CA1159039A - Hydrotreating catalyst and use thereof - Google Patents
Hydrotreating catalyst and use thereofInfo
- Publication number
- CA1159039A CA1159039A CA000389545A CA389545A CA1159039A CA 1159039 A CA1159039 A CA 1159039A CA 000389545 A CA000389545 A CA 000389545A CA 389545 A CA389545 A CA 389545A CA 1159039 A CA1159039 A CA 1159039A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- pores
- diameter
- hydrotreating
- nickel
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 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 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000011269 tar Substances 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Abstract of the Disclosure A catalyst for hydrotreating of heavy feedstocks comprised of nickel and molybdenum, supported on alumina having a defined pore size distribution which has been cal-cined at a temperature of from 1150°F - 1300°F,and process for hydrotreating using the catalyst. Calcining of such catalyst at such temperatures is required in order to pro-vide for effective use thereof as a hydrotreating catalyst for higher boiling feedstocks.
Description
This invention relates to hydrotreating, and more particularly, to an improved hydrotreating catalyst and process using the catalyst.
In the hydrotreating of hydrocarbon containiny feed-stock, such hydrotreating is generally accomplished in the presence of a hydrotreating catalyst comprised of Group VI and Group VIII
metals supported on a suitable support. There is a continued need for improvements in such catalysts so as to provide improved activity and longer catalyst life.
In accordance with one aspect of the present invention, there is provided an improved hydrotreating catalyst which is comprised of catalytically effective amounts of nickel and molybdenum supported on alumina wherein the catalyst has a total porosity of at least 0.5 cc/g and most generally from 0.75 to O.9S
cc/g, a pore size distribution as defined in the following Table and wherein the catalyst has been calcined at a temperature of from 1150 F to 1300 F.
TABLE
Pore Diameter, A Porosity (cc/g) . _ _ ~250 0.25 - 0.40 250 - 500 0.10 - 0.25 500 - 1500 0.20 - 0.30 1500 - 4000 0.05 - 0.15 ~400Q 0.03 - 0.10 The inventor has found that such catalyst has improved hydrotreating activity and improved catalyst life, provided that the catalyst is calcined at such temperatures. The inventor has found that calcining of such catalyst at temperatures ' . . .
.~ ~. . ..
o~
normally used for the calcining of supported nickel-containing catalysts (about 1000 - 1050F) does not provide a useable catalyst for the hydrotreating of higher boiling feedstocks in that severe coking of the catalyst occurs after only a short period of operation.
The catalyst of the invention is comprised of nickel and molybdenum and may further include cobalt.
The catalyst of the invention generally contains from 1% to 6%, preferably from 1% to 4% of nickel; and from 5% to 16%, preferably from 6% to 10% of molybdenum, and 0% to 6% of cobalt, all by weight. If cobalt is employed, the cobalt is generally present in an amount of from 1%
to 6~, by weight.
The particle size of the catalyst of the invention is generally in the order of from 0.005 to 0.125 inch, with the catalyst, if in extruded form, generally having a size in the order of from O.OlS to 0.125 inch, and, if in spherical form, a size in the order of from 0.005 to 0.125 inch.
In general, the surface area of the catalyst is at least 125 m2/G, and most generally from 150 - 300 m /g.
The alumina of the catalyst is generally the gamma form thereof. In some cases, the alumina support could include up to 10% of silica.
The nickel and molybdenum and optionally also cobalt are supported on the alumina by procedures generally known in the art. Thus, for example, a molybdenum compound, such as ammonium molybdate may be added to an aqueous slurry of the alumina having a porosity and pore size distribution 90~
to provide a finished catalyst having the hereinabove defined porosity and pore size distribution, followed by spray drying and formation, for example, into spheres. Optionally the supported molybdenum may be calcined at this time; however, such calcining would be additional to and not in lieu of the final calcination in accordance with the invention.
The molybdenum supported on the alumina is then impregnated with nickel, for example as aqueous nickel nitra-te, and optionally also cobalt, followed by drying.
The supported catalyst is then calcined in accordance with the invention at a temperature of from 1150F to 1300F,`
preferably at a temperature of from 1150F to 1250F, with the calcination temperature in most cases being about 1200F.
As hereinabove notea the use of lower calcination temperatures, as conventionally employed for suppor~ted catalysts containing nlckel, does not provide an acceptable catalyst (excessive coke lay-down), and temperatures above 1300F would not be suitable because of molybdenum volatility. In using the higher portions of the disclosed calcining temperatures there may be some deactivation of the nickel component of the catalyst, and as a result, in most cases the calcination temperature should not exceed 1250F.
In accordance with anothe~r aspect of the present invention, the hereinabove described hydrotreating catalyst is employed for hydrotreating of hydrocarbon-containing feed~
stocks which contain heavier (higher boiling components), with such feedstocks generally being characterized by having at least 50~ of components boiling above 975F.
~ I .
., .: . . . .
\
~lS~ 9 Such feedstocks are generally derived from either petroleum or coal sources, and as representative examples of such feed-stocks, there may be mentioned: heavy petroleum crudes, petro-leu~ rPsidues from atmospheric or vacuum distillatibns, shale oil, shale oil residues, tar sands, bitumen, coal tar pitches, solvent refined coal, solvent deasphalted oils, etc~
The hydrotreating of the feedstock is accomplished at conditions which are generally known in the art to be effec-tive for upgrading of the feedstock. The catalyst is preferably presulfided. In qeneral, the hydrotreating is accomplished at temperatures of the order of from 700 to 900~, preferably from 750 to 850F, and at pressures of the order of from 1000 to 3500 psig, preferably from 1500 to 3000 psig The liquid hourly space velocity is generally of the order of from 0.05 to 2.0 hr, preferably 0.1 to 1.0 hr 1 The hydrogen is supplied in an amount sufficient to accomplish the hydrotreat-ing, with such hydrogen generally being employed in an amount of from 2000 to 6000 SCF/bbl. preferably from 4000 to 5000 SCF/b~l.
The hydrotreating may be effected in any one o~ a wide variety of reactors. Thus, for example, such hydrotreating may be effected in a fixed bed reactor, a moving bed reactor, a fluidized bed reactor, an expanded bed reactor, etc., which may contain one or more beds of the catalyst.
As known in the art such hydrotreating upgrades the feed-s~ock by conversion of higher boiling cornponents to lower boiling S ~ components. In addition, desulfurization and/or denitrogenation is also accomplished.
The invantion will be fur~her described with respect to the ~ollowing example:
EXAMPLE.
_ A catalyst was prepared which w~scomprised of 12.0~
Moo3; 1.5~ CoV and 1.5% NiO supported on gamma-alumina having a total porosity of 0.87-0.89 cc/g and a pore size distribution as follows:
Pore Diameter, A Porosity cc/~
~ 250 0.34 - 0.36 250 - 500 0.19 - 0~15 _ 500 - 1500 0.22 - 0.23 1500 - 4000 0.10 - 0.11 ~4000 0.04 - 0.07 The catalystwas in the form of sphercs having a diameter of the order of .015-.035 inch.
In one case ~case A) the catalyst was calcined at 1050F
and in the other case (case B) the catalyst wa~ calcined in accordance with the inventionat 1200F.
'!
, Each of the catalysts was presulfided in the reactor and tested or the hydrotreating of Cold ~ake Atmospheric and at Residue,as an ebullated catalyst bed,at 730~ 7~~hydrogen pres-~ure o~ 2000 psig, with hydrogen being used at a rate of 5000 S SCF/bbl of feed.
The case A catalyst coked up wi~hin 24 hours.
The case B cataly~t in accordance with the invention operated for 35 days with the temperature eventually being raised to 8~0F. The conversion rate was of the order of ~0~, based on the 975F+ components of the feed.
_ Thus, in accordance with the present invention, ther~
is provided an effective hydrotreating catalyst for upgrading of heavier hydrocarbon feedstocks. The catalyst is capable of operating over long perio~ of time and ~t conversion rates of 40~ and greater, in most cases in excess of 50~ and of the order of 60~, based on the 975F~ components of the feed.
In the hydrotreating of hydrocarbon containiny feed-stock, such hydrotreating is generally accomplished in the presence of a hydrotreating catalyst comprised of Group VI and Group VIII
metals supported on a suitable support. There is a continued need for improvements in such catalysts so as to provide improved activity and longer catalyst life.
In accordance with one aspect of the present invention, there is provided an improved hydrotreating catalyst which is comprised of catalytically effective amounts of nickel and molybdenum supported on alumina wherein the catalyst has a total porosity of at least 0.5 cc/g and most generally from 0.75 to O.9S
cc/g, a pore size distribution as defined in the following Table and wherein the catalyst has been calcined at a temperature of from 1150 F to 1300 F.
TABLE
Pore Diameter, A Porosity (cc/g) . _ _ ~250 0.25 - 0.40 250 - 500 0.10 - 0.25 500 - 1500 0.20 - 0.30 1500 - 4000 0.05 - 0.15 ~400Q 0.03 - 0.10 The inventor has found that such catalyst has improved hydrotreating activity and improved catalyst life, provided that the catalyst is calcined at such temperatures. The inventor has found that calcining of such catalyst at temperatures ' . . .
.~ ~. . ..
o~
normally used for the calcining of supported nickel-containing catalysts (about 1000 - 1050F) does not provide a useable catalyst for the hydrotreating of higher boiling feedstocks in that severe coking of the catalyst occurs after only a short period of operation.
The catalyst of the invention is comprised of nickel and molybdenum and may further include cobalt.
The catalyst of the invention generally contains from 1% to 6%, preferably from 1% to 4% of nickel; and from 5% to 16%, preferably from 6% to 10% of molybdenum, and 0% to 6% of cobalt, all by weight. If cobalt is employed, the cobalt is generally present in an amount of from 1%
to 6~, by weight.
The particle size of the catalyst of the invention is generally in the order of from 0.005 to 0.125 inch, with the catalyst, if in extruded form, generally having a size in the order of from O.OlS to 0.125 inch, and, if in spherical form, a size in the order of from 0.005 to 0.125 inch.
In general, the surface area of the catalyst is at least 125 m2/G, and most generally from 150 - 300 m /g.
The alumina of the catalyst is generally the gamma form thereof. In some cases, the alumina support could include up to 10% of silica.
The nickel and molybdenum and optionally also cobalt are supported on the alumina by procedures generally known in the art. Thus, for example, a molybdenum compound, such as ammonium molybdate may be added to an aqueous slurry of the alumina having a porosity and pore size distribution 90~
to provide a finished catalyst having the hereinabove defined porosity and pore size distribution, followed by spray drying and formation, for example, into spheres. Optionally the supported molybdenum may be calcined at this time; however, such calcining would be additional to and not in lieu of the final calcination in accordance with the invention.
The molybdenum supported on the alumina is then impregnated with nickel, for example as aqueous nickel nitra-te, and optionally also cobalt, followed by drying.
The supported catalyst is then calcined in accordance with the invention at a temperature of from 1150F to 1300F,`
preferably at a temperature of from 1150F to 1250F, with the calcination temperature in most cases being about 1200F.
As hereinabove notea the use of lower calcination temperatures, as conventionally employed for suppor~ted catalysts containing nlckel, does not provide an acceptable catalyst (excessive coke lay-down), and temperatures above 1300F would not be suitable because of molybdenum volatility. In using the higher portions of the disclosed calcining temperatures there may be some deactivation of the nickel component of the catalyst, and as a result, in most cases the calcination temperature should not exceed 1250F.
In accordance with anothe~r aspect of the present invention, the hereinabove described hydrotreating catalyst is employed for hydrotreating of hydrocarbon-containing feed~
stocks which contain heavier (higher boiling components), with such feedstocks generally being characterized by having at least 50~ of components boiling above 975F.
~ I .
., .: . . . .
\
~lS~ 9 Such feedstocks are generally derived from either petroleum or coal sources, and as representative examples of such feed-stocks, there may be mentioned: heavy petroleum crudes, petro-leu~ rPsidues from atmospheric or vacuum distillatibns, shale oil, shale oil residues, tar sands, bitumen, coal tar pitches, solvent refined coal, solvent deasphalted oils, etc~
The hydrotreating of the feedstock is accomplished at conditions which are generally known in the art to be effec-tive for upgrading of the feedstock. The catalyst is preferably presulfided. In qeneral, the hydrotreating is accomplished at temperatures of the order of from 700 to 900~, preferably from 750 to 850F, and at pressures of the order of from 1000 to 3500 psig, preferably from 1500 to 3000 psig The liquid hourly space velocity is generally of the order of from 0.05 to 2.0 hr, preferably 0.1 to 1.0 hr 1 The hydrogen is supplied in an amount sufficient to accomplish the hydrotreat-ing, with such hydrogen generally being employed in an amount of from 2000 to 6000 SCF/bbl. preferably from 4000 to 5000 SCF/b~l.
The hydrotreating may be effected in any one o~ a wide variety of reactors. Thus, for example, such hydrotreating may be effected in a fixed bed reactor, a moving bed reactor, a fluidized bed reactor, an expanded bed reactor, etc., which may contain one or more beds of the catalyst.
As known in the art such hydrotreating upgrades the feed-s~ock by conversion of higher boiling cornponents to lower boiling S ~ components. In addition, desulfurization and/or denitrogenation is also accomplished.
The invantion will be fur~her described with respect to the ~ollowing example:
EXAMPLE.
_ A catalyst was prepared which w~scomprised of 12.0~
Moo3; 1.5~ CoV and 1.5% NiO supported on gamma-alumina having a total porosity of 0.87-0.89 cc/g and a pore size distribution as follows:
Pore Diameter, A Porosity cc/~
~ 250 0.34 - 0.36 250 - 500 0.19 - 0~15 _ 500 - 1500 0.22 - 0.23 1500 - 4000 0.10 - 0.11 ~4000 0.04 - 0.07 The catalystwas in the form of sphercs having a diameter of the order of .015-.035 inch.
In one case ~case A) the catalyst was calcined at 1050F
and in the other case (case B) the catalyst wa~ calcined in accordance with the inventionat 1200F.
'!
, Each of the catalysts was presulfided in the reactor and tested or the hydrotreating of Cold ~ake Atmospheric and at Residue,as an ebullated catalyst bed,at 730~ 7~~hydrogen pres-~ure o~ 2000 psig, with hydrogen being used at a rate of 5000 S SCF/bbl of feed.
The case A catalyst coked up wi~hin 24 hours.
The case B cataly~t in accordance with the invention operated for 35 days with the temperature eventually being raised to 8~0F. The conversion rate was of the order of ~0~, based on the 975F+ components of the feed.
_ Thus, in accordance with the present invention, ther~
is provided an effective hydrotreating catalyst for upgrading of heavier hydrocarbon feedstocks. The catalyst is capable of operating over long perio~ of time and ~t conversion rates of 40~ and greater, in most cases in excess of 50~ and of the order of 60~, based on the 975F~ components of the feed.
Claims (13)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A hydrotreating catalyst having an improved catalyst life, comprising: a catalytically effective amount of nickel and molybdenum supported on an alumina support, said catalyst having a total porosity of at least 0.5 cc/g and a pore size distribution of from 0.25 to 0.40 cc/g of pores with a dia-meter of less than 250 °A, 0.10 to 0.25 cc/g of pores with a diameter of from 250 - 500 °A, from 0.20 to 0.30 cc/g of pores with a diameter of from 500 - 1500 °A, from 0.05 to 0,15 cc/g of pores with a diameter of from 1500 - 4000 °A, and from 0.03 to 0.10 cc/g of pores with a diameter of greater than 4000°A, said catalyst comprised of nickel and molybdenum sup-ported on alumina having been prepared with calcining at a temperature of from 1150°F to 1300°F.
2. The catalyst of Claim 1, wherein the surface area of the catalyst is at least 125 m2/g.
3. The catalyst of Claim 1, wherein the surface area of the catalyst is from 150 - 300 m2/g.
4. The catalyst of Claim 1, wherein there is from 0.34 to 0.36 cc/g of pores of a diameter of less than 250 A, from 0.14 to 0.15 cc/g of pores with a diameter of from 250 to 500 °A, from 0.22 to 0.23 cc/g of pores with a diameter of from 500 -1500 °A, from 0.10 to 0.11 cc/g of pores having a diameter of from 1500 to 4000 °A, and from 0.04 to 0.07 cc/g of pores with a diameter of greater than 4000 °A.
5. The catalyst of Claim 1, wherein the catalyst includes from 1% to 6% of nickel and from 5% to 16% of molybdenum, by weight.
6. The catalyst of Claim 1, wherein the said temperature of calcining is from 1150° to 1250°F.
7. The catalyst of Claim 1, wherein the total porosity is from 0.75 to 0.95 cc/g.
8. The catalyst of Claim 1, wherein the alumina is gamma-alumina.
9. The catalyst of Claim 1, wherein the catalyst further includes a catalytically effective amount of cobalt.
10. A process for the catalytic hydrotreating of a heavier hydrocarbon-containing feedstock in the presence of a hydrotreat-ing catalyst, which comprises effecting the hydrotreating in the presence of a hydrotreating catalyst, comprising: a catalytically effective amount of nickel and molybdenum supported on an alumina support, said catalyst having a total porosity of at least 0.5 cc/g and a pore size distribution of from 0.25 to 0.40 cc/g of pores with a dia-meter of less than 250 °A, 0.10 to 0.25 cc/g of pores with a diameter of from 250 - 500 °A, from 0.20 to 0.30 cc/g of pores with a diameter of from 500 - 1500 °A, from 0.05 to 0.15 cc/g of pores with a diameter of from 1500 - 4000 °A, and from 0.03 to 0.10 cc/g of pores with a diameter of greater than 4000 °A, said catalyst comprised of nickel and molybdenum supported on alumina having been prepared with calcining at a temperature of from 1150°F to 1300°F.
11. The process of Claim 10, wherein the hydrocarbon feed-stock is characterized by having at least 50% of its components boiling above 975°F.
12. The process of Claim 10, wherein the hydrotreating is at a temperature of from 700°F to 900°F.
13. The process of Claim 10, wherein the hydrotreating is operated at a conversion of at least 50%,based on components boiling above 975°F.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20894880A | 1980-11-21 | 1980-11-21 | |
| US208,948 | 1980-11-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1159039A true CA1159039A (en) | 1983-12-20 |
Family
ID=22776714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000389545A Expired CA1159039A (en) | 1980-11-21 | 1981-11-05 | Hydrotreating catalyst and use thereof |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5946666B2 (en) |
| AU (1) | AU540245B2 (en) |
| CA (1) | CA1159039A (en) |
| DE (1) | DE3145718A1 (en) |
| ES (1) | ES507340A1 (en) |
| FR (1) | FR2494597A1 (en) |
| GB (1) | GB2087747B (en) |
| IT (1) | IT1143446B (en) |
| MX (2) | MX172430B (en) |
| NL (1) | NL8105267A (en) |
| SE (1) | SE448951B (en) |
| ZA (1) | ZA817732B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3522538A1 (en) * | 1984-06-22 | 1986-01-02 | Chiyoda Chemical Engineering & Construction Co. Ltd., Yokohama, Kanagawa | Process and catalyst for the hydrogenation of coal tar pitch |
| EP0178774B1 (en) * | 1984-09-12 | 1991-02-20 | Nippon Kokan Kabushiki Kaisha | A hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke from the hydrogenation product of coal tar |
| GC0000065A (en) | 1998-09-01 | 2004-06-30 | Japan Energy Corp | Hydrocracking catalyst, producing method threof, and hydrocracking method. |
| JP4493997B2 (en) * | 2003-12-10 | 2010-06-30 | 財団法人石油産業活性化センター | Hydrodesulfurization catalyst for hydrocarbon oil and method for producing the same |
| WO2008019581A1 (en) | 2006-08-11 | 2008-02-21 | China Petroleum & Chemical Corporation | Alumina having a complex pore structure, and catalyst and process for selective hydrogenation of cracking gasoline |
| 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 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL261905A (en) * | 1960-03-02 | |||
| US3361526A (en) * | 1964-06-19 | 1968-01-02 | Grace W R & Co | Process for producing alumina having a narrow pore size distribution |
| CA943944A (en) * | 1967-10-27 | 1974-03-19 | Michael C. Chervenak | Catalysts, methods of preparation of same and processes for using same |
| JPS5141641B2 (en) * | 1972-01-06 | 1976-11-11 | ||
| US3952069A (en) * | 1973-01-26 | 1976-04-20 | Gulf Research & Development Company | Hydrogenation of aromatics |
| JPS51122105A (en) * | 1975-04-18 | 1976-10-26 | Toa Nenryo Kogyo Kk | Process for hydrofining of hydrocarbon oil |
| US4013547A (en) * | 1976-01-22 | 1977-03-22 | Union Oil Company Of California | Desulfurization of residual petroleum oils with a catalyst calcined at higher temperatures |
| US4301037A (en) * | 1980-04-01 | 1981-11-17 | W. R. Grace & Co. | Extruded alumina catalyst support having controlled distribution of pore sizes |
-
1981
- 1981-11-05 CA CA000389545A patent/CA1159039A/en not_active Expired
- 1981-11-09 ZA ZA817732A patent/ZA817732B/en unknown
- 1981-11-13 AU AU77476/81A patent/AU540245B2/en not_active Ceased
- 1981-11-19 DE DE19813145718 patent/DE3145718A1/en active Granted
- 1981-11-19 FR FR8121684A patent/FR2494597A1/en active Granted
- 1981-11-19 MX MX016070A patent/MX172430B/en unknown
- 1981-11-19 MX MX190208A patent/MX160789A/en unknown
- 1981-11-20 JP JP56187655A patent/JPS5946666B2/en not_active Expired
- 1981-11-20 NL NL8105267A patent/NL8105267A/en not_active Application Discontinuation
- 1981-11-20 ES ES507340A patent/ES507340A1/en not_active Expired
- 1981-11-20 GB GB8135076A patent/GB2087747B/en not_active Expired
- 1981-11-20 SE SE8106925A patent/SE448951B/en not_active IP Right Cessation
- 1981-11-20 IT IT49747/81A patent/IT1143446B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| ZA817732B (en) | 1982-10-27 |
| AU540245B2 (en) | 1984-11-08 |
| GB2087747B (en) | 1984-07-04 |
| DE3145718C2 (en) | 1987-06-19 |
| IT1143446B (en) | 1986-10-22 |
| ES507340A0 (en) | 1985-03-01 |
| JPS57117343A (en) | 1982-07-21 |
| IT8149747A0 (en) | 1981-11-20 |
| ES507340A1 (en) | 1985-03-01 |
| AU7747681A (en) | 1982-05-27 |
| SE8106925L (en) | 1982-05-22 |
| DE3145718A1 (en) | 1982-06-16 |
| MX160789A (en) | 1990-05-17 |
| FR2494597B1 (en) | 1985-01-04 |
| NL8105267A (en) | 1982-06-16 |
| SE448951B (en) | 1987-03-30 |
| JPS5946666B2 (en) | 1984-11-14 |
| FR2494597A1 (en) | 1982-05-28 |
| MX172430B (en) | 1993-12-16 |
| GB2087747A (en) | 1982-06-03 |
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