||||||||||||| 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. Surface areas precursor annonium salt to molybdenum sulfide and between 25 and 75 or 100 m2/g give good catalyst activ did not teach ammonia removal during catalyst prepa ities while surface areas above 75 or 100 cc/g and up to ration. That method of catalyst preparation is referred 400 cc/g, or higher, give preferable activity. to herein as the oil method and results in a molybdenum The following equations are used to calculate the sulfide catalyst having a pore volume in pores in the 10 pore volume and surface area of the catalysts on a car to 300A radius range of between about 0.1 to about 0.4 bon-free basis. cc/g and a surface area in the range of about 20 to about 65 75 m/g. An improvement in catalyst activity can be EQUATIONS FOR PORE VOLUME AND achieved by performing a portion of the multistage SURFACE AREA sulfiding of the precursor ammonium salt in an aqueous Pore Volume, phase in the substantial absence of any hydrocarbon oil 5,094,991 3 4. and by separating ammonia from the system in advance separator zone and separated from slurry-containing of the addition of an oil phase. For example, the low separator residue in advance of the high-temperature temperature sulfiding stage or the low and intermediate sulfiding stage and prior to addition of oil. Feed oil is temperature sulfiding stages can be operated in the added to the separator residue and the separator residue absence of hydrocarbon oil. If oil is first added to the 5 with feed oil is passed to the high-temperature sulfiding intermediate temperature sulfiding stage, then ammonia Stage. can be vented after the low-temperature sulfiding stage. If the temperature in the high-temperature sulfiding If oil is first added to the high-temperature sulfiding reactor is sufficiently high for hydroprocessing metals stage, then ammonia can be vented after the intermedi containing or refractory hydrocarbon feed oil, the resi ate temperature sulfiding stage. This method is referred O dence time in the high-temperature reactor can be suffi to herein as the water method and results in a molybde cient to accomplish both the high-temperature sulfiding num sulfide catalyst having a pore volume in pores in and the required hydroprocessing reactions. If a higher the 10 to 300A unit radius range of between about 0.1 temperature is required to accomplish hydroprocessing and about 1 cc/g and a surface area of about 20 to about of the feed oil, the effluent stream from the high-tem 350 m2/g, or higher. 15 perature reactor is passed to a hydroprocessing reactor The ammonium molybdate used can be prepared by operated at a hydroprocessing temperature which is dissolving a molybdenum compound, such as Mo.O3, in higher than the temperature in the high-temperature aqueous ammonia to form annonium molybdates, with sulfiding reactor. or without the subsequent injection of hydrogen sulfide Although not to be bound by any theory, it is be to the dissolving stage. The ammonium molybdates are 20 lieved that the following reactions occur in the various generally soluble in the aqueous ammonia but the addi catalyst preparation steps described above. In the first tion of hydrogen sulfide causes some dissolved molyb catalyst preparation step, insoluble, crystalline MoC)3 is denum to separate as ammonium molybdenum oxysul mixed with water to form a non-oleaginous slurry fide solids. which is reacted with ammonia to form soluble ammo Aqueous annonium molybdenum oxysulfide from 25 nium molybdates according to the following general the dissolving stage can be mixed with all or a portion of ized equation: the feed oil stream as described below using the dis persal power of a hydrogen-hydrogen sulfide stream and the admixture can be passed through a plurality of 7MoO3 + 6NH3 + 3H2O-Ge (NH)6. Mo, O24 sulfiding zones of ascending temperature. The sulfiding 30 Insoluble Soluble zones can be three in number, to provide a time-temper Crystalline ature sequence which is necessary to complete the prep aration of the slurry catalyst prior to passing it to a The MoC)3 is dissolved under the following condi higher temperature exothermic hydroprocessing reac tions: tor Zone. Each sulfiding zone is operated at a tempera 35 ture higher than its predecessor. The residence time in NH3/Mo Weight Ratio 0.1 to 0.6; preferably 0.5 to 0.3 each sulfiding zone is sufficient to inhibit excessive Temperature, F. 33 to 350; preferably 120 to 180 coking and can be, for example, 0.02 to 0.5 hours, or Pressure: psig 0 to 400; preferably 0 to 10 more. The various sulfiding zones can employ the same or different residence times. For example, the high-tem 40 perature sulfiding reactor can employ a residence time The pressure and temperature are not critical. In of 2 hours, or more. In general, the residence time in creased pressure is required to maintain the ammonia in each sulfiding zone can be at least 0.02, 0.1 or 0.2 hours. aqueous solution at elevated temperatures. Elevated The residence time in each zone can also be at least 0.3, temperature is necessary to insure reaction and vary the 0.4 or 0.5 hours. Each sulfiding zone is constituted by a 45 concentration of molybdenum dissolved in the solution. time-temperature relationship and any single reactor The solution of ammonium molybdate, which may be can constitute one or more than one sulfiding zones presulfided to form some ammonium molybdenum oxy depending upon whether the stream is heated or is at a sulfides, is passed to a series of sulfiding reactors or constant temperature in the reactor and upon the dura zones operated at ascending temperatures. It is first tion of the stream time within a particular temperature 50 passed to a relatively low-temperature sulfiding reactor range during stream residency in the reactor. where it is contacted with gaseous hydrogen sulfide, The first sulfiding stage is operated at a relatively low preferably a hydrogen/hydrogen sulfide blend, with or temperature with an aqueous phase and with or without without feed oil. The generalized sulfiding reaction is as feed oil. The second sulfiding stage is operated at an follows: intermediate temperature which is higher than the ten 55 perature of the low-temperature sulfiding stage with an aqueous phase and either with or without feed oil. The (NH4)6MoTO24 + H2S -G (NH4)Moors, third sulfiding stage is a high-temperature stage and is amorphous operated at a temperature which is higher than the temperature in the intermediate temperature stage. It is The above is a generalized equation. The reaction performed with both an aqueous and oil phase. products in the low-temperature sulfiding reactor in The sulfiding reactions occurring in the low and clude ammonium molybdates, ammonium molybdenum intermediate temperature sulfiding stages generate am oxysulfides and possibly molybdenum sulfides. monia from gradual decomposition of annonium mo Following are the conditions in the low temperature lybdates and/or ammonium molybdenum oxysulfides. 65 sulfiding reactor: If no oil is present, this annonia, together with any excess ammonia present from the earlier reaction of SCF H2S/lbs Mo above 2.7; preferably above 12 ammonia with molybdenum oxide, can be flashed in a ratio 5,094,991 5 6 -continued be employed as the hydroprocessing reactor if the feed Temperature, "F. 70 to 350; preferably 130 to 180 oil is capable of being hydroprocessed at the tempera Hydrogen sulfide 3 to 400; preferably 150 to 250 ture of the high-temperature sulfiding reactor. How partial pressure, psi ever, feed oils commonly require hydroprocessing at temperatures above the temperature of the high-tem It is important not to exceed the above temperature perature sulfiding reactor. In such case, a downstream range in the low-temperature reactor. At temperatures hydroprocessing reactor is required. In general, the above 350 F. ammonia loss from the catalyst precursor temperature in the hydroprocessing reactor is 650 to to produce a lower ammonia entity will occur faster 950 F. and is above the temperature of the high-tem than thiosubstitution can proceed and the molybdenum O perature sulfiding reactor. compound will precipitate and possibly plug the reac The total pressure in the sulfiding zones and the hy tor. It is possible to operate the low-temperature reactor droprocessing reactor can be between about 500 and at a temperature below 325 or 350 F. for a relatively about 5,000 psi. long duration to allow the thiosubstitution reaction to If the aqueous catalyst precursor leaving the interme proceed faster than ammonia loss so that the molybde- 1 5 diate temperature reactor were to be passed together num compound rich in oxygen will not precipitate. with feed oil and hydrogen sulfide directly to a hydro The effluent stream from the low-temperature reac processing reactor operated at a temperature above the tor is passed to an intermediate temperature reactor, temperature of the high-temperature sulfiding reactor, which may or may not contain oil, operated under the such as 800 F., or above, the molybdenum compound following conditions: 20 would react with the water present to lose sulfur rather than gain it to form an inactive catalyst according to the Temperature, F. 180 to 700; preferably 300 to 550 following reaction: Hydrogen sulfide 3 to 440; preferably 150 to 250 partial pressure, psi 25 Moos, + H2O 9 Fe Moos, + The temperature in the intermediate temperature Inactive reactor is higher than the temperature in the low-tem Catalyst perature reactor. The following generalized reaction may occur in the H2S or (MoC)2/MoS2 + H2S) intermediate temperature reactor: Mixtures where y' is less than 2. This material is not a sufficiently active catalyst to inhibit coking reactions. It is noted where that the MoC)Sy(where x is about 1, y is about 2) in the x' is about 1. 35 presence of hydrogen sulfide and water reacts preferen y' is about 2. tially with the hydrogen sulfide to become sulfided at a The molybdenum compound in the intermediate tem temperature between 500 to 750 F. It has been found perature reactor is sufficiently sulfided so that upon loss that the MoS2 catalyst formed in the temperature range of ammonia it is in a particulate form which is suffi 500 to 750 F. is a low-coking catalyst. However, at a ciently fine that it can remain dispersed with sufficient temperature above this range, the Mo0S (where x is agitation. In addition, the molybdenum compound is about 1 and y is about 2) in the presence of hydrogen sufficiently sulfided that a crystalline structure is evolv sulfide and water reacts to form Moor,S, (where y' is ing from the amorphous form it exhibited in the low less than 2), which is inactive temperature sulfiding temperature reactor where its It will be appreciated that the low, intermediate and level of sulfiding was so low that a loss of ammonia 45 high-temperature sulfiding zones, stages or steps de would induce precipitation and reactor plugging. The molybdenum compound leaving the intermedi scribed herein can constitute separate reactors, as illus ate temperature sulfiding stage requires further conver trated, or some or all of these zones, stages or steps can sion of oxygen to sulfur to achieve the molybdenum be merged into a single reactor. In terms of concept, sulfide active catalyst state. This further conversion 50 each of these sulfiding zones, stages or steps is repre occurs in the presence of feed oil in a high-temperature sented by a residence time-temperature relationship. If sulfiding reactor, which is operated a temperature the stream is heated through the temperature range above the temperature of the intermediate temperature indicated above for any sulfiding zone, stage or step for sulfiding reactor. The reaction occurring in the high the time indicated above, then the performance of the temperature sulfiding reactor in the presence of an oil/- 55 process requirements to satisfy that zone, stage or step water phase may be expressed by the following equa has occurred. tion: If desired, the hydrogenation, desulfurization and denitrogenation activities of Group VIB metal catalysts of this invention can be improved by promotion with at Moos - G). MoS2 + H2O least one Group VIII metal, such as nickel or cobalt. Highly The Group VIII metal can be added to the Group VIB Active slurry catalyst in any convenient form, e.g., as water soluble inorganic salts or as organometallic compounds. where The weight ratio of Group VIII metal to Group VIB x is about 1 65 metal can be 0.001 to 0.75, generally; 0.01 to 0.03, pref. y is about 2. erably; and 0.08 to 0.20, most preferably. Examples of The high-temperature sulfiding reactor is operated at suitable water-soluble inorganic salts of Group VIII a temperature in the range 500 to 750 F. and can also metals are sulfates, nitrates, etc. Examples of suitable 5,094,991 7 8 organometallic compounds of Group VIII metals in FIG. 5 relates to the ratio of nitrogen contents in the clude naphthenates, porphyrins, etc. The Group VIII product and feed oils to the surface area of the molybde metal compound can be added to the slurry of Group num sulfide slurry catalyst; VIB metal flowing to or within the low, intermediate or FIG. 6 relates to the ratio of sulfur contents in the high-temperature sulfiding steps described herein and is product and feed oils to the surface area of the molybde preferably added to the catalyst precursor after it de num sulfide slurry catalyst; parts from the ammonia dissolving stage. FIG. 7 illustrates a flow scheme for the preparation of The catalyst preparation method described above a slurry catalyst by the water method and the use of said uses MoC3 as a starting material for preparing the cata catalyst in a hydroprocess; and lyst precursor. However, other molybdenum com 10 FIG. 8 illustrates a flow scheme for the preparation of pounds are also useful. For example, thiosubstituted a slurry catalyst by the oil method and the use of said ammonium molybdates, such as ammonium oxythi catalyst in a hydroprocess. omolybdate or ammonium thiomolybdate can be em Before referring to the figures, the following exam ployed. Since these materials are produced from MoO3 ples will further illustrate the present invention. Exam in the first two catalyst preparation steps described 15 ples 1 and 4 show the preparation of catalysts by the oil above, i.e., the reaction of MoO3 with ammonia step and method. Examples 2, 5, 8, 9, 10, 11 and 12 show the the low-temperature sulfiding step, these two steps can preparation of catalysts by the water method. Examples be by-passed by employing these thiosubstituted com 3, 6 and 7 show the preparation of catalysts by prior art pounds as starting materials. Therefore, when these methods. thiosubstituted compounds are used as catalyst precur 20 sors, a water slurry thereof can be injected with hydro EXAMPLES gen sulfide and hydrogen and passed directly to the Example 1 intermediate temperature sulfiding reactor described above, followed by separation of ammonia and then the In this example the catalyst was prepared according high-temperature sulfiding reactor and the hydroproc 25 to the oil method. The method of preparation was as essing reactor, as described above. follows: To complete the cycle for the process of slurry cata Step 1-1884.1 Grams of molybdenum trioxide (Cli lyst preparation and use as described above, it is neces max Molybdenum Grade L) was slurred in 7309.4 sary to recover and recycle the catalyst. Following the grams of distilled water. To this slurry, 1307.5 grams of hydroprocessing operation, an oil product can be re 30 ammonium hydroxide (23.2 weight percent ammonia) covered in atmospheric and vacuum distillation towers. was added and mixed well. The resulting mixture was The vacuum tower bottoms contains the catalyst, possi exposed to the following conditions: bly with contaminant metals acquired from the feed oil. Some or all of the vacuum tower bottoms is treated Temperature: "F. 150.0 with a solvent to separate non-asphaltic oils from as 35 Pressure; psia 14. phalt containing catalyst with metallic contaminants. Time: hrs 2.0 The deactivated catalyst can comprise molybdenum sulfide catalyst and can be contaminated with vana Step 2-A portion of the resultant mixture from Step dium, nickel and some iron, derived from the oil being 1 was introduced to a reactor and heated to 150.0 F. treated, all as sulfides. The catalyst-containing mixture and the pressure was increased to 35.0 psig. At this time can be passed to a combustion zone to burn off coke and a flow of 92% hydrogen - 8% hydrogen sulfide gas was asphalt and to convert the metal sulfides to the corre introduced into the reactor. The reactor was maintained sponding metal oxides of their highest stable oxidation at these conditions for 0.5 hours and at a gas flow rate state. The oxidized spent catalyst can then be passed to and for a time such that 2.7 SCF of H2S was contacted an aqueous ammonia dissolving zone to dissolve molyb 45 per pound of molybdenum. This level of presulfiding is denum in preference to the contaminating metals. not enough to decompose the molybdate formed in the Thereupon, to repeat the catalyst preparation proce first step and thus liberate a substantial amount of an dure, the resulting aqueous ammonium molybdate solu monia. At the end of this low-temperature sulfiding tion is reacted with hydrogen sulfide in a plurality of step, the reactor was cooled and depressurized; the sulfiding stages as described above to prepare a molyb 50 resulting catalyst is removed from the reactor. This denum sulfide catalyst for return to the oil hydrotreat catalyst is identified as Catalyst A. ing process. Step 3-Catalyst A was then charged with a de The present invention is illustrated by reference to canted oil, inspections of which are found in Table I, to the figures in which: a rocker-bomb reactor. The rocker-bomb reaction was 55 pressurized with a 92% hydrogen - 8% hydrogen sul BRIEF DESCRIPTION OF THE FIGURES fide gas mixture and heated to run temperature. This FIG. 1 relates to the AI gravity of a hydroprocessed heat-up period lasted about 6 hours and constituted the oil to the 10 to 300A radius pore volume in the molyb intermediate temperature sulfiding step. The high-tem denum sulfide slurry catalyst; perature sulfiding step occurred under hydroprocessing FIG. 2 relates to the ratio of nitrogen contents in the 60 conditions, which were as follows: product and feed oils to the 10 to 300A radius pore volume in the molybdenum sulfide slurry catalyst; FIG. 3 relates to the ratio of sulfur contents in the Pressures, Hydrogen: psi S- 2200.0 product and feed oils to the 10 to 300A radius pore Hydrogen Sulfide: psi 1820 volume in the molybdenum sulfide catalyst; 65 Water Vapor; psi 390.0 FIG. 4 relates to the API gravity in a hydroprocessed Temperature: "F. 720.0 oil to the surface area of the molybdenum sulfide slurry Time at Temperature: hrs 6.0 catalyst; Catalyst to Oil Ratio, 5,094,991 9 10 Step 1-Ammonium tetrathiomolybdate was pre -continued pared following the procedure described by G. Kruss Mo/Oil: wit/wt 0.042 Justus Liebigs Mann Chem., 229, 29 (1884)). 75.0 Grams of ammonium tetrathiomolybdate was slurried in 225.0 The results of this screening run are shown in Table 5 grams of distilled water. To this slurry, 417.0 cc of II under the column labeled Catalyst A. ammonium hydroxide (23.2 weight percent ammonia) was added and mixed well. The resulting mixture was EXAMPLE 2 maintained in an ice bath while the mixture was treated In this example, the catalyst was prepared according with gaseous hydrogen sulfide until blood-red crystals to the water method. The method of preparation was as 10 precipitated out. These crystals were filtered and follows: washed with cold water. Step 1-1884.1 Grams of molybdenum trioxide (Cli Step 2-The thermochemical decomposition was max Molybdenum Grade L) was slurried in 7309.4 performed following the procedure described by Taus grams of distilled water. To this slurry, 1307.5 grams of ter, Pecoraro and Chianelli Journal of Catalysis, 63, annonium hydroxide (23.2 weight percent ammonia) 15 515-519 (180). The ammonium tetra-thiomolybdate was added and mixed well. The resulting mixture was from Step 1 was decomposed by heating the material in . exposed to the following conditions: a furnace tube from 25.0 C. to 400 C. in a 120 cc/min flow of a 92% hydrogen - 8% hydrogen sulfide gas mixture over a period of 1.5 hours, when maximum Temperature: "F. 50.0 20 temperature was reached the material was allowed to Pressure: psia 14.7 cool. The gas flow was continued until the material had Time: hrs 2.0 cooled to 25 C. The furnace was nitrogen swept and the material was removed. This catalyst as identified as Step 2-A portion of the resultant mixture from Step Catalyst C. 1 was introduced to a reactor and heated to 150.0 F. 25 Step 3-Catalyst C was then charged with the de and the pressure was increased to 2500.0 psig. At this canted oil of Table I to a rocker-bomb reactor. The time a flow of a 92% hydrogen - 8% hydrogen sulfide rocker-bomb reactor was pressurized with a 92% hy gas was introduced into the reactor. After a 0.5 hours drogen - 8% hydrogen sulfide gas mixture and heated to time period the temperature was increased to 450 F. run temperature. Operating conditions were as follows: and maintained for 0.5 hours. At the end of this period 30 the gas flow was stopped and the pressure was reduced to 750.0 psig while maintaining temperature, this hold cycle was held for 0.5 hours. At the end of this sulfiding Pressures, Hydrogen: psi 2200.0 step, the reactor was cooled and depressurized and Hydrogen Sulfide: psi 182.0 gaseous annonia was flashed off. The gas flow rate and 35 Water Vapor: psi 390.0 time of reaction were such that at least 10.5 SCF of H2S Temperature: "F. 720.0 was contacted per pound of molybdenum. This level of Time at Temperature: hrs 6.0 sulfiding is sufficient to decompose the molybdate Catalyst to Oi Ratio, formed in the first step, therefore liberating a substantial Mo/Oil: wit/wt 0.042 amount of ammonia. The resulting catalyst was re moved from the reactor. This catalyst is identified in The results of this screening run are shown in Table II Catalyst B. under the column labeled Catalyst C. Step 3-Catalyst B was then charged with the de canted oil of Table I to a rocker-bomb reactor. The EXAMPLE 4 rocker-bomb reactor was pressurized with a 92% hy- 45 In this example, the catalyst was prepared according drogen - 8% hydrogen sulfide gas mixture and heated to to the oil method utilizing acidic decomposition of an run temperature. This heat-up period lasted about 6 monium tetra-thiomolybdate to form molybdenum tri hours and constituted the high-temperature sulfiding sulfide. The preparation was as follows: step. Hydroprocessing then occurred under the follow ing conditions: 50 Pressures, Hydrogen; psig 2200.0 Pressures, Hydrogen Sulfide: psi 182.0 Hydrogen; psi 2200.0 Water Vapor: psi 390.0 Hydrogen Sulfide: psi 182.0 Temperature: "F. 720.0 Water Vapor; psi 390.0 55 Time at Temperature: hrs 6.0 Temperature: "F. 720.0 Catalyst to Oil Ratio, Time at Temperature: hrs 6.0 Mo/Oil: wit/wt 0.042 Catalyst to Oil Ratio Mo/Oil: wit/wt 0.042 The results of this screening run are shown in Table 60 II under the column labeled Catalyst D. The results of this screening run are shown in Table II under the column labeled Catalyst B. Example 5 In this example, the catalyst was prepared according EXAMPLE 3 to the water method utilizing acidic decomposition of In this example, the catalyst is a prior art catalyst and 65 ammonium tetra-thiomolybdate to form molybdenum was prepared by thermochemical decomposition of trisulfide. The preparation was as follows: annonium tetra-thiomolybdate. The preparation was Step l-Ammonium tetrathiomolybdate was pre as follows: pared following the procedure described by G. Kruss 5,094,991 11 12 Justus Liebigs Nann Chem., 229, 29 (1884)). 75.0 Grams atmosphere. The precipitate (MoS3) was filtered and of ammonium tetrathiomolybdate was slurried in 225.0 washed with water. This formic acid decomposition grams of distilled water. To this slurry, 417.0 cc of method is described in Tauster, Pecoraro, and Chianelli ammonium hydroxide (23.2 weight percent ammonia) Journal of Catalysis, 63,515-519 (1980). was added and mixed well. The resulting mixture was Step 2-The thermochemical decomposition was maintained in an ice bath while the mixture was treated performed following the procedure described by Taus with gaseous hydrogen sulfide until blood-red crystals ter, Pecoraro and Chianelli Journal of Catalysis, 63, precipitated out. These crystals were filtered and 515-519 (1980). The molybdenum trisulfide from Step washed with cold water. 100 Grams of the resultant 1 was decomposed by heating the material in a furnace crystals were redispersed in 165.9 grams of distilled O tube from 25 C. to 400 C. in a 120-cc/min flow of a water. To this slurry and while stirring, 51.1 grams of 92% hydrogen - 8% hydrogen sulfide gas mixture over formic acid, 90 percent by weight, were added. The a period of 1.5 hours, when maximum temperature was resultant mixture was heated at 50° C. for 0.5 hours reached the material was allowed to cool. The gas flow under a nitrogen atmosphere. The precipitate (MoS3) was continued until the material had cooled to 25 C. was filtered and washed with water. 15 The furnace was nitrogen-swept and the material was This formic acid decomposition method is described removed. This catalyst is identified as Catalyst F. in Tauster, Pecoraro, and Chianelli Journal of Catalysis, Step 3-Catalyst F was then charged with the de 63, 515-519 (1980). The precipitate was then redis canted oil of Table I to a rocker-bomb reactor. The persed in distilled water. rocker-bomb reactor was pressurized with a 92% hy Step 2-The resultant slurry was introduced to a 20 drogen - 8% hydrogen sulfide gas mixture and heated to reactor, pressured to 2300 psig with 92% H2-8% H2S run temperature. Operating conditions were as follows: gas and heated to 300 F. The reactor was maintained at these conditions for 0.5 hours. At the end of this inter mediate temperature sulfiding step, the reactor is cooled and depressurized. The resulting catalyst was filtered 25 Pressures, Hydrogen; psi 2200.0 and redispersed in distilled water. This catalyst is identi Hydrogen Sulfide: psi 82.0 fied as Catalyst E. Water Vapor: psi 390.0 Step 3-Catalyst E was then charged with a decanted Temperature: "F. 20.0 oil, inspections of which are found in Table I, to a rock Time at Temperature: hrs 6.0 er-bomb reactor. The rocker-bomb reactor was pressur 30 Catalyst to Oil Ratio, ized with a 92% hydrogen - 8% hydrogen sulfide gas Mo/Oil: wit/wt 0.042 mixture and heated to run temperature. This heat-up period lasted about 6 hours and constituted a high-tem The results of this screening run are shown in Table II perature sulfiding step, The high-temperature sulfiding under the column labeled Catalyst F. step continued under hydroprocessing conditions, 35 which were as follows: EXAMPLE 7 The catalyst of this example is suspension grade mo lybdenum disulfide (Climax Molybdenum Disulfide Pressures, Hydrogen: psi 2200.0 Suspension Grade) of the prior art. There was no prepa Hydrogen Sulfide: psi 182.0 ration necessary for the catalyst. The material was used Water Vapor: psi 3900 as received. This catalyst is identified as Catalyst G. Temperature: F. 720.0 Catalyst G was then charged with the decanted oil of Time at Temperature: hrs 6.0 Table I to a rocker-bomb reactor. The rocker-bomb Catalyst to Oil Ratio, reactor was pressurized with a 92% hydrogen - 8% Mo/Oil: wawt 0.042 45 hydrogen sulfide gas mixture and heated to run temper ature. Operating conditions were as follows: The results of this screening run are shown in Table II under the column labeled Catalyst E. Pressures, EXAMPLE 6 Hydrogen: psi 2200.0 50 Hydrogen Sulfide: psi 182.0 In this example, the catalyst was prepared by the Water Vapor: psi 390.0 prior art method of thermochemical decomposition of Temperature: "F. 7200 molybdenum trisulfide. The preparation was as follows: Time at Temperature: hrs 6.0 Step l-Ammonium tetrathiomolybdate was pre Catalyst to Oil Ratio, pared following the procedure described by G. Kruss 55 MoAOil: witAwt 0.042 Justus Liebigs Nann Chem, 229, 29 (1884). 75.0 Grams of ammonium tetrathiomolybdate was slurried in 225.0 The results of this screening run are shown in Table grams of distilled water. To this slurry 417.0 cc of an II under the column labeled Catalyst G. monium hydroxide (23.2 weight percent ammonia) was added and mixed well. The resulting mixture was main Example 8 tained in an ice bath while the mixture was treated with In this example, the catalyst was prepared according gaseous hydrogen sulfide until blood-red crystals pre to the water method. The preparation was as follows: cipitated out. These crystals were filtered and washed Step 1-4.15 Pounds of molybdenum trioxide (Cli with cold water. 100 Grams of the resultant crystals max Molybdenum Grade L) was slurried in 16.1 pounds were redispersed in 165.9 grams of distilled water. To 65 of distilled water. To this slurry, 2.88 pounds of ammo this slurry and while stirring, 51.1 grams of formic acid, nium hydroxide (25.1 weight percent ammonia) was 90 percent by weight, were added. The resultant mix added and mixed well. The resulting mixture was ex ture was heated at 50° C. for 0.5 hours under a nitrogen posed to the following conditions: 5,094,991 13 14 Example 10 Temperature: "F. 150.0 In this example, the catalyst was prepared according Pressure; psia 14.7 to the water method and is a duplicate of Example 9. the Time: hrs 2.0 preparation was as follows: Step 1-4.15 Pounds of molybdenum trioxide (Cli Step 2-The resultant mixture from Step 1 was intro max Molybdenum Grade L) was slurried in 16.1 pounds duced to a reactor and heated to 200 F. and the pres of distilled water. To this slurry, 2.88 pounds of ammo sure was increased to 400.0 psig. At this time a 14.0 nium hydroxide (25.1 weight percent ammonia) was SCFH flow of a 92% hydrogen - 8% hydrogen sulfide 10 added and mixed well. gas was introduced into the reactor. At the end of this The resulting mixture was exposed to the following low-temperature sulfiding step, the reactor was depres conditions: surized and gaseous ammonium was flashed off. The resulting catalyst is removed from the reactor. This 15 Temperature: "F. 150.0 catalyst is identified as Catalyst H. Pressure: psia 14. Time: hrs 2.0 Example 9 In this example, the catalyst was prepared according Step 2-A portion of the resultant mixture from Step to the water method. The preparation was as follows: 20 1 was introduced to a reactor and heated to 150 F. and Step 1-4.15 Pounds of molybdenum trioxide (Cli the pressure was increased to 400.0 psig. At this time a max Molybdenum Grade L) was slurried in 16.1 pounds 14.0 SCFH flow of a 92% hydrogen-8% hydrogen of distilled water. To this slurry, 2.88 pounds of ammo sulfide gas was introduced into the reactor. The reactor nium hydroxide (25.1 weight percent ammonia) was was maintained at these conditions for 6.0 hours. At the 25 end of this low-temperature sulfiding step, the reactor is added and mixed well. The resulting mixture was ex depressurized and gaseous ammonia was flashed off. posed to the following conditions. The resulting catalyst is removed from the reactor. This catalyst is identified as Catalyst J. Temperature: "F. 150.0 Step 3-Catalyst J was then charged with the de Pressure: psia 14.7 30 canted oil of Table I to a rocker-bomb reactor. The Time: hrs 2.0 rocker-bomb reactor was pressurized with a 92% hy drogen - 8% hydrogen sulfide gas mixture and heated to run temperature. This heat-up period lasted about 6 Step 2-The resultant mixture from Step 1 was intro hours and constituted both the intermediate and high duced to a reactor and heated to 150 F. and the pres 35 temperature sulfiding steps because both the intermedi sure was increased to 400 psig. At this time a 14.0 SCFH ate and high-temperature sulfiding temperature ranges flow of a 92% hydrogen-8% hydrogen sulfide gas was were traversed for the designated durations. The high introduced to the reactor. The reactor was maintained temperature sulfiding step continued under hydroproc at these conditions for 6.0 hours. At the end of this low-temperature sulfiding step, the reactor is depressur essing conditions, which are as follows: ized and gaseous ammonia was flashed off. The result ing catalyst is removed from the reactor. This catalyst is Pressures, Hydrogen; psi 2200.0 identified as Catalyst I. Hydrogen Sulfide: psi 182.0 Step 3-Catalyst I was then charged with the de Water Vapor: psi 390.0 canted oil of Table I to a rocker-bomb reactor. The 45 Temperature: "F. 720.0 rocker-bomb reactor was pressurized with a 92% hy Time at Temperature: hrs 6.0 drogen - 8% hydrogen sulfide gas mixture and heated to Catalyst to Oil Ratio, run temperature. This heat-up period lasted about 6 Mo/Oil: wit/wt 0.042 hours and constituted both the intermediate and high SO temperature sulfiding steps because both the intermedi The results of this screening run are shown in Table ate and high-temperature sulfiding temperature ranges II under the column labeled Catalyst J. were traversed for the designated durations. The high Example 11 temperature sulfiding step continued under hydroproc In this example, the catalyst was prepared according essing conditions, which are as follows: 55 to the water method. The preparation was as follows: Step 1-0.63 Pounds of molybdenum trioxide (Climax Pressures,- Molybdenum Grade L) was slurried in 2.73 pounds of Hydrogen: psi 2200.0 distilled water. To this slurry, 0.23 pounds of ammo Hydrogen Sulfide: psi 182.0 nium hydroxide (25.1 weight percent ammonia) was Water Vapor: psi 390.0 added and mixed well The resulting mixture was ex Temperature: "F. 720.0 posed to the following conditions: Time at Temperature: hrs 6.0 Catalyst to Oil Ratio, Mo/Oil: wit/wt 0.042 Temperature: "F. 150.0 65 Pressure: psia 4.7 Time: hrs 2.0 The results of this screening run are shown in Table Step 2-A portion of the resultant mixture from Step 1 II under the column labeled Catalyst I. was introduced to a reactor and heated to 150' F. and 5,094,991 15 16 the pressure was increased to 400 psig. At this time a Step 2-A portion of the resultant mixture from Step 14.0 SCFH flow of a 92% hydrogen - 8% hydrogen 1 was introduced to a reactor and heated to 150 F. and sulfide gas was introduced into the reactor. The reactor the pressure was increased to 400.0 psig. At this time a was maintained at these conditions for 8.0 hours. At the 14.0 SCFH flow of a 92% hydrogen - 8% hydrogen end of this low-temperature sulfiding step, the reactor is 5 sulfide gas was introduced into the reactor. The reactor depressurized and ammonia was flashed off. The result was maintained at these conditions for 8 hours. At the ing catalyst is removed from the reactor. This catalyst is end of this low-temperature sulfiding step, the reactor is identified as Catalyst K. depressurized and ammonia was flashed off. The result Step 3-Catalyst K was then charged with the de ing catalyst is removed from the reactor. This catalyst is canted oil of Table I to a rocker-bomb reactor. The 10 identified as Catalyst L. rocker-bomb reactor was pressurized with a 92% hy Step 3-Catalyst L was then charged with the de drogen - 8% hydrogen sulfide gas mixture and heated to canted oil of Table I to a rocker-bomb reactor. The run temperature. The heat-up period lasted about 6 rocker-bomb reactor was pressurized with a 92% hy hours and constituted the intermediate and high-tem drogen - 8% hydrogen sulfide gas mixture and heated to perature sulfiding steps because both the intermediate 15 run temperature. This heat-up period lasted about 6 and high-temperature sulfiding temperature ranges wee hours and constituted the intermediate and high-tem traversed for the designated durations. The high-tem perature sulfiding steps because both the intermediate perature step was continued under hydroprocessing and high-temperature sulfiding temperature ranges conditions which were as follows: were traversed for the designated durations. The high 20 temperature sulfiding step was continued under hydro Pressures, processing conditions, which were as follows: Hydrogen: psi 2200.0 Hydrogen Sulfide: psi 182.0 Water Vapor: psi 390.0 Pressures, Temperature: "F. 720.0 25 Hydrogen; psi 2200.0 Time at Temperature: hrs 6.0 Hydrogen Sulfide: psi 182.0 Catalyst to Oil Ratio, Water Vapor; psi 390.0 Temperature: "F. 720.0 Mo/Oil: wit/wt 0.042 Time at Temperature: hrs 6.0 Catalyst to Oil Ratio, The results of this screening run are shown in Table 30 Mo/Oil: wit/wt 0.042 II under the column labeled Catalyst K. The results of this screening run are shown in Table Example 12 II under the column labeled Catalyst L. In this example, the catalyst was prepared according TABLE I to the water method. The preparation was as follows: 35 Oil F Step 1-0.63 Pounds of molybdenum trioxide (Cli- FCC Decanted Oil Feedstock max Molybdenum Grade L) was slurried in 2.73 pounds API Gravity S.0 off distidistilled water. To this slurry, 0.16 pounds of ammo- Sulfur:Hydrogen: w %wt % 8.371. nium hydroxide (25.1 weight percent ammonia) WaS Nitrogen: wppm 846.0 added and mixed well. The resulting mixture was ex- 40 Distillation: 'F. - posed to the following conditions: 10% 662 30% 70 50% 732 Temperature: "F. 1500 70% 78 Pressure: psia 14.7 90% 887 Time: hrs 2.0 45

TABLE II Slurry Catalytic Processing Example Number: 1 2 3 4. 5 6 7 8 9 0 11 12 Catalyst Designation: A B C D E F G H I K L Prior Prior Prior Preparation Method: Oil Water Art Oil Water Art Art Water Water Water Water Water Product Quality: API Gravity 13.0 17.4 10.4 10.9 11.5 8.8 9.4 6.1 7.0 16.4 19.0 19.5 Sulfur, wt.% 0.52 0.16 0.68 0.70 0.65 0.84 0.8 0.26 0.12 0.16 0.09 0.07 Nitrogen, ppm 116 8 290 255 230 533 57 18 S 8 7 6 Hydrogen, wt.% 9.79 11.19 9.53 9.52 9.71 9.04 9.29 10.60 10.92 10:48 10,93 .29 Catalyst: Sulfur/Molybdenum Ratio 2.0 1.5 1.8 2.1 1.8 2. 1.8 1.8 1.0 2.2 1.9 2.7 Carbon, wt.% 15.8 8.2 5.6 6.0 12. 3.1 2.4 13.2 12.0 1.2 15.1 17.1 Spent Catalyst: BET Surface Area, m/g 43.5 44.4 7.3 23.4 39.4 7.3 0.7 76.3 74.6 75.8 282. 29.6 Avg. Pore Radius, A 54 37 49 31 30 52 62 29 23 25 27 36 Pore Volune, cc/g.: 10-300A 0.17 0.264 0.018 0.036 0.208 1.019 0.033 0.09 0.087 0.094 0.38 0.519 Crystallite Thickness, A Angle 28 = 19' (XRD) 22 24 24 14 432 557 13 16 19 Particle Diameter, micron 10.6 4.5 4.4 4.8 4.S. 7.6 2.5 4.8 5.1 11.8 5.0 9. 5,094,991 17 18 TABLE II-continued Slurry Catalytic Processing Example Number: l 2 3 4 5 6 7 8 9 O 2 Catalyst Designation: A. B C D E F G H I K L Prior Prior Prior Preparation Method: Oil Water Art Oil Water Art Art Water Water Water Water Water Carbon-Free Basis: BET Surface Area, m2/g 52 157 8 28 159 8 11 88 85 85 332 352 Avg. Pore Radius, A 26 48 203 168 47 137 107 63 55 54 38 47 Pore Volume, cc/g.: 10–300A Radius 0.327 0.377 0.078 0.233 0.374 0.052 0.058 0.278 0.235 0.232 0.627 0.823 Pore Size Distribution: A Radius: 250-300 15.6 12.7 15.4 7.3 4.0 19.6 12.0 7.2 4.0 4.3 6.3 5.5 200-250 9.6 13.0. 7.5 7.9 4.6 18.5 12.7 10.0 5.2 5.0 4.5 5.3 S0-200 13.9 19.5 25.6 12.7 6.3 23.5 19.4 9.8 6.0 7.0 8.3 8.9 00-50 6.2 26.7 15.6 12.5 9.7 18.7 16.1 10.5 7.7 10.4 8.2 14.8 90-100 3.2 5.1 4.1 3.7 2.3 3.8 3.9 2.7 2.7 2.4 2.0 3.3 80-90 4.6 5.6 3.8 3.3 2.7 2.5 4.6 2.3 2.7 3.0 2.2 3.5 70-80 5.3 5.3 3.5 3.0 2.7 9 4.6 2.3 2.6 3.6 2.2 2.8 60-70 6.2 4.5 4.4 4.5 2.7 3.4 3.8 2.8 4.3 3.5 2.7 3.1 50-60 6. 4.5 3.0 4.9 4.3 4.3 3.9 3.6 4.9 4.6 3.3 4.0 40-50 5.1 2.3 2.8 5.7 6. 2.8 3.9 4.4 6.0 6.0 4.5 4.9 30-40 4.1 0.7 3.2 6.2 7.7 .0 4.4 5.9 7.6 8.3 6.8 6.5 20-30 4.9 0.0 1.0 7. 13.8 0.0 4.3 10.9 4.0 12.1 11.6 10.3 10-20 5.2 0.0 0.0 21.2 33.0 0.0 6.5 27.5 32.3 29.8 37.2. 26.9 Total 100.0 99.9 99.9 100.0 99.9 100.0 00.1 99.9 100.0 100.0 99.8 99.8 Table I shows specifications including API gravity, FIGS. 4, 5 and 6 show that the catalysts prepared by sulfur content and nitrogen content of the FCC de- prior art methods have the lowest surface area while canted oil feed-stock hydroprocessed in the tests of the catalysts prepared by the oil method have a higher above examples. 30 surface area and the catalysts prepared by the water Table II shows specifications including API gravity, sequential sulfiding method have by far the highest sulfur content and nitrogen content of the oil after hy- surface areas. droprocessing. These results are presented graphically FIGS. 4, 5 and 6, respectively, show that the indi in FIGS. 1 through 6 for all the examples, except Exam- cated surface areas are generally correlatable to prod ple 5. The results of Example 5 are unaccountably er-35 uct API gravity, ratio of product to feed nitrogen levels ratic and therefore are not included in the figures. and ratio of product to feed sulfur levels. FIG. 4 shows FIGS. 1, 2 and 3 show that the catalysts prepared by that the prior art catalyst, which has by far the lowest prior art methods have the smallest 10 to 300A radius surface area, provides by far the lowest product API pore volume while catalysts prepared by the oil and gravity. FIG. 4 shows that the catalyst prepared by the water sequential sulfiding methods of this invention 40 oil method, which has an intermediate surface area, have higher 10 to 300A radius poor volumes. The indi- provides an intermediate product API gravity. Finally, cated ore volumes for the oil and water methods over- FIG. 4 shows that the catalyst prepared by the water lap, but certain of the catalysts prepared by the water method, which has the highest surface area, provides method have the highest indicated pore volumes. the highest API gravity. FIGS. 1, 2 and 3 show that the indicated ore volumes 45 FIG. 5 shows that the catalyst prepared by the prior are generally correlatable to product API gravity, to art method, which has the lowest surface area, provides the ratio of product to feed nitrogen levels and to the the highest product nitrogen level. FIG. 5 shows that ratio of product to feed sulfur levels, respectively. In the catalyst prepared by the oil method, which has an each figure, the poorest results are obtained with the intermediate surface area, provides a lower product prior art catalyst, which has the lowest 10 to 300A 50 nitrogen level. Finally, FIG. 5 shows that the catalyst radius pore volume. FIG. 1 shows that the prior art prepared by the water method, which has by far the catalyst provides the lowest product API gravity. FIG. largest surface area, provides by far the lowest product 2 shows that the prior art catalyst provides the highest nitrogen level. FIG. 6 shows that the prior art catalyst, product nitrogen levels. FIG.3 shows that the prior art which has the lowest surface are, a provides the highest catalyst provides the highest product sulfur levels. 55 product sulfur level. FIG. 6 shows that the catalyst FIGS. 1, 2 and 3, respectively, show that improved prepared by the oil method, which has an intermediate product API gravity, nitrogen and sulfur levels are surface area, provides a lower product sulfur level. obtained with the catalyst prepared by the oil method, Finally, FIG. 6 shows that the catalyst prepared by the which has an intermediate 10 to 300A radius pore vol- water method, which has by far the largest surface area, ume. FIGS. 1, 2 and 3 show that the oil method catalyst 60 provides by far the lowest product sulfur level. provides an intermediate product API gravity and in- FIGS. 1, 2 and 3 indicate that to provide high catalyst termediate product nitrogen and sulfur levels. FIGS. 1, activity, the 10 to 300A radius pore volume (cc/g) of 2 and 3 show that the best results are obtained with the catalyst should be at least 0.1, preferably at least 0.15 those catalysts prepared by the water method which and most preferably at least 0.2. The indicated pore have the highest 10 to 300A radius pore volumes. FiGS. 65 volume range can be between 0.2 and 0.4, but is gener 1, 2 and 3, respectively, show that the water method ally between 0.15 and 1, preferably between 0.2 and 1 catalyst provides the highest product API gravity and and most preferably between 0.3, 0.4 or 0.5 and 1, or the lowest product nitrogen and sulfur levels. higher than 1. 5,094,991 19 20 FIGS. 4, 5 and 6 indicate that to provide high catalyst ate temperature sulfiding zone 30. In high-temperature activity the surface area (m2/g) of the catalyst should be sulfiding zone 48, molybdenum oxysulfide or tungsten generally at least 20, preferably at least 25 and most oxysulfide is converted to highly active molybdenum preferably at least 50 or 100. The surface area range can sulfide or tungsten sulfide. The preparation of the cata be between 25 and 75, but is generally between 20 and lyst is now complete. Some hydroprocessing of the feed 400, preferably between 25 and 400 and most preferably oil entering through line 40 is performed in high-tem between 75 and 400, or higher than 400. perature sulfiding zone 48. The water method for preparing a catalyst of this High-temperature sulfiding zone 48 is operated at a invention is illustrated in the FIG.7. According to FIG. temperature higher than the temperature in intermedi 7, molybdenum or tungsten, in the form of water-insolu 10 ate temperature sulfiding zone 30. In high-temperature ble Mo03 or WO3, is introduced through lines 10 and 12 sulfiding zone 48, molybdenum oxysulfide or tungsten to dissolver zone 14. Recycle molybdenum or tungsten, oxysulfide is converted to highly active molybdenum from a source described below, is introduced through sulfide or tungsten sulfide. The preparation of the cata line 16. Water and ammonia are added to dissolver zone lyst is now complete. Some hydroprocessing of the feed 14 through line 18. Water-insoluble molybdenum oxide 15 oil entering though line 40 is performed in high-temper or tungsten oxide is converted to a water-soluble ammo ature sulfiding zone 48. nium molybdate salt or ammonium tungstate salt in An effluent stream from high-temperature sulfiding dissolver zone 14. zone 48 is passed through lines 50 and 52 to hydroproc Aqueous ammonium molybdate or ammonium tung essing reactor 56. Hydroprocessing reactor 56 is oper state containing excess ammonia is discharged from 20 zone 14 through line 20, admixed with hydrogen sul ated at a temperature higher than the temperature in fide, preferably mixed with hydrogen, entering through high-temperature sulfiding zone 48. If the slurry cata line 22 and then passed through line 24 to low-tempera lyst bypassed high-temperature sulfiding zone 48 enr ture sulfiding zone 26. In low-temperature sulfiding oute to hydroprocessing reactor 56, the high-tempera zone 26, ammonium molybdate or annonium tungstate 25 ture of hydroprocessing reactor 56 would cause the is converted to thiosubstituted ammonium molybdates - water in hydroprocessing reactor 56 to oxygenate the or thiosubstituted ammonium tungstates. In zone 26 the catalyst and compete with sulfiding, thereby causing sulfiding temperature is sufficiently low that the ammo the catalyst to be converted into a sulfur-deficient high nium salt is not decomposed while thiosubstitution is coke producer. When high-temperature sulfiding zone beginning. If the ammonium salt were decomposed in 30 48 precedes the hydroprocessing reactor, the relatively the early stages of thiosubstitution, an insoluble molyb lower temperature in zone 48 allows the sulfiding reac date or oxythiomolybdate in a mixture with MoC)3, or tion to prevail over any competing oxidation reaction in an insoluble tungstate or oxythiotungstate in a mixture the presence of water to complete the sulfiding of the with WoO3 would precipitate out, inhibiting further catalyst and render it stable at the higher temperature of thiosubstitution. 35 hydroprocessing zone 56. With certain oil feedstocks, An effluent stream from low-temperature sulfiding the relatively lower temperature of high-temperature zone 26 is passed through line 28 to intermediate tem sulfiding zone 48 will suffice for performing the oil perature sulfiding zone 30. Intermediate temperature hydroprocessing reactions, in which case hydroprocess sulfiding zone 30 is operated at a temperature higher ing reactor 56 can be dispensed with. However, most than the temperature in low-temperature sulfiding zone feed oils will require the relatively higher temperature 26. The sulfiding reaction is continued in zone 30 and in hydroprocessing reactor 56 to complete the oil hy ammonium oxythiomolybdate or ammonium oxythi drotreating reactions. otungstate is converted to molybdenum oxysulfide or An effluent stream is removed from hydroprocessing tungsten oxysulfide and/or molybdenum trisulfide or reactor 56 through line 60 and passed to flash separator tungsten trisulfide, thereby freeing ammonia. 45 62. An overhead gaseous stream is removed from sepa An effluent stream from intermediate temperature rator 62 through line 64 and is passed through a scrub sulfiding zone 30 is passed through line 32 to ammonia ber 66 wherein impurities such as ammonia and light separator or flash chamber 36. In flash separator 36, hydrocarbons are removed and discharged from the cooling and depressurizing of the effluent stream from system through line 68. A stream of purified hydrogen line 32 causes vaporization of ammonia and hydrogen 50 and hydrogen sulfide is recycled through lines 70, 44 sulfide, which are discharged through line 33. Flash and 46 to high-temperature sulfiding reactor 48. conditions are established so that only a minor amount A bottoms oil is removed from separator 62 through of water is vaporized and sufficient water remains in the line 72 and passed to atmospheric distillation tower 74. flash residue to maintain an easily pumpable slurry sus As indicated in the figure, various fractions are sepa pension of the catalyst. 55 rated in tower 74 including a refinery gas stream, a Flash separator residue is removed from flash separa C3/C4 light hydrocarbon stream, a naphtha stream, a tor 36 through line 38. The flash residue in line 38 is No. 2 fuel oil and a vacuum charge oil stream for pas essentially free of oil since no oil was introduced to sage to a vacuum distillation tower, not shown. low-temperature sulfiding zone 26 or intermediate ten A concentrated catalyst slurry stream is removed perature sulfiding zone 30. Feed oil is introduced to the from the bottom of tower 74 through line 76. Some of system for the first time through line 40 and is admixed this catalyst-containing stream can be recycled to hy with a hydrogen-hydrogen sulfide mixture entering droprocessing reactor 56 through lines 58 and 52, if through lines 42 and 44. The flash residue in line 38 desired. Most, or all, of the heavy catalytic slurry in line together with feed oil, hydrogen and hydrogen sulfide 76 is passed to deasphalting chamber 78 from which a is introduced through line 46 to high-temperature sul 65 deasphalted oil is removed through line 81. A highly fiding zone 48. concentrated deactivated catalyst stream is removed High-temperature sulfiding zone 48 is operated at a from deasphalting chamber 78 through line 80 and temperature higher than the temperature in intermedi passed to catalyst generation zone 82. 5,094,991 21 22 The catalyst entering regeneration zone 82 comprises fide and/or tungsten trisulfide, thereby freeing ammo molybdenum sulfide or tungsten sulfide together with a. impurity metals acquired from the feed oil. The impu An effluent stream from intermediate temperature rity metals comprise primarily vanadium sulfide and sulfiding zone 134 is passed through line 136 to high nickel sulfide. In regeneration chamber 82 all of the temperature sulfiding zone 138. High-temperature sul metal sulfides are oxidized by combustion to the oxide fiding zone 138 is operated at a temperature higher than state. The metal oxides are then passed through line 84 the temperature in intermediate temperature sulfiding to catalyst reclamation zone 86. In reclamation zone 86 zone 134. In high-temperature sulfiding zone 138, no molybdenum oxide or tungsten oxide is separated from lybdenum oxysulfide or tungsten oxysulfide is con impurity metals including vanadium oxide and nickel O verted to highly active molybdenum sulfide or tungsten oxide by any suitable means. Non-dissolved impurity sulfide. The preparation of the catalyst is now complete. metals including vanadium and nickel are discharged Some hydroprocessing of the feed oil entering through from the system through line 88 while purified and line 126 is performed in high-temperature sulfiding zone concentrated molybdenum oxide or tungsten oxide is 138. passed through line 16 for mixing with nake-up molyb 15 An effluent stream from high-temperature sulfiding denum or tungsten oxide entering through line 10, to zone 138 is passed through lines 140 and 142 to hydro repeat the cycle. processing reactor 144. Hydroprocessing reactor 144 is If desired, the process shown in FIG. 7 can be modi operated at a temperature higher than the temperature fied by inserting ammonia flash chamber 36 in advance in high-temperature sulfiding zone 138. If the slurry 20 catalyst bypassed high-temperature temperature reactor of intermediate temperature sulfiding reactor 30. In that 138 enroute to hydroprocessing reactor 144, the high case, the hydrogen and hydrogen sulfide mixture in line temperature of hydroprocessing reactor 144 would 42 and the feed oil in line 40 can be charged to interme cause the water in hydroprocessing reactor 144 to oxy diate temperature sulfiding reactor 30. The effluent genate the catalyst and compete with sulfiding thereby from intermediate temperature sulfiding reactor 30 then 25 causing the catalyst to be converted into a sulfur-defi would be passed directly to high-temperature sulfiding cient high coke producer. When high-temperature sul reactor 48, without any intermediate separation. fiding zone 138 precedes the hydroprocessing reactor, FIG. 8 illustrates a process for preparing a catalyst by the relatively lower temperature in zone 138 allows the the oil method As shown in FIG. 8, catalytic molybde sulfiding reaction to prevail over any competing oxida num or tungsten, in the form of water-insoluble MoC)3 30 tion reaction in the presence of water to complete the or. WoO3, is introduced through lines 110 and 112 to sulfiding of the catalyst and render it stable at the higher dissolver zone 114. Recycle molybdenum or tungsten, temperature of hydroprocessing zone 144. With certain from a source described below, is introduced through oil feedstocks, the relatively lower temperature of high line 116. Water and annonia are added to dissolver temperature sulfiding zone 138 will suffice for perform zone 114 through line 118. Water-insoluble molybde 35 ing the oil hydroprocessing reactions, in which case num oxide or tungsten oxide is converted to water solu hydroprocessing reactor 144 can be dispensed with. ble ammonium molybdate salts or ammonium tungstate However, most feed oils will require the relatively salts in dissolver zone 114. higher temperature in hydroprocessing reactor 144 to Aqueous annonium molybdate or ammonium tung complete the oil hydrotreating reactions. state containing excess ammonia is discharged from An effluent stream is removed from hydroprocessing zone 114 through line 120 and then passed through reactor 144 through line 146 and passed to flash separa presulfiding zone 121 to which hydrogen sulfide is tor 148. An overhead gaseous stream is removed from added through line 123. The effluent from zone 121 is separator 148 through line 150 and is passed through a passed through line 125 and admixed with hydrogen scrubber 152 wherein impurities such as annonia and and hydrogen sulfide entering through lines 122 and 124 45 light hydrocarbons are removed and discharged from and feed oil entering through line 126 and then passed the system through line 154. A stream of purified hydro through line 128 to low-temperature sulfiding zone 130. gen and hydrogen sulfide is recycled through lines 156, In low-temperature sulfiding zone 130, ammonium mo 124 and 128 to low-temperature sulfiding reactor 130. lybdate or ammonium tungstate is converted to thiosub A bottoms oil is removed from separator 148 through stituted annonium molybdates or thiosubstituted an 50 line 158 and passed to atmospheric distillation tower monium tungstates. In low-molybdates temperature 160. Various fractions are separated in tower 160 in sulfiding zone 30 the sulfiding temperature is suffi cluding a refinery gas stream, a C3/C4 light hydrocar ciently low that the ammonium salt is not decomposed bon stream, a naphtha stream, a No. 2 fuel oil and a while thiosubstitution is beginning. If the ammonium vacuum charge oil stream for passage to a vacuum salt were decomposed in the early stages of thiosubstitu 55 distillation tower, not shown. tion, an insoluble molybdate or oxythiomolybdate in a A concentrated catalyst slurry stream is removed mixture with MoC3, or an insoluble tungstate or oxythi from the bottom of tower 160 through line 162. Some of otungstate or in a mixture with WO3 would precipitate this catalyst-containing stream can be recycled to hy out in zone 130 and tend to plug zone 130. droprocessing reactor 144 through lines 162 and 164, if An effluent stream from low-temperature sulfiding desired. Most, or all, of the heavy catalytic slurry in line zone 130 is passed through line 132 to intermediate 162 is passed through line 166 to deasphalting chamber temperature sulfiding zone 134. Intermediate tempera 168 from which a deasphalted oil is removed through ture sulfiding zone 134 is operated at a temperature line 170. A highly concentrated deactivated catalyst higher than the temperature in low-temperature sulfid stream is removed from deasphalting chamber 168 ing zone 130. The sulfiding reaction is continued in zone 65 through line 170 and passed to catalyst generation zone 134 and ammonium oxythiomolybdate or ammonium 172. oxythiotungstate is converted to molybdenum oxysul The catalyst entering regeneration zone 172 com fide and/or molybdenum trisulfide or tungsten oxysul prises molybdenum sulfide or tungsten sulfide together 5,094,991 23 24 with any impurity metals acquired from the feed oil. (b) separating ammonia from said presulfided product The impurity metals comprise primarily vanadium sul to form a sulfided product; fide and nickel sulfide. In regeneration chamber 172 all (c) charging said sulfided product into a hydroproc of these metal sulfides are oxidized by combustion to the essing reactor zone at a temperature sufficient to oxide state. The metal oxides are then passed through 5 convert said sulfided product into an active hydro line 174 to catalyst reclamation zone 176. In reclamation processing catalyst; zone 176 molybdenum oxide or tungsten oxide is sepa wherein said catalyst is characterized by a pore volume rated from impurity metals including vanadium oxide in the range of 10 to 300A radius pore size of from about and nickel oxide by any suitable means. 0.1 to about 1 cc/g and a surface area of from about 20 Non-dissolved impurity metals including vanadium 10 to about 400 m2/g. and nickel are discharged from the system through line 2. The catalyst of claim 1 wherein said Group VIB 178 while purified and concentrated molybdenum oxide metal is tungsten. or tungsten oxide is passed through line 116 for mixing 3. The catalyst of claim 1 wherein said sulfided prod with make-up molybdenum or tungsten oxide entering uct is approximately of the empirical formula of a through line 110, to repeat the cycle. 15 Group VIB metal disulfide. What is claimed is: 4. The catalyst of claim 1 wherein said Group VIB 1. A Group VIB metal sulfide slurry catalyst for the metal is molybdenum. hydroprocessing of heavy hydrocarbonaceous oil or 5. The catalyst of claim 4 wherein said Group VIB residue prepared by a process comprising the steps of: metal sulfide is approximately of the empirical formula (a) sulfiding a Group VIB metal, ammonia-containing 20 of molybdenum disulfide. compound in an aqueous phase, in the substantial 6. The catalyst of claim 1 including a Group VIII absence of hydrocarbon oil, with hydrogen sulfide, metal. at a temperature less than about 350 F., to form a 7. The catalyst of claim 1 including nickel. presulfided product without substantial loss of am 8. The catalyst of claim 1 including cobalt. monia; 25 t x

30

35

45

SO

55

65