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US5094991.Pdf ||||||||||||| USOO5094.991A United States Patent (19) 11 Patent Number: 5,094,991 Lopez et al. 45) Date of Patent: Mar. 10, 1992 54 SLURRY CATALYST FOR (56) References Cited HYDROPROCESSING HEAVY AND REFRACTORY OLS U.S. PATENT DOCUMENTSMEN 4,234,554 l/1981 Naumann et al. ................... 502/220 a 4,430,442 2/1984 Sawyer et al. ...................... 502A200 75 Inventors: Jaime Lopez, Benicia, Calif.; Eugene 4,430,443 2/1984 Seiver et al. ....... ...... 502/200 A. Pasek, Monroeville, Pa. 4,528,089 7/1985 Pewraro et al. ... 208/26 R 4,548,710 10/1985 Simpson ......... ... 208/26 PP 4,557,821 12/1985 Lopez et al. ... ... 208/26 R (73) Assignee: Chevron Research Company, San 4,581,125 4/1986 Stiefec et al. ...... ... 208/26 R Francisco, Calif. 4,592,827 6/1986 Galiasso et al. ... ... 208/26 R 4,595,672 6/1986 Hu et al. ............ ... 208/26 R w 4,650,563 3/1987 Jacobson et al. ...... ... 208/26 R (21) Appl. No.: 657,351 4,705,619 11/1987 McCandlish et al. .......... 208A216 R - a. Primary Examiner-Oik Chaudhuri 22 Filed: Feb. 15, 1991 Assistant Examiner-G. Fourson 57 ABSTRACT Related U.S. Application Data Group VIB metal sulfide slurry catalysts having a pore 63 Continuation of Ser. No. 275,235, Nov. 22, 1988, aban- volume in the pore size range 10 to 300A radius of at doned, which is a continuation-in-part of Ser. No. least 0.1 cc/g. Also, Group VIB metal sulfide catalysts 767,822, Aug. 21, 1985, abandoned, which is a con having a surface' area of at least 20 m2/g. Suitable tinuation-in-part of Ser. No. 527,414, Aug. 29, 1983, Group VIB metals are molybdenum and tungsten, pref. Pat. No. 4,557,821. erably molybdenum. The Group VIB metal sulfide can be approximately a Group VIB metal disulfide. The 51 Int. Cl.5 ... ... B01J 27/047; B01J 27/051 slurry catalyst can be promoted with a Group VIII 52 U.S. Cl. ..................................... 502/219; 502/220 metal, such as nickel or cobalt. 58) Field of Search ............. 208/215, 216 PP, 216 R; 502/219, 220 8 Claims, 5 Drawing Sheets 2 Catalyst Preparator cefalyst 9 Prepare tiers oil athed oil ited later the Water the a rior Art s a Prior Art 8. 3 da 3.s d6 of . 0.9 as s as ses d sts to so. A relius Pere weurs: cc fg Surfect are: reas anary as Cses epitha a2 Futil gifts U.S. Patent Mar. 10, 1992 Sheet 1 of 5 5,094,991 Cotolyst Preporotion O Oil Method O. Water Method A Prior Art e s s d C s 9. Ol O O. O.2 O.3 O.4 O,5 O.6 O.7 O.8 O.9 IO to 300 A Rodius Pore Volume : cc /g Fig.2. Cotolyst Preparation O Oil Method O Woter Method 5 O. A Prior Art sm 9 o 9 s N as O.Ot s 0. 5. s O.OO O O. O2 O.S O.4 O.S. O.6 O.7 O. O.9 IO to 3OO A Radius Pore Volume: CC/g U.S. Patent Mar. 10, 1992 Sheet 2 of 5 5,094,991 Cotolyst Preporotion o Oil Method O Woter Method A Prior Art O. O O. O.2 O.3 O.4 O.5 O.S O.7 O.8 O.9 O to SOO A Rodius Pore Volume: ce/ Fig. 4. Cotolyst Preportion O Oil Method Woter Method A Prior Art SO 2OO 2SO 3OO 35O O 25 SO 75 OO 25 75 225 275 325 375 Sur foce Areo : m/g U.S. Patent Mar. 10, 1992 Sheet 3 of 5 5,094,991 Cotolyst Preporation O Oil Method O Woter Method O. A Prior Art n O.O. O 5O OO so 200 250 soo 35o 25 75 - 25 75 225 275 325 375 Surface Areo: m2/g Cotolyst Proporation O Oil Method Water Method A Prior Art O. O SO OO 5O 2OO 250 3OO 3SO 25 75 25 75 225 275 325 375 Sur foce Areo: m/g U.S. Patent Sheet 4 of 5 5,094,991 O C s 5 i O8 5 as d N NA10OW U.S. Patent Mar. 10, 1992 Sheet 5 of 5 5,094,991 uo?,ououo698u04,Duo1998 5,094,991 1. SLURRY CATALYST FOR HYDROPROCESSING HEAVY AND REFRACTORY OLS (Pore Volume of Used Catalyst, cc/g) - (Percent Carbon) CROSS-REFERENCE TO RELATED 5 cc/g = 100 (100 - Percent Carbon) APPLICATIONS where d is the density of the carbonaceous material, This application is a continuation of application Ser. assumed to be 1.0 for "coke' make from decant oil. No. 275,235, filed Nov. 22, 1988 now abandoned, which Surface Area, is a continuation-in-part of Ser. No. 767,822, filed Aug. 10 21, 1985, by J. Lopez and E. A. Pasek, now abandoned, which is a continuation-in-part of Ser. No. 527,414, filed (Surface Area of Used Catalyst, m/g)100 Aug. 29, 1983, by J. Lopez, J. D. McKinney and E. A. (100 - Percent Carbon) Pasek now U.S. Pat. No. 4,557,821. The hydrogen associated with the coke is disregarded 15 BACKGROUND OF THE INVENTION for both equations. The slurry catalyst as described is prepared directly This invention relates to Group VIB metal sulfide as dispersed particles of a highly active form of molyb slurry catalysts used for the catalytic hydroprocessing denum sulfide, as contrasted to a granulated precipitate. of heavy hydrocarbonaceous oils including crude oils, In general, the catalyst is prepared by presulfiding a heavy distillates, such as FCC decanted oils and lubri 20 Group VI metal compound in an aqueous environment, cating oils. The catalysts can also be used for the hydro and charging said sulfided compound into a hydroproc processing of shale oils, oils from tar sands and coal essing reactor zone at a temperature sufficient to con liquids. vert said sulfided compound into an active hydroproc The Group VIB metal sulfide slurry catalyst particles essing catalyst. of this invention can exist as a substantially homogene 25 More specifically, the first step in the preparation of ous dispersion in a water/oil mixture of very small parti this catalyst comprises formation of oxygen containing cles made up of extremely small crystallites. Examples generally soluble ammonium salts of molybdenum for of suitable Group VIB metals include molybdenum and sulfiding. Ammonium molybdate is a suitable soluble tungsten. Each of these metals can be present in approx salt. The ammonium molybdate can be presulfided to imately the disulfide form. However, the apparent 30 form some annonium molybdenum oxysulfide solids. atomic ratio of sulfur to metal can be greater or less than The ammonium molybdate and any oxysulfides is then 2. The preferable metal is molybdenum and the molyb sulfided with a sulfiding agent in a plurality of zones of denum catalyst will be particularly described herein. increasing temperature, including low, internediate and The catalyst is probably structured molecularly as 35 high-temperature sulfiding zones. Hydrogen sulfide, platelets formed from hexagonal sheets of molybdenum preferably with hydrogen, is a suitable sulfiding agent. or tungsten atoms separated by two hexagonal layers of Each sulfiding step replaces a portion of the oxygen sulfur atoms with activity sites concentrated at the edge associated with the molybdenum with sulfur. The low of each basal plane of the molybdenum or tungsten and intermediate temperature sulfiding zones contain atOS. water and can be operated either in the presence offeed We have found that the activity of the catalyst of this oil or in the substantial absence of feed oil. Feed oil and invention can be defined by the pore volume expressed water are both present in the high temperature sulfiding as cubic centimeters per gram (cc/g) based on pores in zone. If feed oil is not present in the low or intermediate the 10 to 300 Angstroms (A) radius size range. The temperature sulfiding zones, ammonia can be separated catalyst of this invention has at least 0.1 cc/g pore vol 45 from the system after the low or intermediate tempera ume in pores between 10 and 300A in radius; preferably ture sulfiding zones and before addition of feed oil. at least 0.15 and most preferably at least 0.2 cc/g in The final catalyst comprises crystallites of molybde pores having a radius between 10 and 300A. Catalysts of num sulfide and can be MoS2. However, frequently the this invention can have a pore volume in pores having a atomic ratio of sulfur to molybdenum is not 2 or is only 50 approximately 2. It is an exceptionally active form of radius between 10 and 300A of between 0.15 or 0.2 to 1 molybdenum sulfide or MoS2. It appears that the activ cc/g. Good activity is obtained in the range 0.2 to 0.4 ity of the final catalyst depends upon the conditions cc/g while preferably activity is obtained by extending employed during its preparation. Application Ser. No. the upper end of the range to 1 cc/g, or higher. 527,414, filed Aug. 29, 1983, now U.S. Pat. No. We have found that the catalyst of this invention can 55 4,557,821, which is hereby incorporated by reference, also be defined by its surface area expressed as square taught the presence of both feed oil and water during meters per gram (m2/g). Good activity is achieved with the majority of stages of multistage sulfiding of the a surface area of at least 20 or 2.5 m2/g.
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