silica-alumina e.g., conventional silica-alumina, silica-coated alumina, alumina-coated silica, or the like, or a combination thereof
- alumina e.g., boehmite, pseudo-boehmite, gib
- the binder can include silica, silica-alumina, alumina, titania, zirconia, and mixtures thereof. These binders may be applied as such or after peptization. It may also be possible to apply precursors of these binders that, during precursor synthesis, can be converted into any of the above-described binders.
- Suitable precursors can include, e.g., alkali metal aluminates (alumina binder), water glass (silica binder), a mixture of alkali metal aluminates and water glass (silica-alumina binder), a mixture of sources of a di-, tri-, and/or tetravalent metal, such as a mixture of water-soluble salts of magnesium, aluminum, and/or silicon (cationic clay and/or anionic clay), chlorohydrol, aluminum sulfate, or mixtures thereof.
- alkali metal aluminates alumina binder
- water glass sica binder
- sica-alumina binder a mixture of alkali metal aluminates and water glass
- sources of a di-, tri-, and/or tetravalent metal such as a mixture of water-soluble salts of magnesium, aluminum, and/or silicon (cationic clay and/or anionic clay), chlorohydrol, aluminum sulfate, or mixtures thereof.
- the binder material to be used can have lower catalytic activity than the remainder of the catalyst composition, or can have substantially no catalytic activity at all (less than about 5%, based on the catalytic activity of the bulk catalyst composition being about 100%). Consequently, by using a binder material, the activity of the catalyst composition may be reduced. Therefore, the amount of binder material to be used, at least in bulk catalysts, can generally depend on the desired activity of the final catalyst composition. Binder amounts up to about 25 wt% of the total composition can be suitable (when present, from above 0 wt% to about 25 wt%), depending on the envisaged catalytic application.
- binder amounts when added, can generally be from about 0.5 wt% to about 20 wt% of the total catalyst composition.
- the binder material can be composited with a source of a Group 6 metal and/or a source of a non-noble Group 8-10 metal, prior to being composited with the bulk catalyst composition and/or prior to being added during the preparation thereof. Compositing the binder material with any of these metals may be carried out by any known means, e.g., impregnation of the (solid) binder material with these metal(s) sources.
- a cracking component may also be added during catalyst preparation.
- the cracking component can represent from about 0.5 wt% to about 30 wt%, based on the total weight of the catalyst composition.
- the cracking component may serve, for example, as an isomerization enhancer.
- Conventional cracking components can be used, e.g., a cationic clay, an anionic clay, a zeolite (such as ZSM-5, zeolite Y, ultra-stable zeolite Y, zeolite X, an AlPO, a SAPO, or the like, or a combination thereof), amorphous cracking components (such as silica-alumina or the like), or a combination thereof. It is to be understood that some materials may act as a binder and a cracking component at the same time.
- the cracking component may be composited with a Group 6 metal and/or a Group 8-10 non-noble metal, prior to being composited with the catalyst composition and/or prior to being added during the preparation thereof.
- Compositing the cracking component with any of these metals may be carried out by any known means, e.g., impregnation of the cracking component with these metal(s) sources.
- the compositing may be done on each component separately or may be accomplished by combining the components and doing a single compositing step.
- cracking components can depend on the intended catalytic application of the final catalyst composition. For instance, a zeolite can be added if the resulting composition is to be applied in hydrocracking or fluid catalytic cracking. Other cracking components, such as silica-alumina or cationic clays, can be added if the final catalyst composition is to be used in hydrotreating applications.
- the amount of added cracking material can depend on the desired activity of the final composition and the intended application, and thus, when present, may vary from above 0 wt% to about 80 wt%, based on the total weight of the catalyst composition.
- the combination of cracking component and binder material can comprise less than 50 wt% of the catalyst composition, for example, less than about 40 wt%, less than about 30 wt%, less than about 20 wt%, less than about 15 wt%, or less than about 10 wt%.
- further materials can be added, in addition to the metal components already added, such as any material that would be added during conventional hydroprocessing catalyst preparation. Suitable examples of such further materials can include, but are not limited to, phosphorus compounds, boron compounds, fluorine-containing compounds, sources of additional transition metals, sources of rare earth metals, fillers, or mixtures thereof.
- the mixed metal oxide catalyst compositions described herein can be used in many hydroprocessing processes to treat any of a plurality of feeds under wide- ranging reaction conditions, such as temperatures from about 200°C to about 450°C, hydrogen pressures from about 5 barg to about 300 barg (about 0.5 MPag to about 30 MPag), LHSVs from about 0.05 hr -1 to about 10 hr -1 , and hydrogen treat gas rates from about 200 scf/bbl to about 10,000 scf/bbl (about 34 Nm 3 /m 3 to about 1700 Nm 3 /m 3 ).
- hydroprocessing should be understood to encompass all processes in which a hydrocarbon feed is reacted with hydrogen (e.g., at the temperatures and pressures noted above), and specifically includes hydrodemetallation, hydrodewaxing, hydrotreating, hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, hydroisomerization, and hydrocracking (including selective hydrocracking), as well as combinations thereof.
- the products of hydroprocessing may show improved viscosities, viscosity indices, saturate contents, low temperature properties, volatilities, depolarization, or the like, or combinations thereof.
- hydroprocessing can be practiced in one or more reaction zones, in either countercurrent flow or co-current flow mode.
- countercurrent flow mode is meant a process mode in which the feedstream flows in a direction opposite to the flow of hydrogen-containing treat gas.
- the hydroprocessing reactor can also be operated in any suitable catalyst-bed arrangement mode (e.g., fixed bed, slurry bed, ebullating bed, or the like).
- Suitable feedstocks can include, but are not limited to, whole and reduced petroleum crudes, atmospheric and vacuum residua, propane deasphalted residua (e.g., brightstock), cycle oils, FCC tower bottoms, gas oils (including atmospheric and vacuum gas oils, as well as coker gas oils), light to heavy distillates (including raw virgin distillates), hydrocrackates, hydrotreated oils, dewaxed oils, slack waxes, Fischer-Tropsch waxes, raffinates, naphthas, and the like, and combinations thereof.
- the feedstock can include renewable or biofeed in the form of lipid material in addition to hydrocarbons , so long as there is sufficient sulfur content in the feedstock to implicate the use of hydroprocessing catalysts.
- lipid material is a composition comprised of biological materials. Generally, these biological materials include vegetable fats/oils, animal fats/oils, fish oils, pyrolysis oils, and algae lipids/oils, as well as components of such materials. More specifically, the lipid material includes one or more type of lipid compounds.
- Lipid compounds are typically biological compounds that are insoluble in water, but soluble in nonpolar (or fat) solvents such as alcohols, ethers, chloroform, alkyl acetates, benzene, and combinations thereof.
- Suitable biofeeds which may be treated with the present catalysts either alone or in combinations with mineral oils are given in Application Serial No. 13/150,662 to which reference is made for a full and detailed description of them.
- One way to judge the effectiveness of the amide impregnation and thermal treatment can be based on relative catalytic activity for a given reaction process (e.g., hydrodenitrogenation, hydrodesulfurization, hydrodeoxygenation, or the like).
- Such relative catalytic activity can further be expressed by comparing standard catalyst characteristics, such as weight, volume, moles of a certain (active metal) component, or the like, to normalize the results for universal comparison amongst catalysts useful in that given reaction process. Even so, such standard characteristics may not be universally comparable– for example, because supported catalysts tend to have most of their catalytically active metal sites spread out over the support surface (and thus available for catalyzation), comparison of relative activities between supported catalysts and bulk catalysts may be inappropriate or uninformative, since proportionally fewer of the catalytically active metal sites in a bulk catalyst are disposed on the surface (and thus available for catalyzation).
- standard catalyst characteristics such as weight, volume, moles of a certain (active metal) component, or the like
- relative catalytic activity can be a particularly useful comparison.
- the relative volumetric activity (RVA), which normalizes the activity of the catalyst to a unit volume based on catalyst loading and catalyst density, and the relative molar activity (RMA), which normalizes activity herein to the collective number of moles of non-Group 8-10 catalytically active metal(s) are based on hydrodenitrogenation (HDN) reactions, assuming ⁇ 1.0 order kinetics.
- the non-Group 8-10 catalytically active metal(s) includes any and all Group 6 catalytically active metal(s) (e.g., Mo and/or W), as well as other catalytically active metal(s) such as Group 5 (e.g., Nb and/or V). All the RMA values herein were taken from experiments where catalyst was“on stream” (i.e., contacting the feed at reaction conditions such as hydroprocessing reaction conditions) for between about 10 days and about 30 days, and RMA values were only reported when they appeared to stabilize.
- Group 6 catalytically active metal(s) e.g., Mo and/or W
- other catalytically active metal(s) such as Group 5 (e.g., Nb and/or V). All the RMA values herein were taken from experiments where catalyst was“on stream” (i.e., contacting the feed at reaction conditions such as hydroprocessing reaction conditions) for between about 10 days and about 30 days, and RMA values were only reported when they appeared to stabilize.
- the present catalysts can exhibit an increase in RMA for amide-impregnated/heat treated catalyst compositions of at least 57%, compared to catalyst compositions without amide impregnation and heat treatment with the RMA varying with the basic nitrogen content of the feed, being greater for feeds with lower basic nitrogen and less for those with higher basic nitrogen.
- the RMA increase can be at least 58%, at least 59%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, or at least 85%.
- the RMA increase can be up to 500%, for example up to 450%, up to 400%, up to 350%, up to 300%, up to 250%, up to 200%, up to 175%, up to 150%, up to 125%, up to 100%, up to 95%, or up to 90%, compared to catalyst compositions without amide impregnation and heat treatment.
- the invention will now be more particularly described with reference to the accompanying drawings and the following Examples.
- EXAMPLES [0075] In the Examples, X-ray diffraction spectra were collected on a Rigaku Dmax diffractometer with Cu K D radiation.
- Thermogravimetry, Dynamic Thermal Analysis, and Mass Spectrometry (TG/DTA/MS) data were collected on a Mettler TGA 851 thermal balance, interfaced with a Balzers Thermostar quadrupole mass spectrometer, which was equipped with a secondary electron multiplier. Weight loss during air oxidation at about 800°C was monitored both before and after the thermal treatment of the organically treated catalyst precursor to estimate the amount of organic components present in the sample. Also, the sulfided phases can be oxidized to form oxides (a weight loss event), thus allowing estimation of additional weight loss due to retention of the organic component in the sulfide phase.
- a metastable hexagonal variant of NiWO 4 is formed by a solid-slurry reaction between nickel carbonate and tungstic acid. About 5.93 grams nickel carbonate and about 12.49 grams tungstic acid were added to about 150mL of water to form a suspension, which was added to a ⁇ 275mL Weflon TM reaction vessel. The vessel was then heated (in a microwave oven) to about 150°C for about 6 hours, cooled to about room temperature (about 20-25°C), and filtered and dried at about 100°C.
- NiWO 4 (1,2DACH) 2 /(citric acid) Into a ⁇ 1000cc glass reaction flask equipped with a reflux condenser, about 16.6 grams nickel carbonate ( ⁇ 0.14 moles Ni) and about 35.0 grams tungstic acid ( ⁇ 0.14 moles W) were added to about 150 mL of water, into which about 32.0 grams 1,2-diaminocyclohexane (1 ,2DACH; ⁇ 0.28 moles, technical grade, Aldrich) had been previously dissolved. A stirrer, thermometer, and reflux condenser was attached to the flask. The reaction mixture was continuously stirred and heated to about 90°C and held overnight (about 18 hours).
- catalyst 1a The solid so obtained was filtered and dried at about 100°C. The weight obtained, about 39.5 g, compares with a calculated weight of about 74.9 g.
- the X-ray diffraction spectrum of the dried product is shown in Figure 2 and was labeled as catalyst 1a.
- a portion of catalyst 1a [NiWO 4 (1 ,2DACH) 2 ] was treated in a flowing nitrogen stream (about 200 cm 3 /min) in a quartz line tube furnace, with a heating rate of about 2°C/min, to a final temperature of about 320°C and was held at that temperature for about 90 minutes. It was then cooled to approximately room temperature and removed from the furnace. This catalyst was labeled as catalyst 1 a//N 2 .
- catalyst 1 a Another portion of catalyst 1 a was impregnated (by incipient wetness) with citric acid such that the molar ratio of tungsten to citric acid was about 1 :0.33. This sample was dried at about 100°C overnight and labeled as catalyst 1 b. A portion of catalyst 1 b was treated in a flowing nitrogen stream (about 200 cm 3 /min) in a quartz line tube furnace, with a heating rate of about 2°C/min, to a final temperature of about 320°C and was held at that temperature for about 90 minutes. It was then cooled to approximately room temperature and removed from the furnace. This catalyst was labeled as catalyst 1b//N 2 .
- Example 2 Preparation of NiWO 4 (ethylenediamine) 3
- a tris-ethylenediamine complex of NiWO 4 was prepared by the reaction of about 5.94 grams nickel carbonate, about 12.49 grams tungstic acid, and about 9.02 grams ethylenediamine, all placed along with about 10 mL water into a ⁇ 275mL Weflon TM reaction vessel. The vessel was sealed and the reaction mixture continuously stirred and heated at about 10°C/min to about 60°C (in a microwave reactor) and was held at that temperature for about 6 hours. After cooling and filtering, about 9.4 grams of the known phase of the tris-ethylenediamine nickel tungstate was identified and labeled catalyst 2.
- Figure 3 shows the X-ray diffraction pattern of this phase.
- Example 3 Preparation of NiWO 4 /(en) 1 /citric acid 0.33 /N 2
- the NiWO 4 precursor produced in Comparative Example 1 was impregnated with ethylenediamine (en), such that the mole ratio of tungsten to en was about 1 :1.
- en ethylenediamine
- a portion of this sample was labeled catalyst 3a.
- Another portion of catalyst 3a was treated in a flowing nitrogen stream (about 200 cm 3 /min) in a quartz line tube furnace, with a heating rate of about 2°C/min, to a final temperature of about 320°C and was held at that temperature for about 90 minutes. It was then cooled to approximately room temperature and removed from the furnace.
- This catalyst was labeled as catalyst 3a//N 2 .
- the portion of the catalyst 3a that had been impregnated with en and dried at about 100°C was then further impregnated (to the incipient wetness point) with citric acid dissolved in water, such that the molar ratio of en to citric acid was about 1 :0.33.
- This sample was then dried again at about 100°C and labeled as catalyst 3b.
- a portion of this catalyst 3b sample was treated in a flowing nitrogen stream (about 200 cm3 /min) in a quartz-lined tube furnace, with a heating rate of about 2°C/min, to a final temperature of about 320°C and was held at that temperature for about 90 minutes. It was then cooled to approximately room temperature and removed from the furnace.
- catalyst 3b//N 2 It was labeled as catalyst 3b//N 2 .
- a separate portion of the NiWO 4 was impregnated with only citric acid, such that the molar ratio of tungsten to citric acid was about 1:0.33. This portion was then dried at about 100°C and labeled as catalyst 3c.
- a portion of catalyst 3c was treated in a flowing nitrogen stream (about 200 cm 3 /min) in a quartz-lined tube furnace, with a heating rate of about 2°C/min, to a final temperature of about 320°C and was held at that temperature for about 90 minutes. It was then cooled to approximately room temperature and removed from the furnace. It was labeled as catalyst 3c//N 2 .
- Figure 4 shows X-ray diffraction spectra of catalysts 3a and 3b and, by comparison, the X-ray diffraction spectra of catalysts A and 2a.
- This Figure shows the partial conversion of the NiWO 4 hexagonal nickel tungstate oxide precursor phase upon addition of ethylenediamine to form tris-ethylenediamine nickel tungstate phase (catalyst 3a compared to catalyst A), and the subsequent reversion of this phase on citric acid impregnation (catalyst 3b) to the nickel tungstate oxide phase (catalyst 2a).
- Figure 5 shows the X-ray diffraction spectra of catalysts 3a, 3a//N 2 , 3b, 3b//N 2 , 3c, and 3c//N 2 after sulfidation, according to the protocol described above, together with the X-ray diffraction spectrum of the sulfided NiWO 4 catalyst of Comparative Example 1 (indicated as A).
- Figure 5 shows that the (002) peak of the sulfide prepared from the neat oxide, the oxide impregnated with either en or citric alone, and the latter two with inert high temperature treatment were all approximately equally sharp (i.e., they appear to have roughly the same width at half-height for the (002) reflection as the neat oxide precursor (6)).
- Example 3 the same hexagonal nickel tungstate oxide precursor (catalyst A) was used.
- the NiWO 4 was then impregnated with an aqueous solution of citric acid, such that the molar ratio of tungsten to citric acid was about 1:0.33.
- This sample was then dried at about 100 o C, after which ethylenediamine (en, dissolved in water) was added (by incipient wetness) to a portion of this sample, such that the molar ratio of en to citric acid was about 1:0.33 and such that the molar ratio of tungsten to en was about 1 :1.
- This sample was then dried again at about 100 o C and labeled as catalyst 4a.
- catalyst 4a was treated in a flowing nitrogen stream (about 200 cm 3 /min) in a quartz-lined tube furnace, with a heating rate of about 2°C/min, to a final temperature of about 320°C and was held at that temperature for about 90 minutes. It was then cooled to approximately room temperature and removed from the furnace. It was labeled as catalyst 4a//N 2 .
- a separate catalyst sample was prepared by combining the aqueous citric acid solution with ethylenediamine and by impregnating this solution (in two incipient wetness steps) onto a portion of catalyst A, with drying in air at about 100°C after each impregnation step. It was labeled as catalyst 4b.
- Example 5 Preparation of other organic promoted NiWO 4 precursors
- a variety of other samples, each containing both (i) a diamine or an alkanolamine and (ii) an organic acid, impregnated onto the NiWO 4 oxide of Comparative Example 1 were prepared in a manner analogous to the description in Example 3.
- the amine was impregnated first, using the tungsten/amine mole ratio indicated in Table 1, followed by drying at about 100°C, then a second impregnation of the organic acid, another drying at about 100°C, and then inert nitrogen treatment at about 320°C.
- Table 1 Table 1
- Example 6 Preparation of organic promoted NiW 0.975 Nb 0.025 O 4 precursors
- a different oxide precursor was used to prepare the dual promoted catalysts.
- a sample of approximate nominal composition NiW 0.975 Nb 0.025 O 4 was synthesized in a manner similar to the preparation of NiWO 4 described in Comparative Example 1 , except that about 2.5 mol% of the tungsten component (tungstic acid) was substituted with the appropriate molar amount of niobic acid.
- the X-ray diffraction spectrum of the resulting product was nearly identical to the material without Nb, as shown in Figure 8.
- the oxidic catalyst precursor containing Nb was designated as catalyst 6a.
- catalyst 6a was impregnated sequentially with ethylenediamine and then citric acid, such that the mole ratios were as follows: [W + Nb]/en of about 1:1 and [W + Nb]/citric acid of about 1:0.33.
- the resultant product was then treated in an inert nitrogen stream in the manner described in Example 3and was labeled as catalyst 6b//N 2 .
- Example 7 Preparation of organic promoted CoW 0.5 V 0.5 O 4 precursors
- a sample of approximate nominal composition Co 1 W 0.5 V 0.5 oxide was prepared by reacting about 7.93 grams cobalt carbonate (about 0.067 moles Co), about 3.03 grams vanadium oxide (V 2 O 5 ; about 0.033 moles V), and about 8.33 grams tungstic acid (about 0.033 moles W) in a water suspension of about 150 mL, while heating to about 150°C for about 8 hours.
- the resulting phase, identified as catalyst 7 exhibited an x-ray diffraction pattern shown in Figure 9, where it is compared to the pattern for NiWO 4 of Comparative Example 1 (and also shown in Figure 13).
- catalyst 7 was used as the host oxide for sequentially impregnation of ethylenediamine and then citric acid in a manner analogous to the description in Example 3.
- the molar ratio of [W + V] to en was about 1:1
- the molar ratio of [W + V] to citric acid was about 1:0.33.
- the samples were dried in air at about 100°C after each of the two impregnation steps, thus forming catalyst 7a.
- a portion of the catalyst 7a sample was then treated in a flowing nitrogen stream (about 200 cm 3 /min) in a quartz-lined tube furnace, with a heating rate of about 2°C/min, to a final temperature of about 360°C and was held at that temperature for about 90 minutes.
- catalyst activity results were obtained using a batch high-pressure reactor unit.
- the batch reactor was initially charged with about 65 ⁇ l of catalyst and about 1.85 ml of sulfiding feed.
- a partially hydrotreated distillate feed (about 570 ppm sulfur content and about 350 ppm nitrogen content) was used for sulfiding the catalyst.
- Catalyst sulfiding was done at about 315°C and at about 400 psig (about 2.9 MPag) using a hydrogen gas mixture containing about 10% H 2 S for about 30 hours.
- the batch reactor assembly was orbitally shaken to ensure good mixing of the gas, liquid, and catalyst. Following sulfiding, the spent feed was removed by de-pressurizing the reactor and cooling the reactor assembly to ambient conditions (approximately room temperature, or about 20-25°C). To minimize air exposure, the feed removal and dispensing was performed inside a glove box kept under a nitrogen atmosphere. Catalyst performance was then evaluated by charging a fresh (1.85 ml) load of vacuum gas oil (VGO) feed. The reactor was then pressurized to about 650 psig (about 4.6 MPag) with ⁇ 100% H 2 and heated to about 357°C (about 675°F).
- VGO vacuum gas oil
- the reference catalyst used for all the runs reported was a relatively high activity catalyst made from an oxide (only) catalyst precursor of approximate stoichiometry NiMo 0.5 W 0.5 O 4 (see catalyst B of Comparative Example 1).
- Comparative Example 2 Testing of Catalysts of Comparative Example 1 [0099] The hydrodenitrogenation (HDN) activity of a sulfided sample of catalyst A (bulk NiWO 4 with no organics present) for the VGO feed of Table 4 was compared to that of a sulfided reference sample made from an oxide (only) catalyst precursor of approximate stoichiometry NiMo 0.5 W 0.5 O 4 (catalyst B).
- HDN hydrodenitrogenation
- Catalyst A was found to have an RWA of 1.02, indicating it to have practically the same HDN activity as the catalyst B.
- Example 8 Testing of Catalysts of Example 1 [00100] The HDN activity of sulfided samples of catalysts 1a, 1 a//N 2 , 1b, and 1 b//N 2 , all of which were described in Example 1, were compared against the HDN activity of a sulfided reference sample made from catalyst B. The activities were normalized on a weight basis, relative to the reference, and are shown in Table 5. Because of the relatively low density of these bimetallic oxide-amine hybrid phases, the activities on a relative volume basis were less than that of the reference catalyst. Table 5
- Example 9 Testing of Catalysts of Example 3 [00102] The HDN activity of sulfided samples of catalysts 3a, 3b, and 3b//N 2 , all of which were described in Example 3, were compared against the HDN activity of a sulfided reference sample made from catalyst B. The activities were normalized on a weight basis relative to the reference and are shown in Table 6. Table 6
- Table 6 shows that HDN activities higher than that of the reference catalyst can be reached by having both the diamine and the organic acid present simultaneously, especially with the sample being treated in an inert stream at elevated temperature before sulfiding. Since the catalyst with both the amine and citric acid treatment exhibited a crystal structure (see Figure 4) of the mixed oxide (NiWO 4 ) with the organic acid-salt coating its surface, the relatively high density of the oxide phase was maintained, and the relative volume activity was also higher than the reference.
- Example 10 Testing of Nitrogen-Treated Catalysts of Examples 3 and 4
- a sulfided sample of catalyst 3b//N 2 was selected together with a repeat sample preparation of same catalyst (catalyst 3b//N 2 repeat) and with a sulfide sample of catalyst precursor 4a//N 2 (having the same composition but with the reverse sequence of addition, i.e., with citric acid added first and then followed by ethylene diamine and subjected to the high temperature nitrogen treatment).
- These three samples, along with a sulfided reference sample made from catalyst B, were compared in a HDN activity test using the vacuum gas oil described in Table 4. The results are shown in Table 7.
- Example 11 Testing of Nitrogen-Treated Catalysts of Example 5 [00106] Sulfided samples of the catalyst precursors with different organic bases were selected from preparations of Example 5 and were tested in an HDN test using the vacuum gas oil of Table 4, together with a sulfided reference sample made from catalyst B. The results are shown in Table 8. Table 8
- Example 12 Testing of Further Nitrogen-Treated Catalysts of Example 5 [00108] Sulfided samples of the catalyst precursors impregnated with maleic acid were selected from preparations of Example 5 and were tested in an HDN test using the vacuum gas oil of Table 4, together with a sulfided reference sample made from catalyst B. The results are shown in Table 9.
- Example 13 Testing of Nitrogen-Treated Catalyst of Example 6
- a sulfided sample of the niobium-containing precursor catalyst 6b//N 2 was compared with a sulfided reference sample made from catalyst B in an HDN test using the vacuum gas oil of Table 4 and was found to have an RWA of about 1.53. This result shows that the addition of Nb to the precursor Ni-W oxide can impart significant additional activity to the Ni-W precursors prepared with the dual organic promotion.
- Example 14 Testing of Catalysts of Example 7 [00111] Sulfided samples of catalyst 7 (approximate stoichiometry Co 1 W 0.5 V 0.5 oxide only) and catalyst 7a//N 2 (approximate stoichiometry Co 1 W 0.5 V 0.5 oxide impregnated with ethylenediamine and citric acid and heated in nitrogen) were compared with a sulfided reference sample made from catalyst B in an HDN test using the vacuum gas oil of Table 4. The results are shown in Table 10. Table 10
- Example 15 Flow Reactor Testing of Catalysts of Example 5 [00113]
- catalyst activity results were obtained using a three phase flow reactor test.
- Each of the three reactors used in the test was a stainless steel U-shaped vessel having a ⁇ 0.28 inch ( ⁇ 0.7 cm) internal diameter, with quartz wool at the inlet and quartz wool and a glass fritted gasket at the exit.
- Each of the three reactors was loaded with a different catalyst precursor to be tested and was placed in a common sand bath and run in an up-flow mode.
- the catalyst precursors employed in the tests were: (a) sample 5b//N 2 (NiWO 4 //o-phenylendiamine 1 //citric 0.33 //N 2 treated at about 320°C), (b) sample 5g//N 2 (NiWO 4 //cyclohexylamine 1 //citric acid 0.33 //N 2 treated at about 320°C), and (c) the reference catalyst, catalyst B, (approximate stoichiometry Ni 1 Mo 0.5 W 0.5 O 4 ).
- the pressure was set to about 100 psig (about 790 kPa), H 2 flow was stopped, and the sulfiding feed (about 7.5 wt% dimethyl disulfide, dissolved in a diesel boiling range stream) was flowed at about 8 ml/hr over each catalyst for about 4 hours. Then, with the sulfiding feed continuing, H 2 was added to each reactor at a flow rate of about 48 sccm, the pressure was raised to about 650 psig (about 4.6 MPag), and then the temperature was increased to about 235°C over about 4 hours. The system was then kept isothermal at about 235°C for about another 12 hours.
- the temperature was raised to about 345°C over a period of about 4.5 hours and was isothermally held for about another 16 hours. This completed the sulfiding of the catalyst. [00115] The temperature was then reduced to about 230°C over an ⁇ 8 hour period, and the sulfiding feed was then replaced by the vacuum gas oil (VGO) specified below in Table 11.
- VGO vacuum gas oil
- the feed vessels, ISCO pumps, reservoirs, and all the unit lines were heated to ⁇ 80-120°C to keep the VGO feed flowing.
- the pressure was raised to about 1200 psig (about 8.4 MPag) and the temperature increased from about 230°C to about 365°C over a period of about 4 hours.
- the VGO flow was set at about 3.3 ml/hr, and the H 2 flow rate was set to about 49.5 sccm equivalent to an LHSV of about 1.1 hr -1 at a hydrogen flow rate of about 5000 scf/bbl. After about 18-24 hours, the first liquid samples were obtained, and sampling was continued once a day for the remainder of the run. A calibrated ANTEKTM 9000 series analyzer was used to measure the sulfur and nitrogen content of the diluted product. Table 11
- the sample was first dried at about 100°C overnight in a drying oven and was then placed in a box furnace, which was programmed at a ramp rate of about 2°C/min up to about 250°C. The sample was held at that temperature for about 4 hours in stagnant air. This sample was then impregnated with an aqueous citric acid solution, such that the NiWO 4 to citric acid mole ratio was about 1:0.19. This sample was again dried at about 100°C overnight in a drying oven and was then placed in a box furnace in air, which was programmed at a ramp rate of about 2°C/min up to about 230°C.
- Example 18 Preparation of NiWO 4 //aniline 1 //citric acid 0.33 //N 2 320°C [00118]
- the NiWO 4 from Example 1 was impregnated with aniline (ACS reagent, 99.5%, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of NiWO 4 to aniline was about 1:1.
- the sample was placed into a drying oven and maintained at about 100°C overnight.
- the sample was then impregnated with an aqueous citric acid solution, such that the NiWO 4 to citric acid mole ratio was about 1:0.33.
- This sample was again dried at about 100°C overnight in a drying oven and was then heated in a flowing nitrogen stream (about 300 cm 3 /min) in a quartz lined tube furnace with a heating rate of about 2°C/min to a final temperature of about 320°C.
- the sample was held at that temperature for about 90 minutes and was then cooled to ambient/room temperature and removed from the furnace. It was labeled as catalyst D.
- Example 19 Example 19
- NiWO 4 //(oleylamine) 0.13 /(citric acid) 0.15 //air 230°C
- the NiWO 4 from Example 1 was impregnated with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of NiWO 4 to oleylamine was about 1:0.13.
- the sample was placed into a drying oven and maintained at about 100°C overnight.
- the sample was then impregnated with an aqueous citric acid solution, such that the NiWO 4 to citric acid mole ratio was about 1:0.15.
- Example 20 Preparation of NiWO 4 //(oleylamine) 0.13 /(citric acid) 0.15 //N 2 320°C [00120]
- the NiWO 4 from Example 1 was impregnated with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of NiWO 4 to oleylamine was about 1:0.13.
- the sample was placed into a drying oven and maintained at about 100°C overnight.
- the sample was then impregnated with an aqueous citric acid solution, such that the NiWO 4 to citric acid mole ratio was about 1:0.15.
- This sample was again dried at about 100°C overnight in a drying furnace and was then placed in a box furnace and heated in a flowing nitrogen stream (about 400 cm 3 /min) in a quartz line tube furnace with a heating rate of about 2°C/min to a final temperature of about 320°C.
- the sample was held at that temperature for about 90 minutes and was then cooled to ambient/room temperature and removed from the furnace. It was labeled as catalyst F.
- the organic contents of the different samples, obtained by thermogravimetric measurements, are listed below in Table 12. Table 12.
- the catalyst precursors compositions were sulfided, as described above, and their sulfided XRD spectra are shown in Figure 11 (the spectrum for Catalyst A is shown in Figure 1, and its synthesis was described in Comparative Example 1 herein).
- the sulfided sample prepared using aniline as the first organic compound exhibited only a slighter broader (002) peak than the samples obtained using propylamine and cyclohexylamine as the first organic compound (Samples 5f and 5g, respectively).
- Catalysts C, E, and F The samples prepared using oleylamine as the first organic (Catalysts C, E, and F) compound show measurably broader (002) peaks, indicating notably smaller numbers of stacks and thus notably smaller crystallites.
- Catalysts A and C-F were compared in two different three phase flow reactor tests using a VGO feed. The VGO used in test had the properties shown below in Table 11 hereinabove.
- Each of the powdered catalyst samples were pilled, crushed, and sieved to approximately 35/60 mesh (about 250-500 ⁇ m diameter), and then mixed w ith ⁇ 40-60 mesh quartz powder to give a total volume of about 6cm 3 , with roughly half of the volume comprising the catalyst sample and roughly half the quartz diluent.
- Each sample was loaded into a stainless steel U-shaped reactor ( ⁇ 0.71 cm diameter) with quartz wool at the inlet and quartz wool and a glass fritted gasket at the exit.
- Each of three reactors was placed in a common sand bath and run in an up-flow mode.
- the pressure was increased to about 100 psig (about 690 kPag), hydrogen flow was stopped, and the sulfiding feed (about 7.5 wt% dimethyl disulfide, or DMDS, dissolved in a diesel boiling range feed) flowing at a rate of about 8 mL/hr was passed over each sample for about 4 hours. Then, with the sulfiding feed continuing, hydrogen was added to each reactor with a flow rate of about 48 sccm, at which point the pressure was raised to about 650 psig (about 4.5 MPag) and then the temperature was increased to about 235°C over about the next 4 hours. The system was then held at approximately isothermal conditions at about 235°C for about another 12 hours.
- DMDS dimethyl disulfide
- the temperature was raised again to about 345°C over a period of about 4.5 hours and held at approximately isothermal conditions for about another 16 hours, at which point catalyst sulfidation was considered complete.
- the temperature was then cooled to about 230°C over about an 8 hour period, and the sulfiding feed was replaced by the vacuum gas oil (VGO).
- VGO vacuum gas oil
- the feed vessels, ISCO pumps reservoirs, and all the unit lines were heated to about 80-120°C to facilitate flow of the VGO (e.g., to put the VGO in a liquid state).
- the pressure was then raised to about 1200 psig (about 8.3 MPag) and the temperature increased from about 230°C to about 365°C over a period of about 4 hours.
- VGO flow was set at about 3.3 mL/hr, and the hydrogen flow rate was set to about 49.5 sccm, which was equivalent to an LHSV of about 1.1 hr -1 and a hydrogen flow of about 5000 scf/bbl (about 845 Sm 3 /m 3 ).
- a calibrated ANTEK 9000 series instrument was used to measure the sulfur and nitrogen content of the diluted product. Catalysts A, C, and D were compared after about 20 days on stream. The nitrogen and sulfur contents are shown in Table 13. Table 13.
- Catalysts A, E, and F were compared in a similar feed under similar conditions. After about 29 days on stream, the nitrogen and sulfur contents in the product, as well as the RVAs and RMAs based on HDN activity, (assuming 1 st order kinetics) were obtained and are shown in Table 14. Table 14.
- NiWO 4 //(oleylamine) 0.1 /(oleic acid) 0.06 //air 220°C
- the NiWO 4 from Example 1 was impregnated with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of NiWO 4 to oleylamine was about 1:0.10.
- the sample was placed into a drying oven and maintained at about 100°C overnight.
- the sample was then impregnated with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the NiWO 4 to oleic acid mole ratio was about 1:0.06.
- This sample was again dried at about 100°C overnight in a drying furnace and was then placed in a box furnace in air and heated at a rate of about 0.5°C/min to a final temperature of about 220°C. The sample was held at that temperature for about 4 hours and was then cooled to ambient/room temperature and removed from the furnace. It was labeled as catalyst G.
- the approximate organic content of Catalyst G (before sulfidation) was found to be about 17.4%.
- Example 22 Preparation of NiWO 4 //(oleylamine) 0.13 //air 230°C
- the NiWO 4 from Example 1 was impregnated with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of NiWO 4 to oleylamine was about 1:0.13.
- the sample was placed into a drying furnace and maintained at about 100°C overnight. This sample was then heated in air at a rate of about 0.5°C/min to a final temperature of about 230°C. The sample was held at that temperature for about 4 hours and was then cooled to ambient/room temperature and removed from the furnace. It was labeled as catalyst H.
- Example 23 Preparation of NiWO 4 //(oleic acid) 0.13 //air 220°C
- the NiWO 4 from Example 1 was impregnated with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of NiWO 4 to oleic acid was about 1 :0.13.
- the sample was placed into a drying furnace and maintained at about 100°C overnight. This sample was then heated in air at a rate of about 0.5°C/min to a final temperature of about 220°C. The sample was held at that temperature for about 4 hours and was then cooled to ambient/room temperature and removed from the furnace.
- Catalyst J It was labeled as catalyst J.
- the approximate organic content of Catalyst J (before sulfidation) was found to be about 14.7%.
- Another run was performed with the same VGO feed from Table 11 herein in the same manner as in Example 20 at the following conditions: a temperature of about 365°C, a total pressure of about 1200 psig (about 8.3 MPag), a hydrogen treat gas rate of about 5000 scf/bbl (about 845 Sm 3 /m 3 ), and a weight hourly space velocity (WHSV) of about 1.1 hr -1 .
- the HDN and HDS capability of Catalysts A, H, and J were compared after about 19 days on stream.
- the nitrogen and sulfur contents, as well as the relative volume and molar HDN activities, were obtained (assuming 1 st order kinetics) and are shown in Table 17 below. Table 17.
- CoWO 4 precursor sample was formed by a solid-slurry reaction between cobalt carbonate and tungstic acid. About 23.79 grams of cobalt carbonate and about 49.97 grams of tungstic acid were added to about 800mL of water to form a suspension (pH ⁇ 6.4 that w as placed into a ⁇ 1L round bottom flask eqipped w ith a condenser, which was then heated to about 90°C for about 16 hours. After cooling to ambient/room temperature, the solid was filtered and dried overnight at about 100°C in a drying oven.
- Figure 13 shows the XRD spectrum of this sample.
- the Co 1 Mo 1 O 4 precursor sample was prepared by reacting about 23.78 grams of cobalt carbonate with about 28.8 grams of MoO 3 slurried in ⁇ 800mL of water. This mixture was placed into a ⁇ 1L round bottom flask equipped with a condenser, which was then heated to about 90°C for about 16 hours. After cooling to ambient/room temperature, the solid was filtered and dried overnight at about 100°C in a drying oven.
- Figure 13 shows the XRD spectrum of this sample.
- Co 2.5 Mo 1 O 5.5 precursor sample was prepared by reacting about 59.5 grams of cobalt carbonate with about 28.8 grams of MoO 3 slurried in ⁇ 800mL of water. This mixture was placed into a ⁇ 1L round bottom flask equipped with a condenser, which was then heated to about 90°C for about 16 hours. After cooling to ambient/room temperature, the solid was filtered and dried overnight at about 100°C in a drying oven. Figure 13 shows the XRD spectrum of this sample.
- the Co 1.5 Mo 1 O 4.5 precursor sample (containing ammonium ions) was prepared by first dissolving about 17.65 grams of ammonium heptamolybdate tetrahydrate (about 0.1 mole Mo) in ⁇ 800mL of water and placing this into a ⁇ 1L round bottom flask equipped with a condenser. To this solution, about 22.5 mL of concentrated NH 4 OH ( ⁇ 3:1 mole ratio of NH 4 OH/Co) was added, thus raising the pH to ⁇ 9.4 (solution A). This solution was then warmed to about 90°C.
- a second solution was prepared by dissolving about 43.64 grams of cobalt nitrate hexahydrate, (about 0.15 moles Co) in about 50mL of water (solution B) and maintaining this solution at a temperature of about 90°C.
- the cobalt solution (solution B) was added dropwise at a rate of about 7 cm 3 /min into the molybdenum solution (solution A).
- a precipitate began to form after about 1/4 of the solution was added.
- the final pH after solutions A and B were mixed together was ⁇ 6.5. This suspension/slurry was stirred for an additional 30 minutes while the temperature was maintained at 90°C, after which it was cooled to ambient/room temperature, filtered, and dried at about 120°C. The total weight after drying was about 30.2 grams.
- Example 25 The XRD spectrum of the dried sample is shown in Figure 13.
- Example 25 Preparation of CoV 0.5 W 0.5 O 4 /(oleylamine) 0.67 /(oleic acid) 0.094 //air 170°C
- the CoV 0.5 W 0.5 O 4 precursor sample from Example 7 was impregnated with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of CoV 0.5 W 0.5 O 4 to oleylamine was about 1 :0.067.
- the sample was placed into a drying furnace and maintained at about 100°C overnight.
- This sample was then impregnated with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the CoV 0.5 W 0.5 O 4 to oleic acid mole ratio was about 1:0.094.
- This sample was then dried at about 100°C overnight, followed by heating in a box furnace in air at a rate of about 0.5°C/min to a final temperature of about 170°C. The sample was held at that temperature for about 2 hours and was then cooled to ambient/room temperature before being removed from the furnace.
- oleic acid 50% technical grade, commercially available from Aldrich of Milwaukee, WI
- CoWO 4 /(oleylamine) 0.13 /(citric acid) 0.15 //air 210°C The CoWO 4 precursor sample from Example 24 was impregnated with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of CoWO 4 to oleylamine was about 1 :0.13. The sample was placed into a drying furnace and maintained at about 100°C overnight. This sample was then impregnated with an aqueous citric acid solution, such that the CoWO 4 to citric acid mole ratio was about 1 :0.15.
- Example 27 Preparation of CoMoO 4 /(oleylamine) 0.059 /(oleic acid) 0.075 //air 200°C
- the CoMoO 4 precursor sample from Example 24 was impregnated with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of CoMoO 4 to oleylamine was about 1 :0.059.
- the sample was placed into a drying furnace and maintained at about 100°C overnight. This sample was then impregnated with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the CoWO 4 to oleic acid mole ratio was about 1:0.075. This sample was then dried at about 100°C overnight, followed by heating in a box furnace in air at a rate of about 0.5°C/min to a final temperature of about 200°C. The sample was held at that temperature for about 2 hours and was then cooled to ambient/room temperature before being removed from the furnace. Example 28.
- oleic acid 50% technical grade, commercially available from Aldrich of Milwaukee, WI
- the Co 1.5 MoO 4.5 precursor sample from Example 24 was impregnated with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of Co 1.5 MoO 4.5 to oleylamine was about 1:0.067.
- the sample was placed into a drying furnace and maintained at about 100°C overnight.
- This sample was then impregnated with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the Co 1.5 MoO 4.5 to oleic acid mole ratio was about 1:0.085.
- Example 29 Preparation of Co 2.5MoO5.5/(oleylamine)0.074/(oleic acid)0.095//air 200°C
- the Co 2.5 MoO 5.5 precursor sample from Example 24 was impregnated with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of Co 1.5 MoO 4.5 to oleylamine was about 1:0.067.
- the sample was placed into a drying furnace and maintained at about 100°C overnight. This sample was then impregnated with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the Co 2.5 MoO 5.5 to oleic acid mole ratio was about 1:0.095. This sample was then dried at about 100°C overnight, followed by heating in a box furnace in air at a rate of about 0.5°C/min to a final temperature of about 200°C. The sample was held at that temperature for about 2 hours and was then cooled to ambient/room temperature before being removed from the furnace. Example 30.
- oleic acid 50% technical grade, commercially available from Aldrich of Milwaukee, WI
- the sulfiding feed (dimethyl disulfide, or DMDS, dissolved in a diesel boiling range feed to attain a sulfur content of about 2.6%) flowing at a rate sufficient to attain an LHSV of about 1.0 hr -1 was passed through each sample for about 5 hours. Then, with the sulfiding and hydrogen feeds continuing to flow, the temperature was raised to about 232°C at a rate of about 14°C/hr and held at approximately isothermal conditions for about 20 hours.
- DMDS dimethyl disulfide
- the temperature was raised again to about 321°C at a rate of about 14°C/hr and held at approximately isothermal conditions for about 12 hours, followed by another temperature increase to about 343°C at a rate of about 14°C/hr and held at approximately isothermal conditions for about 8 hours, at which point catalyst sulfidation was considered complete.
- reaction conditions were as follows: a temperature of about 655°F (about 346°C) EIT, a total pressure of about 575 psig (about 3.97 MPag), an LHSV of about 0.85 hr -1 , and a hydrogen treat gas rate of about 936 scf/bbl (about 159 Nm 3 /m 3 ).
- sulfided catalysts were used to hydroprocess a diesel boiling range feed having the following properties: a sulfur content of about 1.37 wt%; a nitrogen content of about 134 wppm; an API gravity of about 33.1 (degrees); and a T 95 of about 709°F (about 376°C).
- Table 18 The sulfur contents of the hydroprocessed diesel boiling range products after about 20 days on stream were obtained and are shown in Table 18 below. Table 18.
- Example 31 Catalyst Performance on Mixed Biofeed
- Three catalysts were compared in a three phase flow reactor test using a predominantly VGO feed, which contained about 20 wt% soybean oil.
- Catalyst K was a commercially available NiMo catalyst supported on alumina.
- Catalyst L was a commercially available bulk NiMoW catalyst.
- Catalyst M was a catalyst according to the invention, with similar composition to Catalysts E and/or G.
- the soybean oil was substantially free of sulfur, nitrogen, and metal heteroatoms and comprised predominantly triglycerides with varying alkyl chain lengths, but mostly C 18 .
- the VGO base used in this Example exhibited the properties delineated in Table 19 below.
- Catalysts were sulfided using a procedure similar to that described in Example 20 herein. Further, in these experiments, the reaction conditions were as follows: a temperature of about 680°F (about 360°C) EIT, a total pressure of about 1287 psig (about 8.87 MPag), and a hydrogen treat gas rate of about 5950 scf/bbl (about 1010 Nm 3 /m 3 ).
- Catalyst K was run at an LHSV of about 0.77 hr -1 , while Catalysts L and M were each run at LHSV values of about 1.08 hr -1 .
- the nitrogen and sulfur contents after about 78 days on stream were obtained and are shown in Table 20 below. Table 20.
- the liquid product obtained was substantially oxygen free, with greater than 99% removal of oxygen.
- the oxygen was removed in various forms, e.g., as water, CO, and/or CO 2 .
- Table 21 shows the H 2 S-free concentrations of these side-products in the reactor gas effluent stream. Table 21.
- Example 32 Catalyst Performance on Mixed Biofeed
- Catalysts K, L, and M were compared in a three phase flow reactor test using a predominantly gasoil feed, which contained about 20 wt% soybean oil.
- the soybean oil was the same as in Example 31, but the gasoil base used in this Example exhibited the properties delineated in Table 22 below. Table 22.
- the catalysts were sulfided using a procedure similar to that described in Example 20. Further, in these experiments, the reaction conditions were as follows: a temperature of about 625°F (about 329°C) EIT, a total pressure of about 1000 psig (about 6.9 MPag), and a treat gas rate of about 2070 scf/bbl (about 350 Nm 3 /m 3 ). Catalyst K was run at an LHSV of about 0.78 hr -1 , while Catalysts L and M were each run at LHSV values of about 1.11 hr -1 . The nitrogen and sulfur contents after about 78 days on stream were obtained and are shown in Table 23 below. Table 23.
- the liquid product obtained was substantially oxygen free, with greater than 99% removal of oxygen.
- the oxygen was removed in various forms, e.g., as water, CO, and/or CO 2 .
- Table 24 shows the H 2 S-free concentrations of these side-products in the reactor gas effluent stream. Table 24.
- Example 33 Catalyst Performance in Hydrocracking Function
- Catalysts K, L, and M were compared in a three phase flow reactor test using two different VGO feeds, labeled VGO1 and VGO2.
- the VGO feeds used in this Example exhibited the properties delineated in Table 25 below.
- the catalysts were sulfided using a procedure similar to that described in Example 20 herein. Further, in these experiments, the reaction conditions were varied. The nitrogen and sulfur contents after about 40 days on stream were obtained for VGO1 feed at the following conditions: a temperature of about 710°F (about 377°C) EIT, an LHSV of about 1.4 hr -1 , and a hydrogen treat gas rate of about 4000 scf/bbl (about 680 Nm 3 /m 3 ). Catalyst K was run at a total pressure of about 1875 psig (about 12.9 MPag), while Catalysts L and M were each run at a total pressure of about 1275 psig (about 8.8 MPag). Results are shown in Table 26 below, which indicate superior performance of the treated catalyst composition, even at relatively lower pressures. Table 26.
- NiMo 0.5 W 0.5 O 4 //(oleylamine) 0.10 /(oleic acid) 0.06 //air 220°C
- NiMo 0.5 W 0.5 O 4 was prepared as described in Comparative Example 1. After it was dried and calcined at about 300°C, it was composited with an inert binder into bound particles, such that about 7 wt% of the weight of the bound particles was the inert binder (with the remainder being the mixed metal oxide).
- This impregnated sample was dried in a drying furnace overnight at about 100°C, placed in a box furnace, heated in air at about 0.5°C/min up to about 220°C, and held for about four hours at that temperature. The heat treated sample was then cooled to ambient/room temperature and removed from the furnace (labeled as catalyst P).
- the catalyst samples were each contacted with the same VGO feed from Table 11 herein in the same manner as in Example 20 at the following conditions: a temperature of about 365°C, a total pressure of about 1200 psig (about 8.3 MPag), a hydrogen treat gas rate of about 5000 scf/bbl (about 845 Sm 3 /m 3 ), and a weight hourly space velocity (WHSV) of about 1.1 hr -1 .
- the HDN and HDS capability of these catalyst samples were compared after about 13 days on stream. The nitrogen and sulfur contents were obtained and are shown in Table 29 below. Table 29.
- NiWO 4 //(ethanolamine) 1 /(citric acid) 0.33 //air 220°C
- NiWO 4 was prepared as described in Comparative Example 1 and was dried and calcined at about 300°C. About 20 grams of the calcined NiWO 4 powder was impregnated with about 3.98 grams of ethanolamine using an incipient wetness technique. The impregnated powder was dried about 100°C overnight and then cooled to ambient/room temperature. Thereafter, an aqueous solution ( ⁇ 4 mL) containing about 4.18 grams of citric acid was impregnated into/onto the ethanolamine- impregnated powder to the incipient wetness point.
- the catalyst samples were each contacted with the same VGO feed from Table 11 herein in the same manner as in Example 20 at the following conditions: a temperature of about 365°C, a total pressure of about 1200 psig (about 8.3 MPag), a hydrogen treat gas rate of about 5000 scf/bbl (about 845 Sm 3 /m 3 ), and a weight hourly space velocity (WHSV) of about 1.1 hr -1 .
- the HDN and HDS capability of these catalyst samples were compared after about 26 days on stream.
- the nitrogen and sulfur contents for catalysts Q and B were obtained and are shown in Table 30 below. Table 30.
- NiWO 4 was prepared as described in Comparative Example 1. After it was dried and calcined at about 300°C, it was composited with an inert binder into bound particles, such that about 7 wt% of the weight of the bound particles was the inert binder (with the remainder being the mixed metal oxide).
- Oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI) was mixed together with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI) and heated to about 100°C to form a solution.
- Another of the three samples was then placed in a box furnace, heated in air at about 0.5°C/min up to about 230°C, and held for about 4 hours at that temperature.
- the high-temperature sample was then cooled to ambient/room temperature and removed from the furnace (labeled as catalyst S).
- the last of the three samples was then treated in a flowing nitrogen stream (about 200 cm 3 /min) in a quartz line tube furnace, with a heating rate of about 2°C/min, to a final temperature of about 230°C and held at that temperature for about 90 minutes. It was then cooled to ambient/room temperature and removed from the furnace (labeled as catalyst T).
- catalysts R and S were sulfided using a procedure similar to that described in Example 20 herein. Upon sulfiding, the catalyst samples were each contacted with a VGO feed having the properties listed in Table 32 below in the same manner and under the same conditions as in Example 35.
- Example 37 Effect of organic treatment environment on NiW catalysts
- two samples were prepared of NiWO 4 //(oleylamine) 0.13 /(citric acid) 0.15 .
- the NiWO 4 was prepared as described in Comparative Example 1 , followed by drying and calcination at about 300°C, and then cooling to ambient/room temperature.
- Oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI) and citric acid were separately impregnated into the metal oxide composition as described in Example 35 to attain a mole ratio of NiWO 4 to oleylamine of about 1:0.13 and to attain a mole ratio of NiWO 4 to citric acid of about 1:0.15.
- the IR spectra were collected, processed and analyzed with Thermo Scientific Omnic V7.1 software. Each reported spectrum is the average of about 256 scans across the range from about 4000 cm–1 to about 1000 cm –1 , with a spectral resolution of about 4 cm –1 . The reported spectra were each normalized by subtracting a background spectrum of an empty IR cell. Peak deconvolution and fitting analysis was done using symmetric Gaussian functions in the 2000–1200 cm –1 region with Omnic V7.1 commercial software, though other commercial software, such as OriginLab or PeakFit, could have alternatively been used.
- the first sample was placed in an IR cell and subject to a flow of ⁇ 20 vol% oxygen in helium (oxidative environment) at about 100°C for about 90 minutes, at which time a transmission IR spectrum was collected ( Figure 15A-1).
- that same sample was subject to a flow of ⁇ 20 vol% oxygen in helium (oxidative environment) at about 230°C for about 240 minutes, at which time another spectrum was collected ( Figure 15A-2).
- the second sample was placed in an IR cell and subject to a flow of ⁇ 100% helium (non-oxidative environment) at about 100°C for about 90 minutes, at which time a transmission IR spectrum was collected (Figure 15B-3).
- the fitting analysis of the sample treated in the higher-temperature oxidative environment (2) identified a peak extending from about 1618 cm –1 to about 1812 cm –1 and centered at about 1715 cm –1 with a height of about 0.40 a.u., a full width at half maximum (FWHM) of about 63 cm -1 , and an integrated area of about 27.0 a.u.
- the feature centered at about 1773 cm -1 was fitted with a peak extending from about 1723 cm –1 to about 1841 cm –1 with a height of about 0.16 a.u., a FWHM of about 51 cm –1 , and an integrated area of about 8.66 a.u.
- the most prominent peak identified at lower wavenumbers extended from about 1290 cm –1 to about 1512 cm –1 and was centered at about 1400 cm –1 with a height of about 0.12 a.u., a FWHM of about 81 cm –1 , and an integrated area of about 9.98 a.u.
- the fitting analysis of the sample treated in the lower-temperature oxidative environment (1 ) identified a peak extending from about 1626 cm –1 to about 1816 cm –1 and centered at about 1722 cm –1 with a height of about 0.26 a.u., a FWHM of about 66 cm –1 , and an integrated area of about 18.1 a.u.
- the peak centered at about 1395 cm –1 (ranging from about 1310 cm –1 to about 1440 cm –1 ) had a height of about 0.30 a.u., a FWHM of about 110 cm –1 , and an integrated area of about 34.8 a.u. No peak was identified in the region around 1773 cm –1 for this sample.
- the ratio of the height and integrated area of the peak centered at about 1715 cm –1 , compared to the one centered at about 1400 cm –1 was about 3.5 and about 2.7, respectively.
- the ratio of the height and integrated area of the peak centered at about 1715 cm –1 , compared to the one centered at about 1400 cm –1 was about 0.87 and about 0.52, respectively.
- the spectra in Figure 15B of particular interest on spectrum (4) were infrared bands centered at maxima of about 1773 cm –1 and about 1698 cm –1 , along with broad bands centered in the ⁇ 1570–1620 cm –1 and ⁇ 1380–1450 cm –1 regions.
- the fitting analysis of the sample treated in the higher-temperature non- oxidative environment (4) identified a peak extending from about 1653 cm –1 to about 1765 cm –1 and centered at about 1706 cm –1 with a height of about 0.15 a.u., a FWHM of about 39 cm –1 , and an integrated area of about 6.17 a.u.
- the feature centered at about 1671 cm –1 was fitted with a peak extending from about 1582 cm –1 to about 1761 cm –1 with a height of about 0.17 a.u., a FWHM of about 64 cm –1 , and an integrated area of about 11.6 a.u.
- the most prominent peak identified at lower wavenumbers extended from about 1416 cm –1 to about 1495 cm –1 and was centered at about 1455 cm –1 with a height of about 0.11 a.u., a FWHM of about 29 cm –1 , and an integrated area of about 3.31 a.u.
- the featured centered at about 1410 cm –1 was fitted with a peak extending from about 1324 cm –1 to about 1482 cm –1 with a height of about 0.10 a.u., a FWHM of about 62 cm –1 , and an integrated area of about 6.85 a.u.
- the fitting analysis of the sample treated in the lower-temperature non-oxidative environment (3) identified a peak extending from about 1630 cm –1 to about 1815 cm –1 and centered at about 1723 cm –1 with a height of about 0.17 a.u., a FWHM of about 66 cm –1 , and an integrated area of about 11.81 a.u.
- the peak centered at about 1415 cm –1 (ranging from about 1284 cm –1 to about 1540 cm –1 ) had a height of about 0.14, a FWHM of about 95 cm –1 , and an integrated area of about 14.27 a.u. No peak was identified in the region around ⁇ 1773 cm –1 for that spectrum.
- the ratio of the height and integrated area of the peak centered at about 1715 cm –1 , compared to the one centered at about 1410 cm –1 was about 1.4 and about 0.9, respectively.
- the ratio of the height and integrated area of the peak centered at about 1715 cm –1 , compared to the one centered at about 1410 cm –1 was about 1.2 and about 0.8, respectively.
- the peaks in these spectra have been identified herein by their wavenumber (cm –1 ), those peaks can be correlated to specific bond excitations (stretches, wags, bends, etc.), based on various factors including (but not necessarily limited to) the wavenumber position of peaks and the physico-chemical nature of bonds known or presumed to exist within each sample.
- One sample of calcined NiWO 4 at ambient/room temperature was exposed to an amount of the oleylamine-oleic acid solution to simultaneously co-impregnate the organic components into/onto the sample, the amount being sufficient to attain a mole ratio of NiWO 4 to oleylamine of about 1:0.074 and to attain a mole ratio of NiWO 4 to oleic acid of about 1:0.094.
- the other sample of calcined NiWO 4 at ambient/room temperature was impregnated first with oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI), such that the mole ratio of NiWO 4 to oleylamine was about 1:0.11.
- the sample was placed into a drying oven and maintained at about 100°C overnight and cooled to ambient/room temperature.
- the dried sample was then impregnated with an aqueous citric acid solution, such that the NiWO 4 to citric acid mole ratio was about 1:0.15.
- the nominal molar ratios do not appear on their face to be equimolar, the actual molar ratios are approximately equimolar when all the amine and carboxylic functionality in the reactants is taken into consideration.
- Both samples were then dried at about 100°C overnight in a drying furnace and were subsequently placed in a box furnace (in air) and heated at a rate of about 0.5°C/min to a final temperature of about 220°C.
- Example 39 Effect of reducing content of Group 8-10 metal
- a first sample containing equimolar amounts of nickel and tungsten (NiWO 4 ) was prepared according to Comparative Example 1. After it was dried and calcined at about 300°C, it was composited with an inert binder and formed into an extrudate having an average diameter of about 1.3 mm, such that about 7 wt% of the weight of the extrudate was the inert binder (with the remainder being the mixed metal oxide).
- Oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI) was mixed together with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI) and heated to about 100°C to form a solution.
- the first sample of calcined equimolar NiWO 4 was likewise heated to about 100°C, and then an amount of the solution was used to simultaneously co-impregnate the organic components into/onto the sample, the amount being sufficient to attain a mole ratio of NiWO 4 to oleylamine of about 1:0.10 and to attain a mole ratio of NiWO 4 to oleic acid of about 1 :0.06.
- This impregnated sample was dried in air in a drying furnace overnight at about 100°C.
- a second sample was prepared using a similar procedure to Comparative Example 1 , but adjusting the ingredients to provide a nickel-to-tungsten molar ratio of only about 0.75:1. After it was dried, calcined at about 300°C, and then cooled to ambient/room temperature, an XRD spectrum was taken (not shown), which appeared to have features roughly similar to the equimolar nickel-tungsten oxide, as calcined.
- Oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI) was mixed together with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI) and heated to about 100°C to form a solution.
- the second sample of calcined Ni 0.75 WO 3.75 was likewise heated to about 100°C, and then an amount of the solution was used to simultaneously co-impregnate the organic components into/onto the sample, the amount being sufficient to attain a mole ratio of Ni 0.75 WO 3.75 to oleylamine of about 1:0.10 and to attain a mole ratio of Ni 0.75 WO 3.75 to oleic acid of about 1 :0.06.
- a third sample was prepared using a similar procedure to Comparative Example 1 , but adjusting the ingredients to provide a nickel-to-tungsten molar ratio of only about 0.5:1.
- the second sample of calcined Ni 0.5 WO 3.5 was likewise heated to about 100°C, and then an amount of the solution was used to simultaneously co-impregnate the organic components into/onto the sample, the amount being sufficient to attain a mole ratio of Ni 0.5 WO 3.5 to oleylamine of about 1:0.10 and to attain a mole ratio of Ni 0.5 WO 3.5 to oleic acid of about 1:0.06.
- This impregnated sample was dried in air in a drying furnace overnight at about 100°C. The sample was then placed in a box furnace, heated in air at about 0.5°C/min up to about 220°C, and held for about 4 hours at that temperature.
- a fourth sample was prepared using a similar procedure to Comparative Example 1 , but adjusting the ingredients to provide a nickel-to-tungsten molar ratio of about 1.2:1, followed by drying, calcination at about 300°C, and then cooling to ambient/room temperature.
- Oleylamine (70% technical grade, commercially available from Aldrich of Milwaukee, WI) was mixed together with oleic acid (90% technical grade, commercially available from Aldrich of Milwaukee, WI) and heated to about 100°C to form a solution.
- the second sample of calcined Ni 1.2 WO 4.2 was likewise heated to about 100°C, and then an amount of the solution was used to simultaneously co- impregnate the organic components into/onto the sample, the amount being sufficient to attain a mole ratio of Ni 1.2 WO 4.2 to oleylamine of about 1:0.10 and to attain a mole ratio of Ni 1.2 WO 4.2 to oleic acid of about 1:0.06.
- This impregnated sample was dried in air in a drying furnace overnight at about 100°C. The sample was then placed in a box furnace, heated in air at about 0.5°C/min up to about 220°C, and held for about 4 hours at that temperature.
- the HDN activity of the 0.75 Ni:W ratio catalyst still exhibited a modest increase, on a molar basis, due to the dual organic treatment, while the HDN activity of the 0.5 Ni:W ratio catalyst showed a decrease, on a molar basis, despite the dual organic treatment. Nevertheless, the equimolar Ni:W catalyst and the catalyst having an Ni:W ratio greater than 1 showed 70% or greater relative molar HDN activity.
- Ni:W ratios at or above 0.75 seem to be desirable, with about equimolar to somewhat above equimolar Ni:W ratios appearing to be particularly desirable on a relative molar activity basis.
- Example 40 Preparation of NiWO 4 //(oleylamine) 0.104 /oleic acid 0.06 /air 230°C
- a co-mixture of amine and acid is impregnated into the metal oxide component and converted into an amide in situ in the metal oxide component.
- NiWO 4 powder was prepared at pilot scale by heating nickel carbonate and tungstic acid at ⁇ 99°C (i.e. sub-hydrothermally) for 48 hours. The NiWO 4 powder was then composited with about 7% binder (a mixture of silica and clay) to form extrudates.
- 50 g of the NiWO 4 extrudates were placed in a small beaker and put in a box furnace at 100°C.
- Example 41 Preparation of NiWO 4 //pre-formed oa-ol ac amide
- the oleic acid and oleylamine are pre-reacted before they are impregnated into the metal oxide component.
- Nominally equimolar mixtures of oleylamine and oleic acid i.e. assuming they are 100% pure components were added together.
- oleylamine and 28.2 g of oleic acid both technical grade, Aldrich
- oleylamine and 28.2 g of oleic acid both technical grade, Aldrich
- the residual air that is left in the flask functions as the atmosphere.
- the flask is additionally open to the ambient atmosphere but no air is deliberately bubbled through the mixture.
- the temperature is raised at about 2°C/min to 175°C and held there for one hour.
- the product appears as a dark brown liquid when it is hot and it lightens up a bit when it solidifies.
- GC-MS identifies it as the C36 oleylamide.
- This amide was impregnated in a similar way as the acid-amine mixture, with both the extrudates and amide held at 100°C just before the impregnation.
- the amount of amide impregnated was 0.20 g of amide per gram of NiWO 4 extrudate or 0.17 g amide/g NiWO 4 .
- the samples are then heated at 0.5°C/min to the final temperature, in most cases 220°C or 230°C, in a box furnace with stagnant air, held for 4 hours and then cooled down to room temperature.
- Two hydroprocessing runs were made to compare the HDN performance of the catalysts prepared by in situ formation of the amide and by ex situ preparation prior to impregnation.
- the first run was made over 24 days with a VGO feed with 1683 ppm N using the catalyst with the nominal 2.2:1 acid:amine ratio.
- the pre-formed amide is superior in its denitrogenation activity.
Abstract
La présente invention concerne un précurseur de catalyseur d'hydrotraitement fabriqué en imprégnant un composant d'oxyde métallique comprenant au moins un métal du groupe 8 du tableau périodique et au moins un métal des groupes 8 à 10 du tableau périodique avec un amide formé à partir d'un premier composé organique contenant au moins un groupe amine, et d'un second composé organique contenant au moins un groupe d'acide carboxylique. L'imprégnation est suivie par un traitement thermique permettant de former in situ une insaturation générée en supplément de celle dans les deux composés organiques. Le précurseur de catalyseur est sulfuré afin de former un catalyseur d'hydrotraitement sulfuré actif.
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CN113663682A (zh) * | 2021-07-12 | 2021-11-19 | 西南林业大学 | 一种非负载介孔加氢脱氧催化剂及其制备和应用 |
CN114432869A (zh) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | 一种燃煤烟气的处理方法及装置 |
US20230095045A1 (en) * | 2021-09-30 | 2023-03-30 | ExxonMobil Technology and Engineering Company | Low pressure hydroprocessing catalyst |
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