CA2081130C - Hydroprocessing catalyst composition - Google Patents
Hydroprocessing catalyst composition Download PDFInfo
- Publication number
- CA2081130C CA2081130C CA002081130A CA2081130A CA2081130C CA 2081130 C CA2081130 C CA 2081130C CA 002081130 A CA002081130 A CA 002081130A CA 2081130 A CA2081130 A CA 2081130A CA 2081130 C CA2081130 C CA 2081130C
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- catalysts
- weight percent
- feedstock
- conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 239000000203 mixture Substances 0.000 title claims description 8
- 239000011148 porous material Substances 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000002459 porosimetry Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- -1 VIB metals Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/647—
-
- B01J35/66—
Abstract
Hydroprocessing catalysts which comprise alumina and Group VIB and VIII metal components having a desired pore size/volume distribution and high surface area, i.e. above 330 m2/g.
Description
_2_ Alumina Supported Group VIB and/ar Group VIII Metal Hydroprocessing Catalyst Compositions The present invention relates to improved hydroprocessing catalysts, and in particular to alumina-Group VIB/VIII metal catalysts that are used in the hydrocracking(HC)/hydrodesulfurization(HDS)/
hydrodenitrogenation(HDN) and hydrodemetallization(HDM) of heavy hydrocarbon feedstocks that contain high levels of asphaltenes, sulfur, nitrogen and metal compounds as well as Conradson Carbon.
Many alumina supported Group VIB/VIII metal containing catalysts have been developed for the hydroprocessing of hydrocarbons. References which disclose a wide variety of hydroprocessing catalysts are as follow:
U.S. 3,622,500 3,692,698 3,770,617 3,876,523 4,048,060 4,051,021 4,066,574 4,082,695 4,089,774 4,113,661 4,297,242 4,306,965 4,309,278 4, 328, 7.27 4,341,625 4,395,328 4,648,963 4,652,545 4,729,826 4,732,886 4,738,994 4,746,419 4,941,964 4,945,079 4,981,832 5,009,771 20~1I30 The above-noted references disclose hydroprocessing catalysts which possess pore volume and pore size distribution characteristics that optimize the performance of the catalysts in various hydroprocessing operations, including HC, HDS, HDM and HDN.
While prior art catalysts having specific pore volume/pore size distribution characteristics are effective for the hydroprocessing of various high molecular weight hydrocarbon feedstocks, it is observed that catalysts which are effective for the processing of feedstocks that contain large quantities of asphaltenes frequently include a macro-pore structure that permits the entry of deactivating metal compounds. In addition, catalysts which are used in the ebullating bed hydrocracking of residual hydrocarbons should possess a high surface area that provides a maximum reactive surface for a given volume of catalyst.
It is therefore an object of the present invention to provide improved alumina supported, Group VIB/VIII metal containing hydroprocessing catalysts.
It is a further object to provide hydroprocessing catalysts which combine a desired pore volume/pore size distribution with high surface area.
It is a further object to provide a hydroprocessing catalyst which is particularly useful for the HC, HDS, HDM and HDN of residual hydrocarbon feedstocks that contain large quantities of asphaltenes.
These and still further objects of our invention shall be readily apparent to one skilled-in-the-art from the following detailed description, specific 2~~~I30 examples and drawings: wherein the Figures 1 to 9 are graphic representations of data which illustrate the Conversion, Conradson Carbon Reduction, Sulfur Reduction, Nitrogen Reduction and Ni & V Reduction capabilities of catalysts of the present invention.
Broadly, our invention contemplates hydroprocessing catalysts which comprise an alumina support and effective amounts of Group VIB and/or Group VIII metals, wherein the catalyst is characterized by a high surface area, and a pore structure in which the pore volume in pores greater than 250 ~ diameter is less than 0.25 cc/g.
More specifically, we have invented an improved hydroprocessing catalyst which is particularly active for the HC, HDS, HDN and HDM of heavy residual hydrocarbon feedstocks which comprises an alumina support having about 5 to 25 weight percent and preferably 12 to 15 weight percent Group VIB metal (preferably W or Mo) and 0 to 10 weight percent and preferably 3 to 5 weight percent Group VIII metal (preferably Ni or Co), expressed as the oxides, wherein the catalyst is particularly characterized by a surface area of above about 330 m2/g, and preferably 330 to 380 m2/g; a total pore volume above 0.5 cc/g, and preferably 0.6 to 0.9 cc/g as determined by mercury porosimetry in pores above 30 ~ diameter up to about 300,000 ~ diameter; and a pore size distribution wherein the pore volume in pores greater than 250 ~ is less than 0.25 cc/g, and preferably 0.01 to 0.25 cc/g.
The catalysts of the present invention are prepared as follows:
1) A particulate alumina powder is thoroughly mixed with about 7 to 22 weight percent water, or 20~I.t 3p preferably a dilute aqueous solution of nitric acid which contains 0.5 to 3.0 weight percent HN03.
2) The mixture ~.s then combined with the desired quantity of Group VIB and Group VIII metal salt solutions such as ammonium dimolybdate and nickel nitrate.
hydrodenitrogenation(HDN) and hydrodemetallization(HDM) of heavy hydrocarbon feedstocks that contain high levels of asphaltenes, sulfur, nitrogen and metal compounds as well as Conradson Carbon.
Many alumina supported Group VIB/VIII metal containing catalysts have been developed for the hydroprocessing of hydrocarbons. References which disclose a wide variety of hydroprocessing catalysts are as follow:
U.S. 3,622,500 3,692,698 3,770,617 3,876,523 4,048,060 4,051,021 4,066,574 4,082,695 4,089,774 4,113,661 4,297,242 4,306,965 4,309,278 4, 328, 7.27 4,341,625 4,395,328 4,648,963 4,652,545 4,729,826 4,732,886 4,738,994 4,746,419 4,941,964 4,945,079 4,981,832 5,009,771 20~1I30 The above-noted references disclose hydroprocessing catalysts which possess pore volume and pore size distribution characteristics that optimize the performance of the catalysts in various hydroprocessing operations, including HC, HDS, HDM and HDN.
While prior art catalysts having specific pore volume/pore size distribution characteristics are effective for the hydroprocessing of various high molecular weight hydrocarbon feedstocks, it is observed that catalysts which are effective for the processing of feedstocks that contain large quantities of asphaltenes frequently include a macro-pore structure that permits the entry of deactivating metal compounds. In addition, catalysts which are used in the ebullating bed hydrocracking of residual hydrocarbons should possess a high surface area that provides a maximum reactive surface for a given volume of catalyst.
It is therefore an object of the present invention to provide improved alumina supported, Group VIB/VIII metal containing hydroprocessing catalysts.
It is a further object to provide hydroprocessing catalysts which combine a desired pore volume/pore size distribution with high surface area.
It is a further object to provide a hydroprocessing catalyst which is particularly useful for the HC, HDS, HDM and HDN of residual hydrocarbon feedstocks that contain large quantities of asphaltenes.
These and still further objects of our invention shall be readily apparent to one skilled-in-the-art from the following detailed description, specific 2~~~I30 examples and drawings: wherein the Figures 1 to 9 are graphic representations of data which illustrate the Conversion, Conradson Carbon Reduction, Sulfur Reduction, Nitrogen Reduction and Ni & V Reduction capabilities of catalysts of the present invention.
Broadly, our invention contemplates hydroprocessing catalysts which comprise an alumina support and effective amounts of Group VIB and/or Group VIII metals, wherein the catalyst is characterized by a high surface area, and a pore structure in which the pore volume in pores greater than 250 ~ diameter is less than 0.25 cc/g.
More specifically, we have invented an improved hydroprocessing catalyst which is particularly active for the HC, HDS, HDN and HDM of heavy residual hydrocarbon feedstocks which comprises an alumina support having about 5 to 25 weight percent and preferably 12 to 15 weight percent Group VIB metal (preferably W or Mo) and 0 to 10 weight percent and preferably 3 to 5 weight percent Group VIII metal (preferably Ni or Co), expressed as the oxides, wherein the catalyst is particularly characterized by a surface area of above about 330 m2/g, and preferably 330 to 380 m2/g; a total pore volume above 0.5 cc/g, and preferably 0.6 to 0.9 cc/g as determined by mercury porosimetry in pores above 30 ~ diameter up to about 300,000 ~ diameter; and a pore size distribution wherein the pore volume in pores greater than 250 ~ is less than 0.25 cc/g, and preferably 0.01 to 0.25 cc/g.
The catalysts of the present invention are prepared as follows:
1) A particulate alumina powder is thoroughly mixed with about 7 to 22 weight percent water, or 20~I.t 3p preferably a dilute aqueous solution of nitric acid which contains 0.5 to 3.0 weight percent HN03.
2) The mixture ~.s then combined with the desired quantity of Group VIB and Group VIII metal salt solutions such as ammonium dimolybdate and nickel nitrate.
3) The metal containing aiumina mixture which contains from about 50 to 56 weight percent moisture is then formed into catalyst particles having a desired shape and size, preferably by extrusion.
4) The formed catalyst particles are dried at a temperature of about 110 to 150°C, and then calcined at a temperature of 500 to 600°C for about one to two hours.
The particulate alumina powder used in the practice of our invention is commercially available from the Davison Chemical Division of W. R. Grace &
Co.-Conn as Grade SRA-46 HR. The preferred alumina has an average particulate size of about 15 to 25 ~cm, an X-ray diffraction pattern which indicates the presence of pseudoboehmite and the absence of Beta alumina trihydrate. The aluminas may be obtained by reacting aqueous solutions of sodium aluminate and alumina sulfate in accordance with the teachings of U.S. 4,154,812.
The catalysts of our invention typically have a density of about 0.8 to 1.1 g/cc and a particle diameter of about 0.8 to 1.6 mm. These catalysts may be used in the hydroprocessing of hydrocarbon feedstocks at temperatures of 350 to 500°C, pressures of 80 to 200 atm, HZ consumption of 500 to 5000 standard cubic feet per barrel, using catalyst/feed weight ratios of 0.2 to 1.8.
Brief description of Figures Figure 1 - Figure 1 is a graphical representation of percentage conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume.
Catalyst of smaller macropores provided higher conversion.
Figure 2 - Figure 2 is a graphical representation of percentage Conradson conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume. Catalyst of smaller macrospores provided higher Conradson conversion.
Figure 3 - Figure 3 is a graphical representation of percentage sulfur conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume. Catalysts of smaller macropores provided higher sulfur conversion.
Figure 4- Figure 4 is a graphical representation of percentage nitrogen conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume. Catalyst of smaller macropores provided higher nitrogen conversion.
Figure 5 - Figure 5 is a graphical representation of percentage nickel and vanadium conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume. Catalyst of smaller macropores provided higher conversion activity for catalyst A to B but then decrease for catalyst C.
Figure 6 - Figure 6 is a graphical representation of percentage conversion as a function of barrels of oil (feedstock) per pound of catalyst at 770° FI0.5 LHSV
and at 800° F/0.8 LHSV. The catalyst of lower macropore volume (Catalyst D) showed high activity for conversion.
Figure 7 - Figure 7 is a graphical representation of percentage Conradson conversion as a function of barrels of oil (feedstock) per pound of catalyst at 770° F/0.5 LHSV and at 800° F/0.8 LHSV. The catalyst of lower macropore volume (Catalyst D) showed high activity for Cvnradson conversion.
Figure 8 - Figure 8 is a graphical representation of percentage sulfur conversion as a function of barrels of oil (feedstack) per pound of catalyst at 770°
F/0.5 LHSV and at 800° F/0.8 LHSV. The catalyst of lower macropore volume (Catalyst D) showed high activity for sulfur conversion.
Figure 9 - Figure 9 is a graphical representation of percentage nickel and vanadium conversion as a function of barrels of oil (feedstock) per pound of catalyst at 770° F/0.5 LHSV and at 800° F/0.8 LHSV. The catalyst of lower macropore volume (Catalyst D) showed high activity for nickel and vanadium conversion.
Having described the basic aspects of our invention, the. following Examples are set forth to illustrate specific embodiments thereof.
Exa~np 1g 1 This example describes the preparation of three catalysts of the present invention (Catalysts B, C &
D), and a comparison prior art catalyst (Catalyst A).
Catalysts B, C, & D are made using the same equipment and similar process steps. Thirty 1b. of pseudoboehmite alumina powder (Davison Chemical Grade SRA 46R) were loaded into an R-7 model Eirich mixer.
2600 and 1820 g respectively of water were mixed with 34 g of nitric acid for catalysts C and D. Catalyst B
was made using 1820 g of water and no nitric acid.
The mixture was mixed for 3 minutes on low speed.
An ammonium dimolybdate solution was prepared by dissolving 1900 g of ammonium dimolybdate crystals into 4400 g of 120°F deionized water. The 6300 g of this 25.3 wt.% (as Moo3) ammonium dimolybdate solution were added to the mixer and mixed for 2 minutes on low. Commercial nickel nitrate solution was diluted with water to 1.33 specific gravity (13.0 wt.% Ni.O).
3120 g of this diluted nickel nitrate solution were added to the mixer and mixed 2 minutes on low. The mixer was run for a final mix cycle on a high setting for 5 minutes.
The resulting mixed powder was extruded through a 4" Bonnot single auger type extruder. A die with nominal 1/32" holes was used to form the catalysts.
Following extrusion the formed catalysts were dried overnight in a 1?roctor and Schwartz static tray dryer at about 250°F. The finished catalyst was calcined in a muffle furnace at 1000°F bed temperature for 2 hours.
Comparison catalyst A, was prepared by a similar procedure used for the preparation of catalysts B, C &
D with the following differences: (1) Da~ison Chemical pseudoboehmite alumina powder Grade 'VFA was used; (2) no acid was added to the water; and (3) water and ammonium dimolybdate solution were added together with no mix cycle in between their additions.
The chemical and physical properties of SRA 46HR
and VFA alumina powder are set forth in Table I(a) below:
TABLE T(a~
Properties of Alumina Powders ~SRA 46HR VFA
Chemical:
A1203 (wt. %) >99. 5 >99. 5 H20 (wt. %) 28 , 28 Na20 (wt.%) 0.08 0.10 SO4 (wt.%) 0.3 0.3 Physical:
Average Particle Size ( 18 18 ft) Surface Area (m2/g) 300 330 *Total Pore Volume cc/g) 0.92 0.90 ~
Pore Volume > 250 0.20 0.30 (cc/g) X-Ray Diffraction:
100% Alpha Alumina Monohydrate (pseudoboehmite) * As determined by mercury porisimetry in pores 30 to 150o A diameter.
The properties of Catalysts A, B, C and D are set !
forth in Table I(b).
J
N
H~
r-'~"'1 C~1 ~
C~
01 N t~
O
.
.
O
O
U
N ~
~ O
~ ~ oW 0 U .-~
~y ~"~ ~
M
,. O
.i O
U
W
H .1J
H N
~" , W r p~ . ,d ~ N
~i ~
~ ~
O .,.~ ri '~ M O G~
H
W W U
a ~' a .u Qe r; i O
'1 r-1 N h h ~ N
U rt3 c~ ~ ~
r~ O O
rt U
w o N
_ O .,-1 ~T
O N
O rt N
v b A
N (p n U U H
H ~ rtiU td O
O ~ ~
rt3 f.aO c~
U '~ ~ H /v ~:
' N
H
H U W
W
Example 2 The test procedures and conditions used to evaluate Catalysts A, B, C & U were as follows:
1. 75 cc of catalyst is charged to the reactor.
2. The catalyst is heated to 30onF in nitrogen.
3. At 300°F, the nitrogen is replaced with a gas consisting of 6 vol % HZS and 94 vol % HZ, at a pressure of one atmosphere and at a flow rate of~30 liters per hour. After 3 hours at 300°F, the temperature is raised to 600°F over a 3 hour period.
4. At 600°F, the 6% H2S/94% H2 gas is replaced with 100% H2, and the unit is pressured with H2 to 2000 psig. The HZ flow rate is set at 3000 SCF/bbl of feedstock when operating at a Liquid Hourly Space Velocity (LHSV) of 0.5, and set at 4800 SCF/bbl of feedstock when operating at a LHSV of 0.8.
The particulate alumina powder used in the practice of our invention is commercially available from the Davison Chemical Division of W. R. Grace &
Co.-Conn as Grade SRA-46 HR. The preferred alumina has an average particulate size of about 15 to 25 ~cm, an X-ray diffraction pattern which indicates the presence of pseudoboehmite and the absence of Beta alumina trihydrate. The aluminas may be obtained by reacting aqueous solutions of sodium aluminate and alumina sulfate in accordance with the teachings of U.S. 4,154,812.
The catalysts of our invention typically have a density of about 0.8 to 1.1 g/cc and a particle diameter of about 0.8 to 1.6 mm. These catalysts may be used in the hydroprocessing of hydrocarbon feedstocks at temperatures of 350 to 500°C, pressures of 80 to 200 atm, HZ consumption of 500 to 5000 standard cubic feet per barrel, using catalyst/feed weight ratios of 0.2 to 1.8.
Brief description of Figures Figure 1 - Figure 1 is a graphical representation of percentage conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume.
Catalyst of smaller macropores provided higher conversion.
Figure 2 - Figure 2 is a graphical representation of percentage Conradson conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume. Catalyst of smaller macrospores provided higher Conradson conversion.
Figure 3 - Figure 3 is a graphical representation of percentage sulfur conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume. Catalysts of smaller macropores provided higher sulfur conversion.
Figure 4- Figure 4 is a graphical representation of percentage nitrogen conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume. Catalyst of smaller macropores provided higher nitrogen conversion.
Figure 5 - Figure 5 is a graphical representation of percentage nickel and vanadium conversion at various rates of feed oil per pound of catalyst using three catalysts of varying macropore volume. Catalyst of smaller macropores provided higher conversion activity for catalyst A to B but then decrease for catalyst C.
Figure 6 - Figure 6 is a graphical representation of percentage conversion as a function of barrels of oil (feedstock) per pound of catalyst at 770° FI0.5 LHSV
and at 800° F/0.8 LHSV. The catalyst of lower macropore volume (Catalyst D) showed high activity for conversion.
Figure 7 - Figure 7 is a graphical representation of percentage Conradson conversion as a function of barrels of oil (feedstock) per pound of catalyst at 770° F/0.5 LHSV and at 800° F/0.8 LHSV. The catalyst of lower macropore volume (Catalyst D) showed high activity for Cvnradson conversion.
Figure 8 - Figure 8 is a graphical representation of percentage sulfur conversion as a function of barrels of oil (feedstack) per pound of catalyst at 770°
F/0.5 LHSV and at 800° F/0.8 LHSV. The catalyst of lower macropore volume (Catalyst D) showed high activity for sulfur conversion.
Figure 9 - Figure 9 is a graphical representation of percentage nickel and vanadium conversion as a function of barrels of oil (feedstock) per pound of catalyst at 770° F/0.5 LHSV and at 800° F/0.8 LHSV. The catalyst of lower macropore volume (Catalyst D) showed high activity for nickel and vanadium conversion.
Having described the basic aspects of our invention, the. following Examples are set forth to illustrate specific embodiments thereof.
Exa~np 1g 1 This example describes the preparation of three catalysts of the present invention (Catalysts B, C &
D), and a comparison prior art catalyst (Catalyst A).
Catalysts B, C, & D are made using the same equipment and similar process steps. Thirty 1b. of pseudoboehmite alumina powder (Davison Chemical Grade SRA 46R) were loaded into an R-7 model Eirich mixer.
2600 and 1820 g respectively of water were mixed with 34 g of nitric acid for catalysts C and D. Catalyst B
was made using 1820 g of water and no nitric acid.
The mixture was mixed for 3 minutes on low speed.
An ammonium dimolybdate solution was prepared by dissolving 1900 g of ammonium dimolybdate crystals into 4400 g of 120°F deionized water. The 6300 g of this 25.3 wt.% (as Moo3) ammonium dimolybdate solution were added to the mixer and mixed for 2 minutes on low. Commercial nickel nitrate solution was diluted with water to 1.33 specific gravity (13.0 wt.% Ni.O).
3120 g of this diluted nickel nitrate solution were added to the mixer and mixed 2 minutes on low. The mixer was run for a final mix cycle on a high setting for 5 minutes.
The resulting mixed powder was extruded through a 4" Bonnot single auger type extruder. A die with nominal 1/32" holes was used to form the catalysts.
Following extrusion the formed catalysts were dried overnight in a 1?roctor and Schwartz static tray dryer at about 250°F. The finished catalyst was calcined in a muffle furnace at 1000°F bed temperature for 2 hours.
Comparison catalyst A, was prepared by a similar procedure used for the preparation of catalysts B, C &
D with the following differences: (1) Da~ison Chemical pseudoboehmite alumina powder Grade 'VFA was used; (2) no acid was added to the water; and (3) water and ammonium dimolybdate solution were added together with no mix cycle in between their additions.
The chemical and physical properties of SRA 46HR
and VFA alumina powder are set forth in Table I(a) below:
TABLE T(a~
Properties of Alumina Powders ~SRA 46HR VFA
Chemical:
A1203 (wt. %) >99. 5 >99. 5 H20 (wt. %) 28 , 28 Na20 (wt.%) 0.08 0.10 SO4 (wt.%) 0.3 0.3 Physical:
Average Particle Size ( 18 18 ft) Surface Area (m2/g) 300 330 *Total Pore Volume cc/g) 0.92 0.90 ~
Pore Volume > 250 0.20 0.30 (cc/g) X-Ray Diffraction:
100% Alpha Alumina Monohydrate (pseudoboehmite) * As determined by mercury porisimetry in pores 30 to 150o A diameter.
The properties of Catalysts A, B, C and D are set !
forth in Table I(b).
J
N
H~
r-'~"'1 C~1 ~
C~
01 N t~
O
.
.
O
O
U
N ~
~ O
~ ~ oW 0 U .-~
~y ~"~ ~
M
,. O
.i O
U
W
H .1J
H N
~" , W r p~ . ,d ~ N
~i ~
~ ~
O .,.~ ri '~ M O G~
H
W W U
a ~' a .u Qe r; i O
'1 r-1 N h h ~ N
U rt3 c~ ~ ~
r~ O O
rt U
w o N
_ O .,-1 ~T
O N
O rt N
v b A
N (p n U U H
H ~ rtiU td O
O ~ ~
rt3 f.aO c~
U '~ ~ H /v ~:
' N
H
H U W
W
Example 2 The test procedures and conditions used to evaluate Catalysts A, B, C & U were as follows:
1. 75 cc of catalyst is charged to the reactor.
2. The catalyst is heated to 30onF in nitrogen.
3. At 300°F, the nitrogen is replaced with a gas consisting of 6 vol % HZS and 94 vol % HZ, at a pressure of one atmosphere and at a flow rate of~30 liters per hour. After 3 hours at 300°F, the temperature is raised to 600°F over a 3 hour period.
4. At 600°F, the 6% H2S/94% H2 gas is replaced with 100% H2, and the unit is pressured with H2 to 2000 psig. The HZ flow rate is set at 3000 SCF/bbl of feedstock when operating at a Liquid Hourly Space Velocity (LHSV) of 0.5, and set at 4800 SCF/bbl of feedstock when operating at a LHSV of 0.8.
5. The catalyst bed temperature is raised to a temperature 50°F below the desired operating temperature. The feedstock described in Table I(c) is then introduced at a rate of 0.5 LHSV ox 0.8 LHSV.
Table I(cl API Gravity 4.5 Amount boiling above ~ooo~F (538°C) (vol.. %) 9i Conradson Carbon Residue (wt.%) 23.0 Nitrogen (wt.%) 0.45 Sulfur (wt. %) 5, 5 Nickel + Vanadium (ppm) 206 Pentane Insolubles (wt.%) 26.6 Toluene Insolubles (wt.%) 0.05 6. After 24 hours on feedstock, the temperature is raised to the desired operating temperature.
Table I(cl API Gravity 4.5 Amount boiling above ~ooo~F (538°C) (vol.. %) 9i Conradson Carbon Residue (wt.%) 23.0 Nitrogen (wt.%) 0.45 Sulfur (wt. %) 5, 5 Nickel + Vanadium (ppm) 206 Pentane Insolubles (wt.%) 26.6 Toluene Insolubles (wt.%) 0.05 6. After 24 hours on feedstock, the temperature is raised to the desired operating temperature.
7. The liquid product is collected periodically and analyzed to determine the following:
(Vol% of feedstock boiling above 1000°F -Vol.% Conversion = Vol % of product boil"_~,n_g above 1000°F1 X
Vol % of feedstock boiling above 1000°F
(Wt% Conradsan carbon residue in feedstock - wt% Conradson Wt.% Conradson Carbon Reduction = Carbon residue in product 1 X 100 Wt% Conradeon carbon residue in feedstock (Wt% Sulfur in feedstock -ld Wt,% Sulfur Reduction = Wt% sulfgr~in product] X 100 Wt% Sulfur in feedstock (Wt% Ni+V in feedstock -Wt.% Ni+V Reduction = WT% Ni+V iQ~raduct L X 100 Wt% Ni+V in feedstock 1~ (Wt% Nitrogen in feedstack -Wt.% Nitrogen Reduction = Wt% Nitroaen in product 1 X 100 Wt% Nitrogen in feedstock Example 3 The test procedure described in Example 2 was used to test catalysts A, B and C, described in Example No. 1.
Catalysts A, B and C were tested at a temperature of 800°F and a liquid hourly space velocity of 0.8.
The test runs were carried out for a total of 22 days so that the catalysts would be subjected to about 2.0 barrels of feedstock per pound of catalyst.
The test results show that as the macropore volume (volume in pores greater than 250 ~) decreases from Catalyst A to Catalyst B to Catalyst C, the activity of the catalysts increases for % Conversion, % Conradson carbon reduction, % Sulfur reduction, and % Nitrogen reduction. For Ni+v reduction, the activity increases from Catalyst A to Catalyst B, but then decreases for Catalyst C.
The test results are Shawn in Figures 1 through 5 as a function of barrels of oil (feedstock) per pound of catalyst. Additionally, the data in Figures 1 through 5 were averaged for the range of 0.4 to 2.0 barrels of oil (feedstock) per pound of catalyst. The averages are given in Table zT.
.,., z N
I ~ N ~ ~ 01 ;
. N
-U
w w ~' ~ ~ +~ ~ ~ c p x ~o a 4"i td A
CO O
G ~
N
4 . U C~k ~ d1 y D
O r7 C1 ~ cr O O
O ~ +1 ~
N
d' O
W U 00 d' N h t~! Qi O da N
td ,y' 11j U
N
N
N
., 4 W . U O
C
N N C~If :ra 5r '~"' N
ri r~i r-i a ro U c~ U
Example 4 The test procedure described in Example 2 was used to test catalysts A and D described in Example 1.
Catalysts A and D were tested at a temperature of 770°F and a LHSV of 0.5 for eleven days. The temperature and the LHSV were then raised to 800°F and 0.8 LHSV. The test run was continued for four days at those conditions, then terminated.
At both sets of test conditions, the results show that Catalyst D, which has a much lower macropore volume (volume in pores greater than 250 ~) than Catalyst A, is much more active than Catalyst A for conversion, Conradson carbon reduction, sulfur reduction and nitrogen reduction. Catalyst D, however, was less active far Ni+V reduction.
The test results are shown in Figures 6 through 9 as a function of barrels of oil (feedstock) per pound of catalyst. (N2 Reduction Data not plotted.) Additionally, the data in Figures 6 through 9 were averaged for the range of 0.4 to 0.9 barrel of oil (feedstock) per pound of catalyst at 770°F and 0.5 LHSV. The data was also averaged for the range of 0.9 to 1.3 barrels of oil (feedstock) per pound of catalyst at 800°F and 0.8 LHSV. These averages are given in Table III.
N
~ ~ a >
-I- M Q M
~a z U
~n zP ~ ~1 M
a '~
o A
W U
~
~
~
f1 O t fd ta'In 01 r~
r-1 ~ ~I v0 ~-1r.
w Gl O
N
>
O ~
W
.~.~
O
O O
H
~
~
( M r-1In M
.
,-1 V .-I
O I
a, >
Q M ~ 0 O .- t!
~t 1 O
w H
H
H N
N
W
a i -- r U
rt U
a c n 4.1 !~ O
O
~
o ~o ~ N
z~ 1 N
o ~; ~
~s y w ~
ca n (C a, M 00 .-1 n-1 ri '.'' c~y o '-,w >
a~
o ~w,~
o .~
.-I
O
I
U M ~ In (31 .N
O
t V' >
~ 01 d' M
O N r-I~
U
~1 ~C Ca ~i it r +a +s rtr r"
U C>
(Vol% of feedstock boiling above 1000°F -Vol.% Conversion = Vol % of product boil"_~,n_g above 1000°F1 X
Vol % of feedstock boiling above 1000°F
(Wt% Conradsan carbon residue in feedstock - wt% Conradson Wt.% Conradson Carbon Reduction = Carbon residue in product 1 X 100 Wt% Conradeon carbon residue in feedstock (Wt% Sulfur in feedstock -ld Wt,% Sulfur Reduction = Wt% sulfgr~in product] X 100 Wt% Sulfur in feedstock (Wt% Ni+V in feedstock -Wt.% Ni+V Reduction = WT% Ni+V iQ~raduct L X 100 Wt% Ni+V in feedstock 1~ (Wt% Nitrogen in feedstack -Wt.% Nitrogen Reduction = Wt% Nitroaen in product 1 X 100 Wt% Nitrogen in feedstock Example 3 The test procedure described in Example 2 was used to test catalysts A, B and C, described in Example No. 1.
Catalysts A, B and C were tested at a temperature of 800°F and a liquid hourly space velocity of 0.8.
The test runs were carried out for a total of 22 days so that the catalysts would be subjected to about 2.0 barrels of feedstock per pound of catalyst.
The test results show that as the macropore volume (volume in pores greater than 250 ~) decreases from Catalyst A to Catalyst B to Catalyst C, the activity of the catalysts increases for % Conversion, % Conradson carbon reduction, % Sulfur reduction, and % Nitrogen reduction. For Ni+v reduction, the activity increases from Catalyst A to Catalyst B, but then decreases for Catalyst C.
The test results are Shawn in Figures 1 through 5 as a function of barrels of oil (feedstock) per pound of catalyst. Additionally, the data in Figures 1 through 5 were averaged for the range of 0.4 to 2.0 barrels of oil (feedstock) per pound of catalyst. The averages are given in Table zT.
.,., z N
I ~ N ~ ~ 01 ;
. N
-U
w w ~' ~ ~ +~ ~ ~ c p x ~o a 4"i td A
CO O
G ~
N
4 . U C~k ~ d1 y D
O r7 C1 ~ cr O O
O ~ +1 ~
N
d' O
W U 00 d' N h t~! Qi O da N
td ,y' 11j U
N
N
N
., 4 W . U O
C
N N C~If :ra 5r '~"' N
ri r~i r-i a ro U c~ U
Example 4 The test procedure described in Example 2 was used to test catalysts A and D described in Example 1.
Catalysts A and D were tested at a temperature of 770°F and a LHSV of 0.5 for eleven days. The temperature and the LHSV were then raised to 800°F and 0.8 LHSV. The test run was continued for four days at those conditions, then terminated.
At both sets of test conditions, the results show that Catalyst D, which has a much lower macropore volume (volume in pores greater than 250 ~) than Catalyst A, is much more active than Catalyst A for conversion, Conradson carbon reduction, sulfur reduction and nitrogen reduction. Catalyst D, however, was less active far Ni+V reduction.
The test results are shown in Figures 6 through 9 as a function of barrels of oil (feedstock) per pound of catalyst. (N2 Reduction Data not plotted.) Additionally, the data in Figures 6 through 9 were averaged for the range of 0.4 to 0.9 barrel of oil (feedstock) per pound of catalyst at 770°F and 0.5 LHSV. The data was also averaged for the range of 0.9 to 1.3 barrels of oil (feedstock) per pound of catalyst at 800°F and 0.8 LHSV. These averages are given in Table III.
N
~ ~ a >
-I- M Q M
~a z U
~n zP ~ ~1 M
a '~
o A
W U
~
~
~
f1 O t fd ta'In 01 r~
r-1 ~ ~I v0 ~-1r.
w Gl O
N
>
O ~
W
.~.~
O
O O
H
~
~
( M r-1In M
.
,-1 V .-I
O I
a, >
Q M ~ 0 O .- t!
~t 1 O
w H
H
H N
N
W
a i -- r U
rt U
a c n 4.1 !~ O
O
~
o ~o ~ N
z~ 1 N
o ~; ~
~s y w ~
ca n (C a, M 00 .-1 n-1 ri '.'' c~y o '-,w >
a~
o ~w,~
o .~
.-I
O
I
U M ~ In (31 .N
O
t V' >
~ 01 d' M
O N r-I~
U
~1 ~C Ca ~i it r +a +s rtr r"
U C>
Claims (7)
1. A catalyst comprising alumina having catalytically effective amount of a metal selected from Group VIB metals, Group VIII metals and mixtures thereof, said catalyst having a surface area greater than 330 m2/g, a total pore volume above 0.5 cc/g as determined by mercury porosimetry, and less than 0.25 cc/g pore volume in pores greater than 250 .ANG. diameter.
2. The catalyst of claim 1 wherein the surface area ranges from 330 to 380 m2/g.
3. The catalyst of claim 1 wherein the total pore volume ranges from 0.6 to 0.9 cc/g.
4. The catalyst of claim 1 wherein said metals are Mo and Ni.
5. The catalyst of claim 1 which contains 5 to 25 weight percent Mo and 0 to 10 weight percent Ni, expressed as the oxides.
6. A method for the hydroprocessing of hycrocarbons which comprises reacting a hydrocarbon feedstock and hydrogen at a temperature of 350 to 500 °C in the presence of the catalyst of claim 1.
7. The method of claim 6 wherein said feedstock comprises a residuum feedstock which contains 3 to 7 weight percent S, 0.3 to 0.7 weight percent N, 100 to 500 ppm Ni+V, and 10 to 30 weight percent Conradson Carbon residue, and up to above 40 weight percent asphaltenes.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US783,067 | 1991-10-25 | ||
US07/783,067 US5192734A (en) | 1991-10-25 | 1991-10-25 | Hydroprocessing catalyst composition |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2081130A1 CA2081130A1 (en) | 1993-04-26 |
CA2081130C true CA2081130C (en) | 2004-01-20 |
Family
ID=25128066
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002081130A Expired - Lifetime CA2081130C (en) | 1991-10-25 | 1992-10-22 | Hydroprocessing catalyst composition |
Country Status (2)
Country | Link |
---|---|
US (2) | US5192734A (en) |
CA (1) | CA2081130C (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5817594A (en) * | 1994-11-03 | 1998-10-06 | Shell Oil Company | Catalyst and hydrotreating process |
JP3378416B2 (en) * | 1995-08-25 | 2003-02-17 | 新日本石油株式会社 | Desulfurization method of catalytic cracking gasoline |
CN1059696C (en) * | 1995-12-11 | 2000-12-20 | 中国石化乌鲁木齐石油化工总厂 | Residual oil-refining modification process |
PL199651B1 (en) * | 1999-02-12 | 2008-10-31 | Johnson Matthey Plc | Nickel catalysts on transition alumina |
US6841512B1 (en) * | 1999-04-12 | 2005-01-11 | Ovonic Battery Company, Inc. | Finely divided metal catalyst and method for making same |
JP2003171671A (en) * | 2000-06-08 | 2003-06-20 | Japan Energy Corp | Method for hydrogenation refining of heavy oil |
US6870014B2 (en) * | 2000-07-03 | 2005-03-22 | Basf Aktiengesellschaft | Catalyst and method for producing polytetrahydrofurane |
JP4638610B2 (en) * | 2001-01-05 | 2011-02-23 | 日本ケッチェン株式会社 | Hydrotreating catalyst and hydrotreating method |
JP4612229B2 (en) * | 2001-06-08 | 2011-01-12 | 日本ケッチェン株式会社 | Catalyst for hydrotreating heavy hydrocarbon oil and hydrotreating method |
AU2003207232A1 (en) * | 2002-02-06 | 2003-09-02 | Japan Energy Corporation | Method for preparing hydrogenation purification catalyst |
US6830725B2 (en) * | 2003-04-01 | 2004-12-14 | Texaco Ovonic Battery Systems, Llc | Hydrogen storage alloys having a high porosity surface layer |
US20050109674A1 (en) * | 2003-11-20 | 2005-05-26 | Advanced Refining Technologies Llc | Hydroconversion catalysts and methods of making and using same |
US7390766B1 (en) * | 2003-11-20 | 2008-06-24 | Klein Darryl P | Hydroconversion catalysts and methods of making and using same |
US7560412B2 (en) * | 2004-08-14 | 2009-07-14 | Sud-Chemie Inc. | Fluid/slurry bed cobalt-alumina catalyst made by compounding and spray drying |
US7615509B2 (en) * | 2006-12-19 | 2009-11-10 | Exxonmobil Research And Engineering Company | High activity supported distillate hydroprocessing catalysts |
JP4902424B2 (en) * | 2007-05-21 | 2012-03-21 | Jx日鉱日石エネルギー株式会社 | Hydrorefining catalyst and hydrorefining method |
RU2749420C2 (en) * | 2016-08-01 | 2021-06-09 | В.Р. Грейс Энд Ко.-Конн. | Method for peptization of aluminum oxide for fluidized catalysts |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3383301A (en) * | 1966-01-20 | 1968-05-14 | Gulf Research Development Co | Residue desulfurization with catalyst whose pore volume is distributed over wide range of pore sizes |
US3622500A (en) * | 1970-04-21 | 1971-11-23 | Hydrocarbon Research Inc | Hydrogenation of hydrocarbons with catalytic microspheres |
US3770617A (en) * | 1970-12-28 | 1973-11-06 | Exxon Research Engineering Co | Hydrodesulfurization with a specified pore size distribution in silica-stabilized alumina |
US4341625A (en) * | 1973-08-09 | 1982-07-27 | Chevron Research Company | Method for preparing a catalyst carrier, a catalyst containing the carrier, and a hydrocarbon hydrodesulfurization process using the catalyst |
US4113661A (en) * | 1973-08-09 | 1978-09-12 | Chevron Research Company | Method for preparing a hydrodesulfurization catalyst |
US3876523A (en) * | 1973-08-29 | 1975-04-08 | Mobil Oil Corp | Catalyst for residua demetalation and desulfurization |
US4082695A (en) * | 1975-01-20 | 1978-04-04 | Mobil Oil Corporation | Catalyst for residua demetalation and desulfurization |
GB1550684A (en) * | 1975-08-28 | 1979-08-15 | Mobil Oil Corp | Demetalation-desulphurisation catalyst and the preparation and use thereof |
CA1069486A (en) * | 1975-11-10 | 1980-01-08 | Nalco Chemical Company | Method of preparing a controlled pore volume alumina with citric acid |
US4048060A (en) * | 1975-12-29 | 1977-09-13 | Exxon Research And Engineering Company | Two-stage hydrodesulfurization of oil utilizing a narrow pore size distribution catalyst |
US4051021A (en) * | 1976-05-12 | 1977-09-27 | Exxon Research & Engineering Co. | Hydrodesulfurization of hydrocarbon feed utilizing a silica stabilized alumina composite catalyst |
US4297242A (en) * | 1978-07-26 | 1981-10-27 | Standard Oil Company (Indiana) | Process for demetallation and desulfurization of heavy hydrocarbons |
US4306965A (en) * | 1979-03-19 | 1981-12-22 | Standard Oil Company (Indiana) | Hydrotreating process |
US4309278A (en) * | 1980-06-02 | 1982-01-05 | Exxon Research & Engineering Co. | Catalyst and hydroconversion process utilizing the same |
US4328127A (en) * | 1980-09-16 | 1982-05-04 | Mobil Oil Corporation | Residua demetalation/desulfurization catalyst |
US4395328A (en) * | 1981-06-17 | 1983-07-26 | Standard Oil Company (Indiana) | Catalyst and support, their methods of preparation, and processes employing same |
JPS614533A (en) * | 1984-06-15 | 1986-01-10 | Res Assoc Residual Oil Process<Rarop> | Hydrogen treating catalyst and method for hydrodesulfurizing and hydrocracking heavy mineral oil by using it |
US4945079A (en) * | 1984-11-13 | 1990-07-31 | Aluminum Company Of America | Catalyst of nickel and molybdenum supported on alumina |
US4652545A (en) * | 1985-05-06 | 1987-03-24 | American Cyanamid Company | Catalyst for hydroconversion of heavy oils and method of making the catalyst |
US4648963A (en) * | 1985-06-24 | 1987-03-10 | Phillips Petroleum Company | Hydrofining process employing a phosphorus containing catalyst |
US4746419A (en) * | 1985-12-20 | 1988-05-24 | Amoco Corporation | Process for the hydrodemetallation hydrodesulfuration and hydrocracking of a hydrocarbon feedstock |
US4729826A (en) * | 1986-02-28 | 1988-03-08 | Union Oil Company Of California | Temperature controlled catalytic demetallization of hydrocarbons |
US4941964A (en) * | 1988-03-14 | 1990-07-17 | Texaco Inc. | Hydrotreatment process employing catalyst with specified pore size distribution |
JP2631704B2 (en) * | 1988-07-01 | 1997-07-16 | コスモ石油株式会社 | Catalyst composition for hydrotreating heavy hydrocarbon oils |
US5009771A (en) * | 1990-03-30 | 1991-04-23 | Amoco Corporation | Hydroconversion process using mixed catalyst system |
-
1991
- 1991-10-25 US US07/783,067 patent/US5192734A/en not_active Expired - Lifetime
-
1992
- 1992-10-22 CA CA002081130A patent/CA2081130C/en not_active Expired - Lifetime
- 1992-10-26 US US07/967,087 patent/US5300214A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US5300214A (en) | 1994-04-05 |
US5192734A (en) | 1993-03-09 |
CA2081130A1 (en) | 1993-04-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2081130C (en) | Hydroprocessing catalyst composition | |
US5435908A (en) | Hydroconversion process employing catalyst with specified pore size distribution | |
US5827421A (en) | Hydroconversion process employing catalyst with specified pore size distribution and no added silica | |
US5399259A (en) | Hydroconversion process employing catalyst with specified pore size distribution | |
EP2411145B1 (en) | A high surface area composition for use in the catalytic hydroconversion of a heavy hydrocarbon feedstock, a method making such composition and its use | |
CA1154736A (en) | Hydroprocessing catalyst having bimodal pore distribution | |
US10118161B2 (en) | Catalyst and process for hydroconversion of a heavy feedstock | |
US5616530A (en) | Hydroconversion process employing catalyst with specified pore size distribution | |
US9669394B2 (en) | Resid hydrotreating catalyst containing titania | |
US5468371A (en) | Catalyst for residual conversion demonstrating reduced toluene insolubles | |
JPH04502776A (en) | Hydrodemetalization and hydrodesulfurization methods, catalysts and catalyst substrates using catalysts with specific macropores | |
KR20030080214A (en) | Hydroprocessing catalyst and use thereof | |
US4657664A (en) | Process for demetallation and desulfurization of heavy hydrocarbons | |
CA2228800C (en) | Hydroconversion process employing a phosphorus loaded nimop catalyst with a specified pore size distribution | |
EP0159705B1 (en) | Catalyst for the hydrotreating of heavy hydrocarbon oils | |
EP0590894A1 (en) | Hydroconversion process | |
WO1999019061A1 (en) | Hydrotreating catalyst for heavy oil, carrier for the catalyst, and process for the preparation of the catalyst | |
EP3448963B1 (en) | A method of operating an ebullated bed process to reduce sediment yield | |
CN116408115A (en) | Hydrodesulfurization catalyst and preparation method and application thereof | |
CN116196949A (en) | Preparation method of sulfur-containing hydrogenation activity protection catalyst | |
JP2003135975A (en) | Catalyst for hydrogenation of hydrocarbon oil and method for manufacturing the same | |
JP2001314770A (en) | Catalyst for hydrogenating heavy hydrocarbon oil and hydrogenating method to use the same | |
JPH07232078A (en) | Catalyst for hydrodesulfurization denitrification and its preparation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKEX | Expiry | ||
MKEX | Expiry |
Effective date: 20121022 |