Mineral oils: processes and products – Refining – Sulfur removal
Reexamination Certificate
1997-11-06
2002-05-14
Griffin, Walter D. (Department: 1764)
Mineral oils: processes and products
Refining
Sulfur removal
C208S25100H, C208S25400R, C208S112000, C502S313000, C502S314000, C502S315000, C502S316000, C502S439000, C502S506000, C502S523000
Reexamination Certificate
active
06387248
ABSTRACT:
BACKGROUND OF THE INVENTION
It is known to convert heavy hydrocarbons, such as those having a boiling point above about 1000° F., such as petroleum residues into lighter hydrocarbons which are characterized by higher economic value through hydrodesulfurization (HDS), hydrodenitrogenation (HDN), carbon residue reduction (CRR), and hydrodemetallation (HDM)—the latter particularly including removal of nickel compounds (HDNi) and vanadium compounds (HDV).
These processes typically employ hydrotreating catalysts with specified ranges of pores having relatively small diameters (i.e., micropores) and pores having relatively large diameters (i.e., macropores). Thus, U.S. Pat. No. 5,399,259 and U.S. Pat. No. 5,435,908 disclose catalysts comprising a porous alumina support bearing 3-6 w % of Group VIII metal oxide, 14.5-24 w % of Group VI-B metal oxide, and 0-6 w % of phosphorus oxide, characterized by a Total Surface Area of 165-230 m
2
/g, Total Pore Volume of 0.5-0.8 cc/g, and a Pore Size Distribution (PSD) whereby less than about 5% of Total Pore Volume (TPV) is present as primary micropores of diameter less than about 80 Å and at least about 65% of the TPV is present as secondary micropores of diameter of ±20 Å of a Pore Mode of about 100-135 Å and about 22-29% of the TPV is present as macropores of diameter ≧250 Å.
The catalysts disclosed in theses patents are prepared by mulling an alumina powder and extruding it to form a support, calcining the support, impregnating the calcined support with the catalytic metals salts and recalcining the impregnated support.
FIELD OF THE INVENTION
This invention relates to a novel method of preparing catalysts and using the catalysts in converting heavy hydro-carbons. The catalysts of the present invention are prepared by mulling the salts of Group VIII, Group VI-B metals with an alumina powder, followed by extrusion and calcination, and have less than 5% of the Group VIII metal oxide in an acid extractable form; the catalyst comprising a porous alumina support containing 3-6 w % of Group VIII metal oxide, 14.5-24 w % of Group VI-B metal oxide, and 0-6 w % of phosphorus oxide, characterized by a Total Surface Area of 165-230 m
2
/g, Total Pore Volume of 0.81-0.98 cc/g, and a Pore Diameter Distribution whereby 22.0-36.0% of the Total Pore Volume is present as macropores of a diameter greater than 250 Å, 64.0-78.0% of the Total Pore Volume is present as micropores of a diameter of less than 250 Å, greater than 60% of the micropore volume is present as micropores of diameter ±25 Å about a pore mode by volume of 100-120 Å, and less than 0.05 cc/g of micropore volume is present in micropores with diameters less than 80 Å.
The method of the present invention does away with the steps of U.S. Pat. No. 5,399,259 and U.S. Pat. No. 5,435,908 that require impregnating the calcined support with the catalytic metals and with the recalcining of the impregnated support.
Since the catalysts of the instant invention are not impregnated, they do not have many of the characteristics of impregnated catalysts. Indeed, the catalysts of the instant invention typically have HDS-MAT C 0.5g @ 550° F. values of only 10-30 and HDS-MAT relative k values of only 0.05 to 0.30.
PRIOR ART
U.S. Pat. No. 5,047,142 (Dai et al.) discloses a catalyst composition useful in the hydroprocessing of a sulfur and metal-containing feedstock comprising an oxide of nickel or cobalt and an oxide of molybdenum on a porous alumina support in such a manner that the molybdenum gradient of the catalyst has value of less than 6.0 and 15-30% of the nickel or cobalt is in an acid extractable form, and having a surface area of 150-210 m
2
/g, a Total Pore Volume (TPV) of 0.50-0.75 cc/g, and a pore size distribution such that less than 25% TPV is in pores having diameters of less than 100 Å, 70.0-85.0% TPV is in pores having diameters of 100 Å-160 Å and 1.0-15.0% TPV is in pores having diameters of greater than 250 Å.
U.S. Pat. No. 4,941,964 (Dai et al.) discloses a process for the hydrotreatment of a sulfur and metal-containing feed which comprises contacting said feed with hydrogen and a catalyst in a manner such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed, the catalyst comprising an oxide of a Group VIII metal, an oxide of a Group VI-B metal and 0-2.0 w % of an oxide of phosphorus on a porous alumina support, and having a surface area of 150-210 m
2
/g and a Total Pore Volume (TPV) of 0.50-0.75 cc/g such that 70-85% TPV is in pores having diameters of 100 Å160 Å and 5.5-22.0% TPV is in pores having diameters of greater than 250 Å.
U.S. Pat. No. 4,738,944 (Robinson et al.) discloses a catalyst composition useful in the hydrotreatment of hydrocarbon oils, the catalyst containing nickel and phosphorus and about 19-21.5% Mo (calculated as the oxide) on a porous refractory oxide, having a narrow pore size distribution wherein at least 10% TPV is in pores having diameters less than 70 Å, at least 75% TPV is in pores having diameters between 50-110 Å, at least 60% TPV is in pores having diameters within about 20 Å above and below the average pore diameter; and at most 25% TPV, most preferably less than 10% TPV, is in pores having diameters greater than 110 Å.
U.S. Pat. No. 4,652,545 (Lindsley et al.) discloses a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing 0.5-5% Ni or Co and 1.8-18% Mo (calculated as the oxides) on a porous alumina support, having 15-30% of the Ni or Co in an acid extractable form, and further characterized by having a Total Pore Volume (TPV) of 0.5-1.5 cc/g with a pore diameter distribution such that (i) at least 70% TPV is in pores having 80-120 Å diameters, (ii) less than 0.03 cc/g of TPV is in pores having diameters of less than 80 Å, and (iii) 0.05-0.1 cc/g of TPV is in pores having diameters of greater than 120 Å.
U.S. Pat. No. 4,395,328 (Hensley, Jr. et al.) discloses a process for the hydroconversion of a hydrocarbon stream containing asphaltenes and a substantial amount of metals, comprising contacting the stream (in the presence of hydrogen) with a catalyst present in one or more fixed or ebullating beds, the catalyst comprising at least one metal which may be a Group VI-B or Group VIII metal, an oxide of phosphorus, and an alumina support, where the alumina support material initially had at least 0.8 cc/gm of TPV in pores having diameters of 0-1200 Å, and at least 0.1 cc/gm of TPV is in pores having diameters of 1200-50,000, and the support material was heated with steam to increase the average pore diameter of the catalyst support material.
U.S. Pat. No. 4,341,625 (Tamm) discloses a process for hydrodesulfurizing a metal-containing hydrocarbon feedstock which comprises contacting the feedstock with a catalyst comprising at least one hydrogenation agent (i.e., Group VI-B or Group VIII metal or combinations thereof) on a porous support, the catalyst being further characterized by having a TPV of 0.5-1.1 cc/g with at least 70% TPV in pores having diameters of 80-150 Å and less than 3% TPV in pores having diameters greater than 1000 Å.
U.S. Pat. No. 4,328,127 (Angevine et al.) discloses a catalyst composition for use in the hydrodemetallation-desulfurization of residual petroleum oils, the catalyst comprising a hydrogenating component (i.e., Group VI-B or Group VIII metal, or combinations thereof) on a porous support, and being further characterized by having a TPV of 0.45-1.5 cc/g with 40-75% TPV in pores having diameters of 150-200 Å, and up to 5% TPV in pores having diameters of greater than 500 Å.
U.S. Pat. No. 4,309,278 (Sawyer) discloses a process for the hydroconversion of a hydrocarbon feedstock comprising contacting the feedstock with hydrogen and a catalyst in a fixed bed, moving bed, ebullating bed, slurry, disperse phase, or fluidized bed reactor, where the catalyst comprises a hy
Dai Pei-Shing Eugene
Sherwood, Jr. David Edward
Griffin Walter D.
Howrey Simon Arnold & White
Reinisch Morris N.
Texaco Inc.
LandOfFree
Method of preparing a catalyst for use in the hydrotreating... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Method of preparing a catalyst for use in the hydrotreating..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Method of preparing a catalyst for use in the hydrotreating... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2829368