CA2003650A1

CA2003650A1 - Slurry catalysts for hydroprocessing heavy and refractory oils

Info

Publication number: CA2003650A1
Application number: CA 2003650
Authority: CA
Inventors: Jaime Lopez; Eugene A. Pasek
Original assignee: Jaime Lopez; Eugene A. Pasek; Chevron Research And Technology Company
Current assignee: Chevron USA Inc
Priority date: 1988-11-22
Filing date: 1989-11-22
Publication date: 1990-05-22
Also published as: AU4740890A; EP0396740A1; JPH03503743A; WO1990005587A1; EP0396740A4

Abstract

ABSTRACT OF THE DISCLOSURE

Group VIB metal sulfide slurry catalysts having a pore volume in the pore size range 10 to 300.ANG. radius of at least 0.1 cc/g. Also, Group VIB metal sulfide catalysts having a surface area of at least 20 m2/g. Suitable Group VIB metals are molybdenum and tungsten, preferably molybdenum. The Group VIB metal sulfide can be approximately a Group VIB
metal disulfide. The slurry catalyst can be promoted with a Group VIII metal, such as nickel or cobalt.

Description

06 This invention relates to Group VIB metal sulfide slurry 07 catalysts used for the catalytic hydroprocessing of heavy 08 hydrocarbonaceous oils including crude oils, heavy dis-09 tillates, such as FCC decanted oils and lubricating oils.
10 The catalysts can also be used for the hydroprocessing of 11 shale oils, oils from tar sands and coal liquids.

13 The Group VIB metal sulfide slurry catalyst particles of 14 this invention can exist as a substantially homogeneous 15 dispersion in a water/oil mixture of very small particles 16 made up of extremely small crystallites. Examples of 17 suitable Group VIB metals include molybdenum and tungsten.
18 Each of these metals can be present in approximately the 19 disulfide form. However, the apparent atomic ratio of 20 sulfur to metal can be greater or less than 2. The pre-21 ferable metal is molybdenum and the molybdenum catalyst will 22 be particularly described herein. The catalyst is probably 23 structured molecularly as platelets formed from hexagonal 24 sheets of molybdenum or tungsten atoms separated by two 25 hexagonal layers of sulfur atoms with activity sites con-26 centrated at the edge of each basal plane of the molybdenum 27 or tungsten atoms.

2~
29 We have found that the activity of the catalyst of this 30 invention can be defined by the pore volume expressed as 31 cubic centimeters per gram (cc/g) based on pores in the 10 32 to 300 Angstroms (A) radius size range. The catalyst of 33 this invention has at least 0.1 cc/g pore volume in pores 34 between 10 and 300A in radius; preferably at least 0.15 and 01most preferably at least 0.2 cc/g in pores having a radius 02between 10 and 300A. Catalysts of this invention can have a 03pore volume in pores having a radius between 10 and 300A of 04between 0.15 or 0.2 to 1 cc/g. Good activity is obtained in 05the range 0.2 to 0.4 cc/g while preferably activity is 06obtained by extending the upper end of the range to 1 cc/g, 07or higher.

09We have found that the catalyst of this invention can also 10 be defined by its surface area expressed as square meters 11 per gram (m2/g). Good activity is achieved with a surface 12 area of at least 20 or 25 m2/g. Surface areas between 25 13 and 75 or 100 m2/g give good catalyst activities while 14 surface areas above 75 or 100 cc/g and up to 400 cc/g, or 15 higher, give preferable activity.

17 The following equations are used to calculate the pore 18 volume and surface area of the catalysts on a carbon-free 19 basis.

23 Pore Volume, cc/g ~
100 (Pore Volume of Used Catalyst, cc/g) + d (Percent Carbon) ( 00 - Percent Car on) 27 where d i6 the density of the carbonaceous material, assumed 28 to be 1.0 for "coke" make from decant oil.

3l Surface Area, m2/g , (Surface Area of Used Catalyst, m2/g) 100 32 (100 - Percent Carbon) 33 The hydrogen associated with the coke is disregarded for both 34 equations.

.

OlThe slurry catalyst as described is prepared directly as 02dispersed particles of a highly active form of molybdenum 03sulfide, as contrasted to a granulated precipitate. In 04general, the catalyst is prepared by presulfiding a Group VI
05metal compound in an aqueous environment, and charging said 06sulfided compound into a hydroprocessing reactor zone at a 07 temperature sufficient to convert said sulfided compound 08into an active hydroprocessing catalyst.

10 More specifically, the first step in the preparation of this 11 catalyst comprises formation of oxygen containing generally 12 soluble ammonium salts of molybdenum for sulfiding. Ammon-13 ium molybdate is a suitable soluble salt. The ammonium 14 molybdate can be presulfided to form some ammonium molyb-15 denum oxysulfide solids. The ammonium molybdate and any 16 oxygulfides is then sulfided with a sulfiding agent in a 17 plurality of zones of increasing temperature, including low, 18 intermediate and high-temperature sulfiding zones. Hydrogen 19 sulfide, preferably with hydrogen, is a suitable sulfiding 20 agent. Each sulfiding step replaces a portion of the oxygen 21 associated with the molybdenum with sulfur. The low and 22 intermediate temperature sulfiding zones contain water and 23 can be operated either in the presence of feed oil or in the 24 6ub6tantial ab6ence of feed oil. Feed oil and water are 25 both pre6ent in the high temperature sulfiding zone. If 26 feed oil 16 not present in the low or intermediate tem-27 perature 6ulfiding zones, ammonia can be separated from the 2~ system after the low or intermediate temperature sulfiding 29 zones and before addition of feed oil.
31 The final catalyst comprises crystallites of molybdenum 32 sulfide and can be MoS2. However, frequently the atomic 33 ratio of sulfur to molybdenum is not 2 or is only approxi-34 mately 2. It is an exceptionally active form of molybdenum lsulfide or MoS2. It appears that the activity of the final 02catalyst depends upon the conditions employed during its 03preparation. Application Serial No. 527,414, filed 04August 29, 19~3, which is hereby incorporated by reference, 05 taught the presence of both feed oil and water during the 06 majority of stages of multistage sulfiding of the precursor 07 ammonium salt to molybdenum sulfide and did not teach ammo-08 nia removal during catalyst preparation. That method of 09 catalyst preparation is referred to herein as the oil method lO and results in a molybdenum sulfide catalyst having a pore 11 volume in pores in the 10 to 300A radius range of between 12 about 0.1 to about 0.4 cc/g and a surface area in the range 13 of about 20 to about 75 m2/g. An improvement in catalyst 14 activity can be achieved by performing a portion of the ~5 multistage sulfiding of the precursor ammonium salt in an 16 aqueous phase in the substantial absence of any hydrocarbon 17 oil and by separating ammonia from the system in advance of 18 the addition of an oil phase. For example, the low-temper-19 ature sulfiding stage or the low and intermediate tempera-20 ture sulfiding stages can be operated in the absence of 21 hydrocarbon oil. If oil is first added to the intermediate22 temperature sulfiding stage, then ammonia can be vented 23 after the low-temperature sulfiding stage. If oil is first 24 added to the high-temperature sulfiding stage, then ammonia 25 can be vented after the intermediate temperature sulfiding 26 ~tage. This method is referred to herein as the water 27 method and results in a molybdenum sulfide catalyst having a 28 ore volume in pores in the 10 to 300A unit radius range of 29 between about 0.1 and about l cc/g and a surface area of 30 about 20 to about 350 m2/g, or higher.

32 The ammonium molybdate used can be prepared by dissolving a 33 molybdenum compound, such as MoO3, in aqueous ammonia to 34 form ammonium molybdates, with or without the subsequent ~,.

~00365Q
01 injection of hydrogen sulfide to the dissolving stage. The 02 ammonium molybdates are generally soluble in the aqueous 03 ammonia but the addition of hydrogen sulfide causes some 04 dissolved molybdenum to separate as ammonium molybdenum 05 oxysulflde solids.

07 Aqueous ammonium molybdenum oxysulfide from the dissolving 08 stage can be mixed with all or a portion of the feed oil 09 stream as described below using the dispersal power of a 10 hydrogen-hydrogen sulfide stream and the admixture can be 11 passed through a plurality of sulfiding zones of ascending 12 temperature. The sulfiding zones can be three in number, to 13 provide a time-temperature sequence which is necessary to 14 complete the preparation of the slurry catalyst prior to 15 passing it to a higher temperature exothermic hydropro-16 cessing reactor zone. Each sulfiding zone is operated at a 17 temperature higher than its predecessor. The residence time 18 in each sulfiding zone is sufficient to inhibit excessive 19 coking and can be, for example, 0.02 to 0.5 hours, or more.
20 The various sulfiding zones can employ the same or different 21 residence times. For example, the high-temperature sul-22 fiding reactor can employ a residence time of 2 hours, or 23 more. In general, the residence time in each sulfiding zone 24 can be at least 0.02, 0.1 or 0.2 hours. The residence time 25 in each zone can also be at least 0.3, 0.4 or 0.5 hours.
26 Each ~ulfiding zone is constituted by a time-temperature 27 relationship and any single reactor can constitute one or 28 more than one sulfiding zones depending upon whether the 29 stream is heated or is at a constant temperature in the 30 reactor and upon the duration of the stream time within a 31 particular temperature range during stream residency in the 32 reactor.

01The first sulfiding stage is operated at a relatively low 02temperature with an aqueous phase and with or without feed 03oil. The second sulfiding stage is operated at an inter-04 mediate temperature which is higher than the temperature of S the low-temperature sulfiding stage with an aqueous phase Q6 and either with or without feed oil. The third sulfiding 07 stage is a high-temperature stage and is operated at a tem-08 perature which is higher than the temperature in the inter-09 mediate temperature stage. It is performed with both an 10 aqueous and oil phase.

12 The sulfiding reactions occurring in the low and inter-13 mediate temperature sulfiding stages generate ammonia from 14 gradual decomposition of ammonium molybdates and/or ammonium 15 molybdenum oxysulfides. If no oil is present, this ammonia, 16 together with any excess ammonia present from the earlier 17 reaction of ammonia with molybdenum oxide, can be flashed in 18 a separator zone and separated from slurry-containing 19 separator residue in advar,ce of the high-temperature sul-20 fiding stage and prior to addition of oil. Feed oil is 21 added to the separator residue and the separator residue 22 with feed oil is passed to the high-temperature sulfiding 23 stage.

25 If the temperature in the high-temperature sulfiding reactor 26 ls gufficiently high for hydroprocessing metals-containing 27 or refractory hydrocarbon feed oil, the residence time in 23 the high-temperature reactor can be sufficient to accomplish 29 both the high-temperature sulfiding and the required hydro-30 processing reactions. If a higher temperature is required 31 to accomplish hydroprocessing of the feed oil, the effluent 32 stream from the high-temperature reactor is passed to a 33 hydroprocessing reactor operated at a hydroprocessing 01 temperature which is higher than the temperature in the 02 high-temperature sulfiding reactor.

04 Although not to be bound by any theory, it is believed that 05 the following reactions occur in the various catalyst pre-06 paration steps described above. In the first catalyst 07 preparation step, insoluble, crystalline MoO3 is mixed with 08 water to form a non-oleaginous slurry which is reacted with 09 ammonia to form soluble ammonium molybdates according to the 10 following generalized equation:

13 7 MoO3 + 6 NH3 + 3 H20 > (NH4)6 7 24 14 Insoluble Soluble Crystalline 17 The MoO3 is dissolved under the following conditions:

19 NH3/Mo Weight Ratio 0.1 to 0.6; preferably 0.15 to 0.3 20 Temperature, F 33 to 350; preferably 120 to 180 21 Pressure: psig 0 to 400; preferably 0 to 10 23 ~he pressure and temperature are not critical. Increased 24 pressure is required to maintain the ammonia in aqueous 25 801ution at elevated temperatures. Elevated temperature is 26 nece8sary to insure reaction and vary the concentration of 27 molybdenum dissolved in the solution.

29 The solution of ammonium molybdate, which may be presulfided 30 to form some ammonium molybdenum oxysulfides, is passed to a 31 series of sulfiding reactors or zones operated at ascending 32 temperatures. It is first passed to a relatively low-33 temperature sulfiding reactor where it is contacted with 34 gaseous hydrogen sulfide, preferably a hydrogen/hydrogen ;~003650 01 sulfide blend, with or without feed oil. The generalized 02 sulfiding reaction is as follows:

04 (NH4)6M724 + H2S > ~N 4)x y z 05 amorphous 07 The above is a generalized equation. The reaction products 08 in the low-temperature sulfiding reactor include ammonium 09 molybdates, ammonium molybdenum oxysulfides and possibly 10 molybdenum sulfides.

12 Following are the conditions in the low temperature 13 sulfiding reactor:

15 SCF H2S/lbs Mo 16 ratio above 2.7; preferably above 12 17 TemperatUre, F 70 to 350; preferably 130 to 180 18 Hydrogen sulfide 19 partial pressure, psi 3 to 400; preferably 150 to 250 21 It is important not to exceed the above temperature range in 22 the low-temperature reactor. At temperatures above 350F
23 ammonia loss from the catalyst precursor to produce a lower 24 ammonia entity will occur faster than thiosubstitution can 25 proceed and the molybdenum compound will precipitate and 26 pos6ibly plug the reactor. It is possible to operate the 27 low-temperature reactor at a temperature below 325 or 350F
28 for a relatively long duration to allow the thiosubstitution 29 reaction to proceed faster than ammonia loss so that the 30 molybdenum compound rich in oxygen will not precipitate.

32 The effluent stream from the low-temperature reactor is 33 passed to an intermediate temperature reactor, which may or ~0036~;0 01 may not contain oil, operated under the following 02 conditions:

04 Temperature, F lB0 to 700; preferably 300 to 550 05 Hydrogen sulfide 06 partial pressure, psi 3 to 440; preferably 150 to 250 08 The temperature in the intermediate temperature reactor is 09 higher than the temperature in the low-temperature reactor.
11 The following generalized reaction may occur in the 12 intermediate temperature reactor:

14 (NH4)XMO6SZ + H2S > MOOX,SY, + NH3 16 where x' is about 1 17 y' is about 2.

19 The molybdenum compound in the intermediate temperature 20 reactor is sufficiently sulfided so that upon loss of 21 ammonia it is in a particulate form which is sufficiently 22 fine that it can remain dispersed with sufficient agitation.
23 In addition, the molybdenum compound is sufficiently 24 sulfided that a crystalline structure is evolving from the 25 amorphous form it exhibited in the low-temperature sulfiding 26 temperature reactor where its level of sulfiding was so low 27 that a loss of ammonia would induce precipitation and 28 reactor plugging.

30 The molybdenum compound leaving the intermediate temperature 31 sulfiding stage requires further conversion of oxygen to 32 sulfur to achieve the molybdenum sulfide active catalyst 33 state. This further conversion occurs in the presence of Z0036~;0 Olfeed oil in a high-temperature sulfiding reactor, which is 02 operated a temperature above the temperature of the inter-03 mediate temperature sulfiding reactor. The reaction 04 occurring in the high-temperature sulfiding reactor in the 05 presence of an oil/water phase may be expressed by the 06 following equation:

MoOxSy > Mo52 + H20 11 Highly 12 Active 13 where x is about 1 14 y is about 2.

16 The high-temperature sulfiding reactor is operated at a 17 temperature in the range 500 to 750F and can also be 18 employed as the hydroprocessing reactor if the feed oil is 19 capable of being hydroprocessed at the temperature of the 20 high-temperature sulfiding reactor. However, feed oils 21 commonly require hydroprocessing at temperatures above the 22 temperature of the high-temperature sulfiding reactor. In 23 such case, a downstream hydroprocessing reactor is required.
24 In general, the temperature in the hydroprocessing reactor 25 is 650 to 950F and is above the temperature of the high-26 tomperature sulfiding reactor.

28 The total pressure in the sulfiding zones and the hydro-processing reactor can be between about 500 and about 30 5,000 psi.

32 If the aqueous catalyst precursor leaving the intermediate 33 temperature reactor were to be passed together with feed oil ... .

20036~i0 01 and hydrogen sulfide directly to a hydroprocessing reactor 02 operated at a temperature above the temperature of the high-03 temperature sulfiding reactor, such as 800F, or above, the 04 molybdenum compound would react with the water present to 05 106e sulfur rather than gain it to form an inactive catalyst 06 according to the following reaction:

08 MoOxSy + H2O 800F~ MoOx,Sy, + H2S or (MoO2/MoS2 + H2S) Inactive Mixtures Catalyst 12 where y' is less than 2. This material is not a suffi-13 ciently active catalyst to inhibit coking reactions. It is 14 noted that the MoOxSy (where x is about 1, y is about 2) in 15 the presence of hydrogen sulfide and water reacts preferen-16 tially with the hydrogen sulfide to become sulfided at a 17 temperature between 500 to 750F. It has been found that 18 the MoS2 catalyst formed in the temperature range 500 to 19 750F is a low-coking catalyst. However, at a temperature 20 above this range, the MoOxSy (where x is about 1 and y is 21 about 2) in the presence of hydrogen sulfide and water 22 reacts to form MoOx,Sy, (where y' is less than 2), which is 23 inactive.

25 It will be appreciated that the low, intermediate and high-26 temperature 8ulfiding zones, stages or steps described 27 hereln can constitute separate reactors, as illustrated, or 2~ some or all of these zones, stages or steps can be merged 29 into a single reactor. In terms of concept, each of these 30 sulfiding zones, stages or steps is represented by a 31 residence time-temperature relationship. If the stream is 32 heated through the temperature range indicated above for any 33 sulfiding zone, stage or step for the time indicated above, 2003~50 01then the performance of the process requirements to satisfy 02that zone, stage or step has occurred.

04If desired, the hydrogenation, desulfuriæation and denitro-05genation activities of Group VI~ metal catalysts of this 06 invention can be improved by promotion with at least one 07 Group VIII metal, such as nickel or cobalt. The Group VIII
08 metal can be added to the Group vIs slurry catalyst in any 09 convenient form, e.g., as water-soluble inorganic salts or 10 as organometallic compounds. The weight ratio of Group VIII
11 metal to Group VIs metal can be 0.001 to 0.75, generally;
12 0.01 to 0.03, preferably; and 0.08 to 0.20, most preferably.
13 Examples of suitable water-soluble inorganic salts of 14 Group VIII metals are sulfates, nitrates, etc. Examples of 15 suitable organometallic compounds of Group VIII metals 16 include naphthenates, porphyrins, etc. The Group VIII metal 17 compound can be added to the slurry of Group VIs metal 18 flowing to or within the low, intermediate or high-tempera-19 ture sulfiding steps described herein and is preferably 20 added to the catalyst precursor after it departs from the 21 ammonia dissolving stage.

23 The catalyst preparation method described above uses MoO3 as 2~ a btarting material for preparing the catalyst precursor.
25 Howevor, other molybdenum compounds are also useful. For 26 example, thiosubstituted ammonium molybdates, such as ammo-27 nium oxythiomolybdate or ammonium thiomolybdate can be 28 employed. Since these materials are produced from MoO3 in 29 the first two catalyst preparation steps described above, 30 i.e., the reaction of MoO3 with ammonia step and the 31 low-temperature sulfiding step, these two steps can be 32 by-passed by employing these thiosubstituted compounds as 33 starting materials. Therefore, when these thiosubstituted 34 compounds are used as catalyst precursors, a water slurry 01 thereof can be injected with hydrogen sulfide and hydrogen 02 and passed directly to the intermediate temperature 03 sulfiding reactor described above, followed by separation of 04 ammonia and then the high-temperature sulfiding reactor and 05 the hydroprocessing reactor, as described above.

07 To complete the cycle for the process of slurry catalyst 08 preparation and use as described above, it is necessary to 09 recover and recycle the catalyst. Following the hydro-10 processing operation, an oil product can be recovered in 11 atmospheric and vacuum distillation towers. The vacuum 12 tower bottoms contains the catalyst, possibly with conta-13 minant metals acquired from the feed oil. Some or all of 14 the vacuum tower bottoms is treated with a solvent to 15 separate non-asphaltic oils from asphalt containing catalyst 16 with metallic contaminants.

18 The deactivated catalyst can comprise molybdenum sulfide 19 catalyst and can be contaminated with vanadium, nickel and 20 some iron, derived from the oil being treated, all as 21 sulfides. The catalyst-containing mixture can be passed to 22 a combustion zone to burn off coke and asphalt and to con-23 vert the metal sulfides to the corresponding metal oxides of 2~ their highest stable oxidation state. The oxidized spent 25 catalyst can then be passed to an aqueous ammonia dissolving 26 zone to dlssolve molybdenum in preference to the contaminat-27 lng metals. Thereupon, to repeat the catalyst preparation 28 procedure, the resulting aqueous ammonium molybdate solution 29 is reacted with hydrogen sulfide in a plurality of sulfiding 30 stages as described above to prepare a molybdenum sulfide 31 catalyst for return to the oil hydrotreating process.

33 The present invention is illustrated by reference to the 34 figures in which:

~0(~3~50 01 ~RI~F DESCRIPTION OF T~E FIGURES

03FIG. 1 relates to the AI gravity of a hydroprocessed oil to 04 the 10 to 300A radius pore volume in the molybdenum sulfide 05 61urry catalyst;

07 FIG. 2 relates to the ratio of nitrogen contents in the 08 product and feed oils to the 10 to 300A radius pore volume 09 in the molybdenum sulfide slurry catalyst;

11 FIG. 3 relates to the ratio of sulfur contents in the prod-12 uct and feed oils to the 10 to 300A radius pore volume in 13 the molybdenum sulfide catalyst;

15 FIG. 4 relates to the API gravity in a hydroprocessed oil to 16 the surface area of the molybdenum sulfide slurry catalyst;

18 FIG. 5 relates to the ratio of nitrogen contents in the 19 product and feed oils to the surface area of the molybdenum 20 sulfide slurry catalyst;

22 FIG. 6 relates to the ratio of sulfur contents in the 23 product and feed oils to the surface area of the molybdenum 24 sulfide slurry catalyst;
26 FIG. 7 illustrates a flow scheme for the preparation of a 27 slurry catalyst by the water method and the use of said 2~ catalyst in a hydroprocess; and 30 FIG. 8 illustrates a flow scheme for the preparation of a 31 slurry catalyst by the oil method and the use of said 32 catalyst in a hydroprocess.

01 sefore referring to the figures, the following examples will 02 further illustrate the present invention. Examples l and 4 03 show the preparation of catalysts by the oil method.
04 Examples 2, 5, 8, 9, 10, 11 and 12 show the preparation of 05 catalysts by the water method. Examples 3, 6 and 7 show the 06 preparation of catalysts by prior art methods.

09 Example 1 11 In this example, the catalyst was prepared according to the 12 oil method. The method of preparation was as follows:

14 Step l - 1884.1 Grams of molybdenum trioxide (Climax 15 Molybdenum Grade L) was slurred in 7309.4 grams of distilled 16 water. To this slurry, 1307.5 grams of ammonium hydroxide 17 (23.2 weight percent ammonia) was added and mixed well.
18 The resulting mixture was exposed to the following 19 conditions:
21 Temperature: F150.0 22 Pressure: psia14.7 23 Time: hrs 2.0 25 Step 2 - A portion of the resultant mixture from Step 1 was 2C introduced to a reactor and heated to 150.0F and the 27 pre66ure was increased to 35.0 psig. At this time a flow of 28 92% hydrogen - 8% hydrogen sulfide gas was introduced into 29 the reactor. The reactor was maintained at these conditions 30 for 0.5 hours and at a gas flow rate and for a time such 31 that 2.7 SCF of H2S was contacted per pound of molybdenum.
32 This level of presulfiding is not enough to decompose the 01 molybdate formed in the first step and thus liberate a 02 substantial amount of ammonia. At the end of this low-03 temperature sulfiding step, the reactor was cooled and 04 depressurized; the resulting catalyst is removed from the 05 reactor. This catalyst is identified as Catalyst A.

07 Step 3 - Catalyst A was then charged with a decanted oil, 08 lnspections of which are found in Table I, to a rocker-bomb 09 reactor. The rocker-bomb reaction was pressurized with a 10 92% hydrogen - 8% hydrogen sulfide gas mixture and heated to 11 run temperature. This heat-up period lasted about 6 hours 12 and constituted the intermediate temperature sulfiding step.
13 The high-temperature sulfiding step occurred under hydro-14 processing conditions, which were as follows:

16 Pressures, 17 Hydrogen: psi 2200.0 18 Hydrogen Sulfide: psi182.0 19 Water Vapor: psi 390.0 Temperature: F 720.0 21 Time at Temperature: hrs6.0 22 Catalyst to Oil Ratio, 23 Mo/Oil: wt/wt 0.042 25 The results of this screening run are shown in Table II
26 under the column labeled Catalyst A.

28 Example 2 31 Tn this example, the catalyst was prepared according to the 32 water method. The method of preparation was as follows:

X0~3650 Olstep 1 - 1884.1 Grams of molybdenum trioxide (Climax 02 Molybdenum Grade L) was slurried in 7309.4 grams of 03distilled water. To this slurry, 1307.5 grams of ammonium 04 hydroxide (23.2 weight percent ammonia) was added and mixed 05 well. The resulting mixture was exposed to the following 06 conditions:

08 Temperature: F 150.0 O9 Pressure: psia 14.7 Time: hrs 2.0 12 Step 2 - A portion of the resultant mixture from Step 1 was 13 introduced to a reactor and heated to 150.0F and the 14 pressure was increased to 2500.0 psig. At this time a flow 15 of a 92% hydrogen - 8% hydrogen sulfide gas was introduced 16 into the reactor. After a 0.5 hours time period the 17 temperature was increased to 450F and maintained for 0.5 18 hours. At the end of this period the gas flow was stopped 19 and the pressure was reduced to 750.0 psig while maintaining 20 temperature, this hold cycle was held for 0.5 hours. At the 21 end of this sulfiding step, the reactor was cooled and 22 depressurized and gaseous ammonia was flashed off. The gas 23 flow rate and time of reaction were such that at least 24 10.5 SCF of H2S was contacted per pound of molybdenum. This 25 level of sulfiding is sufficient to decompose the molybdate 26 formed in the fir6t 8tep, therefore liberating a substantial 27 amount of ammonia. The resulting catalyst was removed from 28 the reactor. This catalyst is identified in Catalyst s.

30 Step 3 - Catalyst ~ was then charged with the decanted oil 31 of Table I to a rocker-bomb reactor. The rocker-bomb 32 reactor was pressurized with a 92~ hydrogen - 8% hydrogen 33 sulfide gas mixture and heated to run temperature. This 34 heat-up period lasted about 6 hours and constituted the lhigh-temperature sulfiding step. Hydroprocessing then 02occurred under the following conditions:

04 Pressures, 05 Hydrogen: psi2200.0 06 Hydrogen Sulfide: psi 182.0 07 Water Vapor: psi390.0 08 Temperature: E 720.0 09 Time at Temperature: hrs 6.0 Catalyst to Oil Ratio 11 Mo/Oil: wt/wt 0.042 13 The results of this screening run are shown in Table II
14 under the column labeled Catalyst ~.
16 Example 3 18 In this example, the catalyst is a prior art catalyst and 19 was prepared by thermochemical decomposition of ammonium 20 tetra-thiomolybdate. The preparation was as follows:

22 Step 1 - Ammonium tetrathiomolybdate was prepared following 23 the procedure described by G. Kruss [Justus Liebigs Mann 24 Chem., 229, 29 ~1884)]. 75.0 Grams of ammonium tetrathio-25 molybdate was slurried in 225.0 grams of distilled water.
26 To thi6 ~lurry, 417.0 cc of ammonium hydroxide (23.2 weight 27 percent ammonia) was added and mixed well. The resulting 28 mixture was maintained in an ice bath while the mixture was 29 t eated with gaseous hydrogen sulfide until blood-red 30 crystals precipitated out. These crystals were filtered and 31 washed with cold water.

33 Step 2 - The thermochemical decomposition was performed 34 following the procedure described by Tauster, Pecoraro and . ~

X003~i50 01 Chianelli lJournal of Catalysis, 63, 515-519 (180)]. The 02 ammonium tetra-thiomolybdate from Step 1 was decomposed by 03 heating the material in a furnace tube from 25.0C to 400C
04 in a 120 cc/min flow of a 92% hydrogen - 8% hydrogen sulfide 05 gas mixture over a period of 1.5 hours, when maximum temper-06 ature was reached the material was allowed to cool. The gas 07 flow was continued until the material had cooled to 25C.
08 The furnace was nitrogen swept and the material was removed.
09 This catalyst as identified as Catalyst C.
11 Step 3 ~ Catalyst C was then charged with the decanted oil 12 of Table I to a rocker-bomb reactor. The rocker-bomb 13 reactor was pressurized with a 92% hydrogen - 8% hydrogen 14 sulfide gas mixture and heated to run temperature.
15 Operating conditions were as follows:

17 Pressures, 18 Hydrogen: psi 2200.0 19 Hydrogen Sulfide: psi 182.0 Water Vapor: psi390.0 21 Temperature: F 720.0 22 Time at Temperature: hrs 6.0 23 Catalyst to Oil Ratio, 24 Mo?Oil: wt/wt 0.042 26 The results of this screening run are shown in Table II
27 under the column labeled Catalyst C.
2~
29 Example 4 31 In this example, the catalyst was prepared according to the 32 oil method utilizing acidic decomposition of ammonium 33 tetra-thiomolybdate to form molybdenum trisulfide. The 34 preparation was as follows:

01 Pressures, 02 Hydrogen: psig2200.0 03 Hydrogen Sulfide: psi 182.0 04 water vapor: psi390.0 05 Temperature: F 720.0 06 Time at Temperature: hrs 6.0 07 Catalyst to Oil Ratio, 08 Mo/Oil: wt/wt 0.042 10 The results of this screening run are shown in Table II
11 under the column labeled Catalyst D.

13 Example 5 15 In thig example, the catalyst was prepared according to the 16 water method utilizing acidic decomposition of ammonium 17 tetra-thiomolybdate to form molybdenum trisulfide. The 18 preparation was as follows:

20 Step 1 - Ammonium tetrathiomolybdate was prepared following 21 the procedure described by G. Kruss IJustus Liebigs Nann 22 Chem., 229, 29 (1884)l. 75.0 Grams of ammonium tetrathio-23 molybdate was slurried in 225.0 grams of distilled water.
24 $o th~s slurry, 417.0 cc of ammonium hydroxide (23.2 weight 25 porcent ammonia~ was added and mixed well. The resulting 26 mixture was maintained in an ice bath while the mixture was 27 treated with gaseous hydrogen sulfide until blood-red 28 crystals precipitated out. These crystals were filtered and 29 washed with cold water. 100 Grams of the resultant crystals 30 were redispersed in 165.9 grams of distilled water. To this 31 slurry and while stirring, 51.1 grams of formic acid, 90 32 percent by weight, were added. The resultant mixture was 33 heated at 50C for 0.5 hours under a nitrogen atmosphere.
34 The precipitate (MoS3) was filtered and washed with water.

2003~50 01 This formic acid decomposition method is described in 02 Tauster, Pecoraro, and Chianelli [Journal of Catalysis, 63, 03 515-519 (1980)]. The precipitate was then redispersed in 04 distilled water.

06 tep 2 - The resultant slurry was introduced to a reactor, 07 pressured to 2300 psig with 92~ H2 ~ 8~ H2S gas and heated 08 to 300F. The reactor was maintained at these conditions 09 for 0.5 hours. At the end of this intermediate temperature 10 sulfiding step, the reactor is cooled and depressurized.
11 The resulting catalyst was filtered and redispersed in 12 distilled water. This catalyst is identified as Catalyst E.

14 Step 3 - Catalyst ~ was then charged with a decanted oil, 15 inspections of which are found in Table I, to a rocker-bomb 16 reactor. The rocker-bomb reactor was pressurized with a 92~
17 hydrogen - 8% hydrogen sulfide gas mixture and heated to run 18 temperature. This heat-up period lasted about 6 hours and 19 constituted a high-temperature sulfiding step. The 20 high-temperature sulfiding step continued under 21 hydroprocessing conditions, which were as follows:

23 Pressures, 24 Hydrogen: psi 2200.0 Hydrogen Sulfide: psi 182.0 26 Water Vapor: psi390.0 27 Temperature: F 720.0 28 Time at Temperature: hrs 6.0 29 Catalyst to Oil Ratio, Mo/Oil: wt/wt 0.042 32 The results of this screening run are shown in Table II
33 under the column labeled Catalyst E.

01 Example 6 03 In this example, the catalyst was prepared by the prior art 04 method of thermochemical decomposition of molybdenum 05 trisulfide. The preparation was as follows:

07 Ste~ Ammonium tetrathiomolybdate was prepared following 08 the procedure described by G. Kruss [Justus Liebigs Nann 09 Chem., 229, 29 (1884)1. 75.0 Grams of ammonium tetrathio-10 molybdate was slurried in 225.0 grams of distilled water.
11 To this slurry,m 417.0 cc of ammonium hydroxide (23.2 weight 12 percent ammonia) was added and mixed well. The resulting 13 mixture was maintained in an ice bath while the mixture was 14 treated with gaseous hydrogen sulfide until blood-red crys-15 tals precipitated out. These crystals were filtered and 16 washed with cold water. 100 Grams of the resultant crystals 17 were redispersed in 165.9 grams of distilled water. To this 18 slurry and while stirring, 51.1 grams of formic acid, 90 19 percent by weight, were added. The resultant mixture was 20 heated at 5CC for 0.5 hours under a nitrogen atmosphere.
21 The precipitate (MoS3) was filtered and washed with water.
22 This formic acid decomposition method is described in 23 Tauster, Pecoraro, and Chianelli [Journal of Catalysis, 63, 24 515-519 (1980)].
26 steP 2 - The thermochemical decomposition was performed 27 following the procedure described by Tauster, Pecoraro and 20 chianelli [Journal of Catalysis, 63, 515-519 (1980)l. The 29 molybdenum trisulfide from Step 1 was decomposed by heating 30 the material in a furnace tube from 25C to 400C in a 31 120-cc/min flow of a 92% hydrogen - 8% hydrogen sulfide gas 32 mixture over a period of 1.5 hours, when maximum temperature 33 was reached the material was allowed to cool. The gas flow 34 was continued until the material had cooled to 25C. The 2003t;50 01furnace was nitrogen-swept and the material was removed.
02This catalyst is identified as Catalyst F.

04 Step 3 - Catalyst F was then charged with the decanted oil 05 of Table I to a rocker-bomb reactor. The rocker-bomb 06 reactor was pressurized with a 92% hydrogen - 8% hydrogen 07 sulfide gas mixture and heated to run temperature.
08 Operating conditions were as follows:

Pressures, 11 Hydrogen: psi 2200.0 12 Hydrogen Sulfide: psi182.0 13 Water Vapor: psi 390.0 14 Temperature: F 720.0 Time at Temperature: hrs6.0 16 Catalyst to Oil Ratio, 17 Mo/Oil: wt/wt 0.042 19 The results of this screening run are shown in Table II
20 under the column labeled Catalyst F.

22 Example 7 24 the catalyst of this example is suspension grade molybdenum 25 disulfide (Climax Molybdenum Disulfide-Suspension Grade) of 26 the prior art. There was no preparation necessary for the 27 catalyst. The material was used as received. This catalyst 28 is identified as Catalyst G.

30 Catalyst G was then charged with the decanted oil of Table I
31 to a rocker-bomb reactor. The rocker-bomb reactor was 32 pressurized with a 92% hydrogen - 8% hydrogen sulfide gas 01 mixture and heated to run temperature. Operating conditions 02 were as follows:

04 Pressures, 05 Hydrogen: psi 2200.0 06 Hydrogen Sulfide: psi 182.0 07 Water Vapor: psi390.0 08 Temperature: F 720.0 09 Time at Temperature: hrs 6.0 Catalyst to Oil Ratio, 11 Mo/Oil: wt/wt 0.042 13 The results of this screening run are shown in Table II
14 under the column labeled Catalyst G.
16 Example 8 18 In this example, the catalyst was prepared according to the 19 water method. The preparation was as follows:
21 Step 1 - 4.15 Pounds of molybdenum trioxide (Climax 22 Molybdenum Grade L) was slurried in 16.1 pounds of distilled 23 water. To this slurry, 2.88 pounds of ammonium hydroxide 24 (25.1 weight percent ammonia) was added and mixed well. The 25 resulting mixture was exposed to the following conditions:

27 Temperature: F150.0 28 Pressure: psia14.7 29 Time: hrs 2.0 31 Step 2 - The resultant mixture from Step 1 was introduced to 32 a reactor and heated to 200F and the pressure was increased 33 to 400.0 psig. At this time a 14.0 SCFH flow of a 92~
34 hydrogen - 8% hydrogen sulfide gas was introduced into the 01 reactor. At the end of this low-temperature sulfiding step, 02 the reactor was depressurized and gaseous ammonium was 03 flashed off. The resulting catalyst is removed from the 04 reactor. This catalyst is identified as Catalyst H.

06 Example 9 08 In this example, the catalyst was prepared according to the 09 water method. The preparation was as follows:
11 Step 1 - 4.15 Pounds of molybdenum trioxide (Climax 12 Molybdenum Grade L) was slurried in 16.1 pounds of distilled 13 water. To this slurry, 2.88 pounds of ammonium hydroxide 14 ~25.1 weight percent ammonia) was added and mixed well. The lS resulting mixture was exposed to the following conditions.

17 Temperature: F150.0 18 Pressure: psia14.7 19 Time: hrs 2.0 21 Step 2 - The resultant mixture from Step 1 was introduced to 22 a reactor and heated to 150F and the pressure was increased 23 to 400 psig. At this time a 14.0 SCFH flow of a 92%
24 hydrogen - 8% hydrogen sulfide gas was introduced to the 25 reactor. The reactor was maintained at these conditions for 26 6.0 hours. At the end of this low-temperature sulfiding 27 step, the reactor is depressurized and gaseous ammonia was 28 flashed off. The resulting catalyst is removed from the 29 reactor. This catalyst is identified as Catalyst I.
31 Step 3 - Catalyst I was then charged with the decanted oil 32 of Table I to a rocker-bomb reactor. The rocker-bomb 33 reactor was pressurized with a 92~ hydrogen - 8~ hydrogen 01sulfide gas mixture and heated to run temperature. This 02heat-up period lasted about 6 hours and constituted both the 03intermediate and high-temperature sulfiding steps because 04 both the intermediate and high-temperature sulfiding temper-05 ature ranges were traversed for the designated durations.
06 The high-temperature sulfiding step continued under hydro-07 processing conditions, which are as follows:

09 Pressures, Hydrogen: psi 2200.0 11 Hydrogen Sulfide: psi 182.0 12 Water Vapor: psi390.0 13 Temperature: F 720.0 14 Time at Temperature: hrs 6.0 Catalyst to Oil ~atio, 16 Mo/Oil: wt/wt 0.042 18 The results of this screening run are shown in Table II
19 under the column labeled Catalyst I.
21 Example 10 23 In this example, the catalyst was prepared according to the 24 water method and is a duplicate of Example 9. the 25 preparation was as follows:

27 Step 1 - 4.15 Pounds of molybdenum trioxide (Climax 28 Molybdenum Grade L) was slurried in 16.1 pounds of distilled 29 water. To this slurry, 2.88 pounds of ammonium hydroxide 30 (25.1 weight percent ammonia) was added and mixed well.

2003~50 01 The resulting mixture was exposed to the following 02 conditions:

04 Temperature: F150.0 05 Pressure: psia14.7 06 Time: hrs 2.0 08 Step 2 - A portion of the resultant mixture from Step 1 was 09 introduced to a reactor and heated to 150F and the pressure 10 was increased to 400.0 psig. At this time a 14.0 SCFH flow 11 of a 92% hydrogen - 8% hydrogen sulfide gas was introduced 12 into the reactor. The reactor was maintained at these 13 conditions for 6.0 hours. At the end of this low-14 temperature sulfiding step, the reactor is depressurized and 15 gaseous ammonia was flashed off. The resulting catalyst is 16 removed from the reactor. This catalyst is identified as 17 Catalyst J.

19 Step 3 - Catalyst J was then charged with the decanted oil 20 of Table I to a rocker-bomb reactor. The rocker-bomb 21 reactor was pressurized with a 92% hydrogen - 8% hydrogen 22 sulfide gas mixture and heated to run temperature. This 23 heat-up period lasted about 6 hours and constituted both the 24 intermediate and high-temperature sulfiding steps because 25 both the intermediate and high-temperature sulfiding 26 temperature range8 were traversed for the designated 27 duration8. The high-temperature sulfiding step continued 2~ under hydroprocessing conditions, which are as follows:

01 Pressures, 02 Hydrogen: psi 2200.0 03 Hydrogen Sulfide: psi 182.0 04 Water Vapor: psi390.0 05 Temperature: F 720.0 06 Time at Temperature: hrs 6~0 07 Catalyst to Oil Ratio, 08 Mo/Oil: wt/wt 0.042 10 The results of this screening run are shown in Table II
11 under the column labeled Catalyst J.

13 Example 11 15 In this example, the catalyst was prepared according to the 16 water method. The preparation was as follows:

18 Step 1 - 0.63 Pounds of molybdenum trioxide (Climax 19 Molybdenum Grade L) was slurried in 2.73 pounds of distilled 20 water. To this slurry, 0.23 pounds of ammonium hydroxide 21 (25.1 weight percent ammonia) was added and mixed well. The 22 resulting mixture was exposed to the following conditions:

24 Temperature: F 150.0 Pressure: psia 14.7 26 Time: hrs 2.0 28 Step 2 - A portion of the resultant mixture from Step 1 was 29 introduced to a reactor and heated to 150F and the pressure 30 was increased to 400 psig. At this time a 14.0 SCFH flow of 31 a 92~ hydrogen - 8% hydrogen sulfide gas was introduced into 32 the reactor. The reactor was maintained at these conditions 33 for 8.0 hours. At the end of this low-temperature sulfiding 34 step, the reactor is depressurized and ammonia was flashed 01Off. The resulting catalyst is removed from the reactor.
02This catalyst is identified as Catalyst K.

04 Step 3 - Catalyst K was then charged with the decanted oil 05 of Table I to a rocker-bomb reactor. The rocker-bomb 06 reactor was pressurized with a 92~ hydrogen - 8~ hydrogen 07 sulfide gas mixture and heated to run temperature. The 08 heat-up period lasted about 6 hours and constituted the 09 intermediate and high-temperature sulfiding steps because 10 both the intermediate and high-temperature sulfiding temper-11 ature ranges wee traversed for the designated durations.
12 The high-temperature step was continued under hydropro-13 cessing conditions which were as follows:

Pressures, 16 Hydrogen: psi 2200.0 17 Hydrogen Sulfide: psi 182.0 18 Water Vapor: psi390.0 19 Temperature: F 720.0 Time at Temperature: hrs 6.0 21 Catalyst to Oil Ratio, 22 Mo/Oil: wt/wt 0.042 24 The results of this screening run are shown in Table II
25 under the column labeled Catalyst K.

27 Example 12 29 In this example, the catalyst was prepared according to the 30 water method. The preparation was as follows:

01step 1 - 0.63 Pounds of molybdenum trioxide (Climax 02 Molybdenum Grade L) was slurried in 2.73 pounds of distilled 03 water. To this slurry, 0.16 pounds of ammonium hydroxide 04 (25.1 weight percent ammonia) was added and mixed well. The 05 resulting mixture was exposed to the following conditions:

07 Temperature: F 150.0 08 Pressure: psia 14.7 09 Time: hrs 2.0 11 Step 2 - A portion of the resultant mixture from Step 1 was 12 introduced to a reactor and heated to 150F and the pressure 13 was increased to 400.0 psig. At this time a 14.0 SCFH flow 14 of a 92% hydrogen - 8% hydrogen sulfide gas was introduced 15 into the reactor. The reactor was maintained at these con-16 ditions for 8 hours. At the end of this low-temperature 17 sulfiding step, the reactor is depressurized and ammonia was 18 flashed off. The resulting catalyst is removed from the 19 reactor. This catalyst is identified as Catalyst L.
21 Step 3 - Catalyst L was then charged with the decanted oil 22 of Table I to a rocker-bomb reactor. The rocker-bomb reac-23 tor was pressurized with a 92% hydrogen - 8% hydrogen 24 sulfide gas mixture and heated to run temperature. This 25 heat-up period lasted about 6 hours and constituted the 26 intermedlate and high-temperature sulfiding steps because 27 both the intermediate and high-temperature sulfiding temper-28 ature ranges were traversed for the designated durations.
29 The high-temperature sulfiding step was continued under 30 hydroprocessing conditions, which were as follows:

01 Pressures, 02 Hydrogen: psi 2200.0 03 Hydrogen Sulfide: psi 182.0 04 Water Vapor: psi 390.0 05 Temperature: F 720.0 06 Time at Temperature: hrs 6.0 07 Catalyst to Oil Ratio, 08 Mo/Oil: wt/wt 0.042 lO The results of this screening run are shown in Table II
11 under the column labeled Catalyst L.

14 FCC Decanted Oil Feedstock 17 API Gravity 5.0 18 Hydrogen: wt% 8.37 19 Sulfur: wt% 1.11 Nitrogen: wppm 846.0 21 Distillation: F
22 10% 662 23 30% 701 24 50% 732 70% 781 26 90~ 887 . .

` ~ ` , ' Slurry Catalytic Processing E~ample Number: 1 2 3 4 5 6 06 Catalyst Designation: A B C D E F
Prior Prior 07 Preparation Method: OilWater Art Oi] Water Art Product Quality:
09 API Gravity 13.0 17.4 10.4 10.9 11.5 8.8 Sulfur, wt.% 0.52 0.16 0.68 0.70 0.65 0.84 Nitrogen, ppm 116 18 290 255 230 533 11 Hydrogen, wt.% 9.7911.19 9.53 9.52 9.71 9.04 Catalyst:
13 Sulfur/Molybdenum Ratio2.0 1.5 1.8 2.1 1.8 2.1 14 Carbon, wt.~ 15.8 8.2 5.6 16.0 12.1 3.1 Spent Catalyst:
BET Surface Area, m2/g43.5144.4 7.3 23.4 139.4 7.3 16 Avg. Pore Radius, A 54 37 49 31 30 52 Pore Volume, cc/g.:
17 10 - 300A 0.1170.264 0.018 0.036 0.208 1.019 18 Crystallite Thickness, A
19 Angle 2~=19 (XRD) 22 24 24 14 1432 2 Particle Diameter, micron10.6 4.5 4.4 4.8 4.5 7.6 Carbon-Free Basis:
21 BET Surface Area, mZ/g52 157 8 28 159 8 22 Avg. Pore Radius, A 126 48 203 168 47 137 Pore Volume, cc/g.:
23 10 - 300A Radius0.327 0.377 0.078 0.233 0.374 0.052 24 Pore Size Distribution:
A Radius;
250-300 15.6 12.7 15.4 7.3 4.0 19.6 26 200-250 9.6 13.0 17.5 7.9 4.6 18.5 27 150-200 13.9 19.5 25.6 12.7 6.3 23.5 28 100-150 16.2 26.7 15.6 12.5 9.7 18.7 90-100 3.2 5.1 4.1 3.7 2.3 3.8 29 80- 90 4.6 5.6 3.8 3.3 2.7 2.5 70- 80 5.3 5.3 3.5 3.0 2.7 1.9 60- 70 6.2 4.5 4.4 4.5 2.7 3.4 31 50- 60 6.1 4.5 3.0 4.9 4.3 4.3 40- 50 5.1 2.3 2.8 5.7 6.1 2.8 32 30- 40 4.1 0.7 3.2 6.2 7.7 1.0 33 20- 30 4.9 0.0 1.0 7.1 13.8 0.0 34 10_ 20 5.2 0.0 0.0 21.2 33.0 0.0 Total 100.0 99.9 99.9 100.0 99.9 100.0 ~003650 Slurry Catalytic Processing Example Number: 7 8 9 10 11 12 06 Catalyst Designation: G H I J K L
Prior 07 Preparation Method: Art Water Water Water Water Water Product Quality:
09 API Gravity 9.4 16.1 17.0 16.4 19.0 19.5 Sulfur, wt.% 0.81 0.26 0.12 0.16 0.09 0.07 Nitrogen, ppm 571 18 15 18 7 6 11 Hydrogen, wt.~ 9.2910.60 10.92 10.48 10.93 11.29 Catalyst:
13 Sulfur/Molybdenum Ratio1.8 1.8 1.0 2.2 1.9 2.7 14 Carbon, wt.~ 2.4 13.2 12.0 11.2 15.1 17.1 Spent Catalyst:
BET Surface Area, mZ/g 10.7 76.3 74.6 75.8 282.1 291.6 Avg. Pore Radius, A 62 29 23 25 27 36 16 Pore Volume, cc/g.:
17 10 - 300A 0.0330.109 0.087 0.094 0.381 0.519 18 Crystallite Thickness, A
Angle 2~k19 (XRD) 557 13 16 19 l9 Particle Diameter, micron2.5 4.8 5.1 11.8 5.0 9.1 Carbon-Free Basis:
BET Surface Area, m~/g 11 88 85 85 332 352 21 Avg. Pore Radius, A107 63 55 54 38 47 22 Pore Volume, cc/g.:
10 - 300A Radius0.0580.278 0.235 0.232 0.627 0.832 24 Pore Size Distribution:
A R~dius:
250-300 12.0 7.2 4.0 4.3 6.3 5.5 26 200-250 12.7 lO.0 5.2 5.0 4.5 5.3 150-200 19.4 9.8 6.0 7.0 8.3 8.9 27 100-150 16.1 10.5 7.7 10.4 8.2 14.8 90-100 3.9 2.7 2.7 2.4 2.0 3.3 28 80- 90 4.6 2.3 2.7 3.0 2.2 3.5 29 70- 80 4.6 2.3 2.6 3.6 2.2 2.8 60- 70 3.8 2.8 4.3 3.5 2.7 3.1 50_ 60 3.9 3.6 4.9 4.6 3.3 4.0 31 40- 50 3.9 4.4 6.0 6.0 4.5 4.9 32 30- 40 4.4 5.9 7.6 8.3 6.8 6.5 20- 30 4.3 10.9 14.0 12.1 11.6 10.3 33 10- 20 6.5 27.5 32.3 29.8 37.2 26.9 34 Total 100.1 99.9 100.0 100.0 99.8 99.8 ,.. .

~0(~3650 01 Table I shows specifications including API gravity, sulfur 02 content and nitrogen content of the FCC decanted oil feed-03 stock hydroprocessed in the tests of the above examples.

05 Table II shows specifications including API gravity, sulfur 06 content and nitrogen content of the oil after hydroproces-07 sing. These results are presented graphically in Figures 1 08 through 6 for all the examples, except Example 5. The 09 results of Example 5 are unaccountably erratic and therefore 10 are not included in the figures.

12 Figures 1, 2 and 3 show that the catalysts prepared by prior 13 art methods have the smallest 10 to 300A radius pore volume 14 while catalysts prepared by the oil and water sequential 15 sulfiding methods of this invention have higher 10 to 300A
16 radius poor volumes. The indicated ore volumes for the oil 17 and water methods overlap, but certain of the catalysts 18 prepared by the water method have the highest indicated pore 19 volumes.
21 Figures 1, 2 and 3 show that the indicated ore volumes are 22 generally correlatable to product API gravity, to the ratio 23 of product to feed nitrogen levels and to the ratio of prod-24 uct to feed sulfur levels, respectively. In each figure, 25 the poorest results are obtained with the prior art cata-26 lyst, which has the lowest 10 to 300A radius pore volume.
27 Figure 1 shows that the prior art catalyst provides the 28 lowest product API gravity. Figure 2 shows that the prior 29 art catalyst provides the highest product nitrogen levels.
30 Figure 3 shows that the prior art catalyst provides the 31 highest product sulfur levels. Figures 1, 2 and 3, respec-32 tively, show that improved product API gravity, nitrogen and 33 sulfur levels are obtained with the catalyst prepared by the ;~003~S0 01 oil method, which has an intermediate 10 to 300A radius pore 02 volume. Figures 1, 2 and 3 show that the oil method cata-03 lyst provides an intermediate product API gravity and inter-04 mediate product nitrogen and sulfur levels. Figures 1, 2 05 and 3 show that the best results are obtained with those 06 catalysts prepared by the water method which have the 07 highest 10 to 300A radius pore volumes. Figures 1, 2 and 3, 08 respectively, show that the water method catalyst provides 09 the highest product API gravity and the lowest product 10 nitrogen and sulfur levels.

12 Figures 4, 5 and 6 show that the catalysts prepared by prior 13 art methods have the lowest surface area while catalysts 14 prepared by the oil method have a higher surface area and 15 the catalysts prepared by the water sequential sulfiding 16 method have by far the highest surface areas.

18 Figures 4, 5 and 6, respectively, show that the indicated 19 surface areas are generally correlatable to product API
20 gravity, ratio of product to feed nitrogen levels and ratio 21 of product to feed sulfur levels. Figure 4 shows that the 22 prior art catalyst, which has by far the lowest surface 23 area, provides by far the lowest product API gravity.
24 Figure 4 shows that the catalyst prepared by the oil method, 25 which has an intermediate surface area, provides an inter-26 medlate product API gravity. Finally, Figure 4 shows that 27 the catalyst prepared by the water method, which has the 28 highest surface area, provides the highest API gravity.

30 Figure 5 shows that the catalyst prepared by the prior art 31 method, which has the lowest surface area, provides the 32 highest product nitrogen level. Figure 5 shows that the 33 catalyst prepared by the oil method, which has an inter-34 mediate surface area, provides a lower product nitrogen ;~0036S0 Ollevel. Finally, Figure 5 shows that the catalyst prepared 02by the water method, which has by far the largest surface 03area, provides by far the lowest product nitrogen level.
04 Figure 6 shows that the prior art catalyst, which has the 05lowest surface are,a provides the highest product sulfur 06 level. Figure 6 shows that the catalyst prepared by the oil 07 method, which has an intermediate surface area, provides a 08 lower product sulfur level. Finally, Figure 6 shows that 09 the catalyst prepared by the water method, which has by far 10 the largest surface area, provides by far the lowest product 11 sulfur level.

13 Figures 1, 2 and 3 indicate that to provide high catalyst 14 activity, the 10 to 300A radius pore volume (cc/g) of the 15 catalyst should be at least 0.1, preferably at least 0.15 16 and most preferably at least 0.2. The indicated pore volume 17 range can be between 0.2 and 0.4, but is generally between 18 0.15 and 1, preferably between 0.2 and 1 and most preferably 19 between 0.3, 0.4 or 0.5 and 1, or higher than 1.
21 Figures 4, 5 and 6 indicate that to provide high catalyst 22 activity the surface area (m2/g) of the catalyst should be 23 generally at least 20, preferably at least 25 and most 24 preferably at least 50 or 100. The surface area range can 25 be between 25 and 75, but is generally between 20 and 400, 26 preferably between 25 and 400 and most preferably between 75 27 and 400, or higher than 400.

29 The water method for preparing a catalyst of this invention 30 is illustrated in the Figure 7. According to Figure 7, 31 molybdenum or tungsten, in the form of water-insoluble MoO3 32 or wo3, is introduced ~hlough lines 10 and 12 to dissolver 33 zone 14. Recycle molybdenum or tungsten, from a source 34 described below, is introduced through line 16. Water and ,~ ~

01 ammonia are added to dissolver zone 14 through line 18.
02 Water-insoluble molybdenum oxide or tungsten oxide is 03 converted to a water-soluble ammonium molybdate salt or 04 ammonium tungstate salt in dissolver zone 14.

06 Aqueous ammonium molybdate or ammonium tungstate containing 07 excess ammonia is discharged from zone 14 through line 20, 08 admixed with hydrogen sulfide, preferably mixed with hydro-09 gen, entering through line 22 and then passed through line lO 24 to low-temperature sulfiding zone 26. In low-temperature ll sulfiding zone 26, ammonium molybdate or ammonium tungstate 12 is converted to thiosubstituted ammonium molybdates or thio-13 substituted ammonium tungstates. In zone 26 the sulfiding 14 temperature is sufficiently low that the ammonium salt is 15 not decomposed while thiosubstitution is beginning. If the 16 ammonium salt were decomposed in the early stages of thio-17 substitution, an insoluble molybdate or oxythiomolybdate in 18 a mixture with MoO3, or an insoluble tungstate or oxythio-19 tungstate in a mixture with WO3 would precipitate out, 20 inhibiting further thiosubstitution.

22 An effluent stream from low-temperature sulfiding zone 26 is 23 passed through line 28 to intermediate temperature sulfiding 24 zone 30. Intermediate temperature sulfiding zone 30 is 25 operated at a temperature higher than the temperature in 26 low-temperature sulfiding zone 26. The sulfiding reaction 27 i~ continued in zone 30 and ammonium oxythiomolybdate or 28 ammonium oxythiotungstate is converted to molybdenum oxysul-29 fide or tungsten axysulfide and/or molybdenum trisulfide or 30 tungsten trisulfide, thereby freeing ammonia.

32 An effluent stream from intermediate temperature sulfiding 33 zone 30 is passed through line 32 to ammonia separator or 34 flash chamber 36. In flash separator 36, cooling and :`

01 depressurizing of the effluent stream from line 32 causes 02 vaporization of ammonia and hydrogen sulfide, which are 03 discharged through line 33. Flash conditions are estab-04 lished so that only a minor amount of water is vaporized and 05 sufficient water remains in the flash residue to maintain an 06 easily pumpable slurry suspension of the catalyst.

08 Flash separator residue is removed from flash separator 36 09 through line 38. The flash residue in line 38 is essen-10 tially free of oil since no oil was introduced to low-tem-11 perature sulfiding zone 26 or intermediate temperature 12 sulfiding zone 30. Feed oil is introduced to the system for 13 the first time through line 40 and is admixed with a 14 hydrogen-hydrogen sulfide mixture entering through lines 42 15 and 44. The flash residue in line 38 together with feed 16 oil, hydrogen and hydrogen sulfide is introduced through 17 line 46 to high-temperature sulfiding zone 48.

19 High-temperature sulfiding zone 48 is operated at a tempera-20 ture higher than the temperature in intermediate temperature 21 sulfiding zone 30. In high-temperature sulfiding zone 48, 22 molybdenum oxysulfide or tungsten oxysulfide is converted to 23 highly active molybdenum sulfide or tungsten sulfide. The 24 preparation of the catalyst is now complete. Some hydro-25 processing of the feed oil entering through line 40 is per-26 formed ln high-temperature sulfiding zone 48.

28 High-temperature sulfiding zone 48 is operated at a tempera-29 ture higher than the temperature in intermediate temperature 30 sulfiding zone 30. In high-temperature sulfiding zone 48, ~003650 01 molybdenum oxysulfide or tungsten oxysulfide is converted to 02highly active molybdenum sulfide or tungsten sulfide. The 03 preparation of the catalyst is now complete. Some hydro-04 processing of the feed oil entering though line 40 is per-05 formed in high-temperature sulfiding zone 48.

07 An effluent stream from high-temperature sulfiding zone 48 08 is passed through lines 50 and 52 to hydroprocessing reactor 09 56. Hydroprocessing reactor 56 is operated at a temperature 10 higher than the temperature in high-temperature sulfiding 11 zone 48. If the slurry catalyst bypassed high-temperature 12 sulfiding zone 48 enroute to hydroprocessing reactor 56, the 13 high-temperature of hydroprocessing reactor 56 would cause 14 the water in hydroprocessing reactor 56 to oxygenate the lS catalyst and compete with sulfiding, thereby causing the 16 catalyst to be converted into a sulfur-deficient high coke 17 producer. When high-temperature sulfiding zone 48 precedes 18 the hydroprocessing reactor, the relatively lower tempera-19 ture in zone 48 allows the sulfiding reaction to prevail 20 over any competing oxidation reaction in the presence of 21 water to complete the sulfiding of the catalyst and render 22 it stable at the higher temperature of hydroprocessing zone 23 56. With certain oil feedstocks, the relatively lower tem-2~ perature of high-temperature sulfiding zone 48 will suffice 25 for performing the oil hydroprocessing reactions, in which 26 ca6e hydroprocesfiing reactor 56 can be dispensed with. How-~7 ever, most feed oils will require the relatively higher tem-28 perature in hydroprocessing reactor 56 to complete the oil 29 hydrotreating reactions.
31 An effluent stream is removed from hydroprocessing reactor 32 56 through line 60 and passed to flash separator 62. An ~.

01 overhead gaseous stream is removed from separator 62 through 02 line 64 and is passed through a scrubber 66 wherein impuri-03 ties such as ammonia and light hydrocarbons are removed and 04 discharged from the system through line 68. A stream of 05 purified hydrogen and hydrogen sulfide is recycled through 06 lines 70, 44 and 46 to high-temperature sulfiding 07 reactor 48.

09 A bottoms oil is removed from separator 62 through line 72 10 and passed to atmospheric distillation tower 74. As indi-11 cated in the figure, various fractions are separated in 12 tower 74 including a refinery gas stream, a C3/C4 light 13 hydrocarbon stream, a naphtha stream, a No. 2 fuel oil and a 14 vacuum charge oil stream for passage to a vacuum distilla-15 tion tower, not shown.

17 A concentrated catalyst slurry stream is removed from the 18 bottom of tower 74 through line 76. Some of this catalyst-19 containing stream can be recycled to hydroprocessing reactor 20 56 through lines 58 and 52, if desired. Most, or all, of 21 the heavy catalytic slurry in line 76 is passed to 22 deasphalting chamber 78 from which a deasphalted oil is 23 removed through line B1. A highly concentrated deactivated 24 catalyst stream i8 removed from deasphalting chamber 78 25 through line B0 and passed to catalyst generation zone 82.

27 The catalyst entering regeneration zone 82 comprises molyb-28 denum sulfide or tungsten sulfide together with impurity 29 metals acquired from the feed oil. The impurity metals 30 comprise primarily vanadium sulfide and nickel sulfide. In 31 regeneration chamber 82 all of the metal sulfides are 32 oxidized by combustion to the oxide state. The metal oxides 33 are then passed through line 84 to catalyst reclamation 34 zone 86. In reclamation zone 86 molybdenum oxide or ;~0036S0 01 tungsten oxide is separated from impurity metals including 02 vanadium oxide and nickel oxide by any suitable ~eans.
03 Non-dissolved impurity metals including vanadium and nickel 04 are discharged from the system through line 887 while puri-05 fied and concentrated molybdenum oxide or tungsten oxide is 06 passed through line 16 for mixing with make-up molybdenum or 07 tungsten oxide entering through line 10, to repeat the 08 cycle.

10 If desired, the process shown in Figure 7 can be modified by 11 inserting ammonia flash chamber 36 in advance of inter-12 mediate temperature sulfiding reactor 30. In that case, the 13 hydrogen and hydrogen sulfide mixture in line 42 and the 14 feed oil in line 40 can be charged to intermediate tempera-15 ture sulfiding reactor 30. The effluent from intermediate 16 temperature sulfiding reactor 30 then would be passed 17 directly to high-temperature sulfiding reactor 4B, without 18 any intermediate separation.

20 Figure 8 illustrates a process for preparing a catalyst by 21 the oil method. As shown in Figure 8, catalytic molybdenum 22 or tungsten, in the form of water-insoluble MoO3 or W03, is 23 introduced through lines llO and 112 to dissolver zone 114.
24 Recycle molybdenum or tungsten, from a source described 25 below, i8 introduced through line 116. Water and ammonia 26 ~re ~dded to di~601ver zone 114 through line 118. Water-27 insoluble molybdenum oxide or tungsten oxide is converted to 28 water soluble ammonium molybdate salts or ammonium.tungstate 29 salts in dissolver zone 114.
31 Aqueous ammonium molybdate or ammonium tungstate containing 32 excess ammonia is discharged from zone 114 through line 120 33 and then passed through presulfiding zone 121 to which 34 hydrogen sulfide is added through line 123. The effluent .

01 from zone 121 is passed through line 125 and admixed with 02 hydrogen and hydrogen sulfide entering through lines 122 and 03 124 and feed oil entering through line 126 and then passed 04 through line 128 to low-temperature sulfiding zone 130. In 05 low-temperature sulfiding zone 130, ammonium molybdate or 06 ammonium tungstate is converted to thiosubstituted ammonium 07 molybdates or thiosubstituted ammonium tungstates. In low-08 temperature sulfiding zone 130 the sulfiding temperature is 09 sufficiently low that the ammonium salt is not decomposed 10 while thiosubstitution is beginning. If the ammonium salt 11 were decomposed in the early staqes of thiosubstitution, an 12 insoluble molybdate or oxythiomolybdate in a mixture with 13 MoO3, or an insoluble tungstate or oxythiotungstate or in a 14 mixture with WO3 would precipitate out in zone 130 and tend 15 to plug zone 130.

17 An effluent stream from low-temperature sulfiding zone 130 18 is passed through line 132 to intermediate temperature sul-19 fiding zone 134. Intermediate temperature sulfiding zone 20 134 is operated at a temperature higher than the temperature 21 in low-temperature sulfiding zone 130. The sulfiding reac-22 tion is continued in zone 134 and ammonium oxythiomolybdate 23 or ammonium oxythiotungstate is converted to molybdenum 24 oxysulfide and/or molybdenum trisulfide or tungsten oxysul-25 fide and/or tungsten trisulfide, thereby freeing ammonia.

27 An effluent stream from intermediate temperature sulfiding 28 zone 134 is passed through line 136 to high-temperature 29 sulfiding zone 138. High-temperature sulfiding zone 138 is 30 operated at a temperature higher than the temperature in 31 intermediate temperature sulfiding zone 134. In high-tem-32 perature sulfiding zone 138, molybdenum oxysulfide or 200365~:) 01 tungsten oxysulfide is converted to highly active molybdenum 02 sulfide or tungsten sulfide. The preparation of the cata-03 lyst is now complete. Some hydroprocessing of the feed oil 04 entering through line 126 is performed in high-temperature 05 sulfiding zone 138.

07 An effluent stream from high-temperature sulfiding zone 138 08 is passed through lines 140 and 142 to hydroprocessing 09 reactor 144. Hydroprocessing reactor 144 is operated at a 10 temperature higher than the temperature in high-temperature 11 sulfiding zone 138. If the slurry catalyst bypassed high-12 temperature reactor 138 enroute to hydroprocessing reactor 13 144, the high-temperature of hydroprocessing reactor 144 14 would cause the water in hydroprocessing reactor 144 to 15 oxygenate the catalyst and compete with sulfiding thereby 16 causing the catalyst to be converted into a sulfur-deficient 17 high coke producer. When high-temperature sulfiding 18 zone 138 precedes the hydroprocessing reactor, the relative-19 ly lower temperature in zone 138 allows the sulfiding 20 reaction to prevail over any competing oxidation reaction in 21 the presence of water to complete the sulfiding of the 22 catalyst and render it stable at the higher temperature of 23 hydroprocessing zone 144. With certain oil feedstocks, the 24 relatively lower temperature of high-temperature sulfiding 25 zone 138 will suffice for performing the oil hydroprocessing 26 roactions, in which case hydroprocessing reactor 144 can be 27 di6pensed with. However, most feed oils will require the 28 relatively higher temperature in hydroprocessing reactor 144 29 to complete the oil hydrotreating reactions.
31 An effluent stream is removed from hydroprocessing reactor 32 144 through line 146 and passed to flash separator 148. An 33 overhead gaseous stream is removed from separator 148 34 through line 150 and is passed through a scrubber 152 01 wherein impurities such as ammonia and light hydrocarbons 02 are removed and discharged from the system through line 154.
03 A stream of purified hydrogen and hydrogen sulfide is 04 recycled through lines 156, 124 and 128 to low-temperature 05 sulfiding reactor 130.

07 A bottoms oil is removed from separator 148 through line 158 08 and passed to atmospheric distillation tower 160. Various 09 fractions are separated in tower 160 including a refinery 10 gas stream, a C3/C4 light hydrocarbon stream, a naphtha 11 stream, a No. 2 fuel oil and a vacuum charge oil stream for 12 passage to a vacuum distillation tower, not shown.

14 A concentrated catalyst slurry stream is removed from the 15 bottom of tower 160 through line 162. Some of this 16 catalyst-containing stream can be recycled to hydropro-17 cessing r actor 144 through lines 162 and 164, if desired.
18 Most, or all, of the heavy catalytic slurry in line 162 is 19 passed through line 166 to deasphalting chamber 168 from 20 which a deasphalted oil is removed through line 170. A
21 highly concentrated deactivated catalyst stream is removed 22 from deasphalting chamber 168 through line 170 and passed to 23 catalyst generation zone 172.

25 The catalyst entering regeneration zone 172 comprises molyb-26 denum sulfide or tunqsten sulfide together with any impurity 27 metals acquired from the feed oil. The impurity metals 28 comprise prlmarily vanadium sulfide and nickel sulfide. In 29 regeneration chamber 172 all of these metal sulfides are 30 oxidized by combustion to the oxide state. The metal oxides 31 are then passed through line 174 to catalyst reclamation 32 zone 176. In reclamation zone 176 molybdenum oxide or 33 tungsten oxide is separated from impurity metals including 34 vanadium oxide and nickel oxide by any suitable means.

01 Non-dissolved impurity metals including vanadium and nickel 02 are discharged from the system through line 178 while puri-03 fied and concentrated molybdenum oxide or tungsten oxide is 04 passed through line 116 for mixing with make-up molybdenum 05 or tungsten oxide entering through line 110, to repeat the 06 cycle.

~2lo

Claims

1. A Group VIB metal sulfide slurry catalyst for the hydroprocessing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range of at least 0.1 cc/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

2. A Group VIB metal sulfide slurry catalyst for the hydroprocessing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range of at least 0.2 cc/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

3. A Group VIB metal sulfide slurry catalyst for the hydroprocessing of heavy hydrocarbonaceous oil or residua having a surface area of at least 50 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

4. A Group VIB metal sulfide slurry catalyst for the hydroprocessing of heavy hydrocarbonaceous oil or residua having a surface area of at least 50 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

5. A Group VIB metal sulfide slurry catalyst for the hydroprocessing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range of at least 0.1 cc/g and a surface area of at least 20 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

6. A Group VIB metal sulfide slurry catalyst for the hydroprocessing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range of at least 0.2 cc/g and a surface area of at least 50 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

7. The catalyst of Claim 1 wherein the Group VIB metal is molybdenum.

8. The catalyst of Claim 1 wherein the Group VIB metal is tungsten.

9. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size radius of at least 0.1 cc/q, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

10. A molybdenum sulfide slurry catalyst for the hydrop-rocessing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range of at least 0.15 cc/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

11. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.2 and 0.4 cc/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

12. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.2 and 0.4 cc/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

13. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.15 and 1 cc/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

14. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.2 and 1 cc/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

15. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.4 and 1 cc/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

16. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a surface area of at least 20 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

17. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a surface area of at least 25 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

18. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a surface area of at least 50 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

19. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a surface area of at least 10 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

20. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a surface area between about 25 and 75 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

21. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a surface area between about 25 and 75 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

22. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a surface area between about 25 and 400 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

23. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a surface area between about 75 and 400 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature sufficient to convert said sulfided compound into an active hydroprocessing catalyst.

24. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range of at least 0.1 cc/g and a surface area of at least 20 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

25. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range of at least 0.2 cc/g and a surface area of at least 50 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

26. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range of at least 0.2 cc/g and a surface area of at least 50 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

27. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.2 and 0.4 cc/g and a surface area of at least 100 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

28. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.15 and 1 cc/g and a surface area bet-ween 25 and 75 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

29. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.2 and 1 cc/g and a surface area between 20 and 400 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

30. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.4 and 1 cc/g and a surface area between 25 and 400 m2/g, wherein said catalyst is prepared by presulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

31. A molybdenum sulfide slurry catalyst for the hydro-processing of heavy hydrocarbonaceous oil or residua having a pore volume in the 10 to 300.ANG. radius pore size range between 0.5 and 1 and a surface area above 400 m2/g, wherein said catalyst is prepared by pre-sulfiding a Group VI metal compound in an aqueous environment, and charging said sulfided compound into a hydroprocessing reactor zone at a temperature suffic-ient to convert said sulfided compound into an active hydroprocessing catalyst.

32. The catalyst of Claim 31 wherein said Group VIB metal sulfide is approximately of the empirical formula of a Group VIB metal disulfide.

33. The catalyst of Claim 30 wherein said Group VIB metal sulfide is approximately of the empirical formula of a Group VIB metal disulfide.

34. The catalyst of Claim 30 wherein said Group VIB metal sulfide is approximately of the empirical formula of a Group VIB metal disulfide.

35. The catalyst of Claim 31 wherein said Group VIB metal sulfide is approximately of the empirical formula of a Group VIB metal disulfide.

36. The catalyst of Claim 1 including a Group VIII metal.

37. The catalyst of Claim 9 including a Group VIII metal.

38. The catalyst of Claim 24 including a Group VIII metal.

39. The catalyst of Claim 1 including nickel.

40. The catalyst of Claim l including cobalt.