HYDROTREATING CATALYST WITH A TITANIUM CONTAINING CARRIER AND SULFUR CONTAINING ORGANIC ADDITIVE

Abstract

Generally, it is disclosed a catalyst for use in a hydrotreating hydrocarbon feedstocks and the method of making such catalyst. It is generically provided that the catalyst comprises at least one Group VIB metal component, at least one Group VIII metal component, about 1 to about 30 wt % C, and preferably about 1 to about 20 wt % C, and more preferably about 5 to about 15 wt % C of one or more sulfur containing organic additive and a titanium-containing carrier component, wherein the amount of the titanium component is in the range of about 3 to about 60 wt %, expressed as an oxide (TiO.sub.2) and based on the total weight of the catalyst. The titanium-containing carrier is formed by co-extruding or precipitating a titanium source with a Al.sub.2O.sub.3 precursor to form a porous support material comprising Al.sub.2O.sub.3 or by impregnating a titanium source onto a porous support material comprising Al.sub.2O.sub.3.

Claims

1. A catalyst comprising at least one Group VIB metal component, at least one Group VIII metal component, at least one sulfur containing organic additive component, and a titanium-containing carrier component, wherein the amount of titanium content is in the range of about 1 to about 60 wt %, expressed as an oxide (TiO.sub.2), based on the total weight of the catalyst.

2. The catalyst of claim 1 wherein the Group VIB metal component is in an amount of about 15 to about 30 wt % expressed as an oxide based on the total weight of the catalyst.

3. The catalyst of claim 1 wherein the Group VIII metal component is in an amount of about 2 to about 8 wt % expressed as an oxide based on the total weight of the catalyst.

4. The catalyst according to claim 1 wherein the Group VIB metal component comprises molybdenum and/or tungsten.

5. The catalyst according to claim 1 wherein the Group VIII metal component comprises nickel and/or cobalt.

6. The catalyst of claim 1 wherein the at least one sulfur containing organic component comprises a mercapto carboxylic acid.

7. The catalyst of claim 6 wherein the mercapto carboxylic acid is thioglycolic acid, thiolactic acid, thiopropionic acid, mercapto succinic acid or cysteine.

8. The catalyst of claim 1 further comprising a phosphorous component in the amount of about 1 to about 8% expressed as oxide based on the total weight of the catalyst.

9. The catalyst of claim 1 wherein the at least one sulfur containing organic additive component is in amount of about 1 to about 30 wt % C.

10. The catalyst of claim 9 wherein the at least one sulfur containing organic additive component is in amount of about 1 to about 20 wt % C.

11. The catalyst of claim 10 wherein the at least one sulfur containing organic additive component is in amount of about 5 to about 15 wt % C.

12. A method of producing a catalyst, the method comprising co-extruding a titanium source with a porous material comprising Al.sub.2O.sub.3 to form a titanium-containing carrier extrudate, drying and calcining the extrudate, and impregnating the calcined extrudate with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source, the amount of the titanium source being sufficient so as to form a catalyst composition at least having a titanium content in the range of about 1 wt % to about 60 wt %, expressed as an oxide (TiO.sub.2), based on the total weight of the catalyst.

13. A method of producing a catalyst, the method comprising precipitating a titanium source with an aluminum source, extruding the precipitate to form a titanium-containing carrier extrudate, drying and calcining the extrudate, and impregnating the calcined extrudate with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source, the amount of the titanium source being sufficient so as to form a catalyst composition at least having a titanium content in the range of about 1 wt % to about 60 wt %, expressed as an oxide (TiO.sub.2), based on the total weight of the catalyst.

14. The method of claim 13 wherein the precipitation comprises the steps of (a) simultaneous dosing of sodium aluminate and aluminum sulfate to water at a fixed pH (b) the formed alumina filter cake is re-slurried in water (c) to this slurry TiOSO.sub.4 or titanium sulfate is added at a fixed pH>7 controlled by an alkaline solution.

15. The method of claim 13 wherein the aluminum source and the titanium source are mixed in one stream and sodium aluminate is dosed either simultaneously or subsequently to water at a pH>7.

16. A method of producing a catalyst, the method comprising impregnating a porous material comprising Al.sub.2O.sub.3 with a titanium source to form a titanium-containing carrier, drying and calcining the carrier, and impregnating the calcined carrier with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source, the amount of the titanium source being sufficient so as to form a catalyst composition at least having a titanium content in the range of about 1 wt % to about 60 wt %, expressed as an oxide (TiO.sub.2), based on the total weight of the catalyst.

17. The method of claim 12, 13 or 16 further comprising the impregnation with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source being performed in a single step with a solution comprising a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source.

18. The method of claim 12, 13 or 16 further comprising the impregnation with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source being performed in more than one step, wherein the carrier is impregnated with a solution comprising at least one Group VIB metal source and/or at least one Group VIII metal source, followed by a step of impregnating the carrier with a solution comprising a sulfur containing organic additive.

19. The method of claim 12, 13 or 16 wherein the titanium source is selected from the group consisting of titanyl sulfate, titanium sulfate, titanium alkoxide or Titanium(IV)bis(ammonium lactato)dihydroxide.

20. A method which comprises contacting a hydrocarbon feed with a catalyst according to any of the preceding claims, under hydrotreating conditions so as to hydrotreat the hydrocarbon feed.

Description

EXAMPLES

Activity Test

[0043] The activity tests were carried out in micro flow reactors. Light Gas Oil (LGO) spiked with dimethyl disulfide (DMDS) (total S content of 2.5 wt %) was used for presulfiding, A Straight-run Gas Oil (SRGO), having a S content of 1.4-1.1 wt. % and a N content of 215-200 ppm, was used for testing in examples A-E. A VGO having a S content of 2.1 wt % and a N content of 1760 ppm N was used in example F. Testing takes place at equal volumetric catalyst intake. The relative volumetric activities for the various catalysts were determined as follows. For each catalyst the volumetric reaction constant kw,′ was calculated using n.sup.th order kinetics and a reaction order of 1.0 for HDN and 1.2 for HDS. The relative volumetric activities (RVA) of the different catalysts of the invention vs a comparative catalyst were subsequently calculated by taking the ratio of the reaction constants.

[0044] In the tables, SA is surface area, PV is pore volume, DMPD is mean pore diameter based on the desorption branch of the N.sub.2 physisorption isother, S is sulfur, N is nitrogen, P is pressure, goat is the amount of catalyst in the reactor, LHSV is liquid hourly space velocity, and r.o. is reaction order.

Support Preparation

[0045] The following supports were made in accordance with the procedures described below. One support was prepared as a reference (Si, Al.sub.2O.sub.3). A summary of the properties for each support can be found in Table 1.

[0046] Example S1: Comparative S1. Comparative S1 was 100% standard Al.sub.2O.sub.3 prepared via a co-precipitation process. Aluminum sulfate (Alum) and sodium aluminate (Natal) were dosed simultaneously to a heel of water at 60° C. and pH 8.5. The flows of Natal and Alum were fixed and the pH was controlled constantly with NaOH or H.sub.2SO.sub.4. Total dosing time was approximately 1 hour and the final Al.sub.2O.sub.3 concentration in the reactor was approximately 4% on weight basis. The pH was then raised with NaOH or Natal to approximately 10 and the slurry was aged for 10 minutes while stirring. The slurry was filtered over a filter cloth and washed with water or a solution of ammonium bi-carbonate in water until sufficient removal of sodium and sulfate. The cake was dried, extruded and calcined.

[0047] Example S2: Support S2. The support S2 was prepared via a co-extrusion process of alumina and titania filter cakes. The alumina filter cake was prepared via the process described in Example S1 (prior extrusion). The titania filter cake was prepared via hydrolysis of an aqueous solution of TiOSO.sub.4 at 99° C. for 5 hours followed by neutralization with NaOH to pH 7. The precipitate was filtered and washed salt free using water or a ammonium bi-carbonate solution. The two filter cakes were mixed in a kneader and extruded. The extrudates were calcined at 650° C. for 1 hour under airflow of ca. 10 nL/min. The final composition of the support (dry base) was found to be 49.7 wt. % TiO.sub.2 and 50.3 wt. % Al.sub.2O.sub.3.

[0048] Example S3: Support S3. The support S3 was prepared via a co-precipitation process. Aluminum sulfate (Alum) and Titanyl sulfate (TiOSO.sub.4) mixed in one stream and sodium aluminate (Natal) were dosed simultaneously to a heel of water at 60° C. and pH 8.5. The flows of Natal and Alum/TiOSO.sub.4 were fixed and the pH was controlled constantly with NaOH or H.sub.2SO.sub.4. Total dosing time was approximately 1 hour and the final solid concentration in the reactor was approximately 4% on weight basis. The pH was then raised with NaOH or Natal to approximately 10 and the slurry was aged for 20 minutes while stirring. The slurry was filtered over a filter cloth and washed with water or a solution of ammonium bi-carbonate in water until sufficient removal of sodium and sulfate. The cake was dried, extruded and calcined at 650° C. for 1 hour under airflow of ca. 10 nL/min. The final composition of the support (dry base) was found to be 48.0 wt. % TiO.sub.2 and 52.0 wt. % Al.sub.2O.sub.3.

[0049] Example S4: Support S4. The support S4 was prepared by co-precipitation using the same process as was used to prepare support S3, but using different amounts of the TiO.sub.2 and Al.sub.2O.sub.3 precursors. The final composition of the support (dry base) was found to be 20.9 wt. % TiO.sub.2 and 79.1 wt. % Al.sub.2O.sub.3.

[0050] Example S5: Support S5. The support S5 was prepared by consecutive (Step-) precipitation of alumina and titania. Firstly alumina (boehmite) was precipitated according to the procedure as described in 51. After filtration and proper washing, the precipitate was transferred back to the reactor. Boehmite filter cake was slurried in a stainless steel vessel with water and stirred while heating up to 60° C. To the slurry TiOSO.sub.4 solution was dosed at a fixed rate and the pH was controlled at 8.5 via addition of NaOH solution. The dosing time was 25 minutes at 60° C. The slurry was thoroughly washed with water or a solution of ammonium bi-carbonate in water to remove salts, dried, extruded and calcined at 650° C. for 1 hour under airflow of ca. 10 nL/min. The final composition of the support (dry base) was found to be 21.1 wt. % TiO.sub.2 and 78.9 wt. % Al.sub.2O.sub.3.

[0051] Example S6: Support S6. The support S6 was prepared by coating an aqueous titania precursor on alumina extrudates. The extrudates used consisted predominantly of γ-alumina and had a surface area of 271 m.sup.2/g, a pore volume of 0.75 ml/g and a mean pore diameter of 8.7 nm as determined from the N.sub.2 physisorption desorption isotherm. The pores of the alumina extrudates were filled with an aqueous solution of Titanium(IV)bis(ammonium lactato)dihydroxide, aged for 2 hours at 60° C. and pre-dried in a rotating pan until the appearance of the extrudates was no longer wet and eventually dried overnight at 120° C. The sample was calcined at 450° C. for 2 hours under airflow. This procedure was repeated a second time reaching higher titania loadings. The final composition of the support (dry base) was found to be 27.8 wt. % TiO.sub.2 and 72.2 wt. % Al.sub.2O.sub.3.

[0052] Example S7: Support S7. The support S7 was prepared by coating an alkoxide titania precursor on alumina extrudates. The extrudates used had the same characteristics as those used in S6. The pores of the alumina were filled with Ti-isopropoxide solution in propanol. The aging process was carried out inside an atmosbag filled with a N.sub.2 atmosphere at room temperature for 2 hours, and then the same was placed outside of the atmosbag for hydrolysis overnight (at RT). Finally the sample was dried at 120° C. overnight and calcined at 450° C. for 2 hours. The final composition of the support (dry base) was found to be 18.9 wt. % TiO.sub.2 and 81.1 wt. % Al.sub.2O.sub.3.

[0053] Example S8: Support S8. The support S8 was prepared by a second coating with an alkoxide titania precursor on the TiO.sub.2—Al.sub.2O.sub.3 extrudates obtained in S7. The procedure as described in S7 was repeated a second time reaching higher titania loadings. The final composition of the support (dry base) was found to be 43.7 wt. % TiO.sub.2 and 56.3 wt. % Al.sub.2O.sub.3.

[0054] Example S9: Support S9. The support S9 was prepared by strike-precipitation of alumina and titania. Natal was diluted in water and under vigorous stirring waterglass was added while heating at 60° C. To this mixture aluminum sulfate and titanyl sulfate were added in 20 min with a final pH of 6.5. NaOH was used to adjust the pH to 7.2 and the mixture was aged for 1 hour at 60° C. while stirring. The cake was re-slurried with water, brought to pH 10 with ammonia and aged at 95° C. for 1 hour while stirring. Then, the slurry was filtered and washed with water to remove excess ammonia, dried, extruded and calcined at 650° C. for 1 hour under airflow of ca. 10 nL/min with 25 vol. % steam. The final composition of the support (dry base) was found to be 23.1 wt. % TiO.sub.2, 3.2 wt. % SiO.sub.2 and 73.7 wt. % Al.sub.2O.sub.3.

[0055] Example S10: Support S10. The support S10 was prepared in the same way as S9, but similar TiO.sub.2 and lower SiO.sub.2 sources were used. The final composition of the support (dry base) was found to be 21.3 wt. % TiO.sub.2, 0.5 wt. % SiO.sub.2 and 78.2 wt. % Al.sub.2O.sub.3.

[0056] Example S11: Support S11. The support S11 was prepared in the same way as S9, but lower TiO.sub.2 and SiO.sub.2 sources were used. The final composition of the support (dry base) was found to be 10.8 wt. % TiO.sub.2, 0.5 wt. % SiO.sub.2 and 88.7 wt. % Al.sub.2O.sub.3.

[0057] Example S12: Support S12. The support S12 was prepared by co-extrusion/kneading of Al.sub.2O.sub.3 cake and a titanium source. The Titanium(IV)isopropoxide (titania source) was added after 15 minutes kneading time. Later a vent hole was opened in order to let the alcohol evaporate. The kneaded material was extruded and then, the plate with wet extrudates was placed in the stove and kept there overnight at 120° C. Finally, the sample was calcined at 650° C. with 25% steam. The final composition of the support (dry base) was found to be 10.6 wt. % TiO.sub.2, 0.87 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0058] The sodium content present is any of these supports is very low (<0.5 wt. %), since it is known as detrimental for the hydroprocessing activity. A summary of the compositions and characteristics of these different supports can be found in Table 1.

TABLE-US-00001 TABLE 1 Summary of supports prepared in Examples S1-12 and some of their physical properties. Weight % Weight % SA PV DMPD Support Procedure TiO.sub.2 (*) SiO2 (*) (m.sup.2/g) (ml/g) (nm) S1 reference 0 — 271 0.84 8.1 S2 co-extrusion 47.9 — 200 0.52 8.7 S3 co-precipitation 48.0 — 258 0.64 7.7 S4 co-precipitation 20.9 — 304 0.86 7.9 S5 step-precipitation 21.1 — 239 0.78 9.4 S6 coating 27.8 — 275 0.48 7.8 S7 coating 18.9 — 271 0.60 8.1 S8 coating 43.7 — 229 0.38 5.5 S9 strike-precipitation 23.1 3.2 293 0.56 6.1 S10 strike-precipitation 21.3 0.5 236 0.56 8.0 S11 strike-precipitation 10.8 0.5 240 0.65 9.0 S12 co-extrusion 10.6 0.87 247 0.54 6.7 (*) based on the total weight of the support dry base

Catalyst Preparation and Testing

Example A: Positive Effect of TiO.SUB.2 .Addition in Different Amounts and Via Different Preparation Methods on the Activity of NiMo Catalysts

[0059] The following examples illustrate the positive effect of TiO.sub.2 addition in the support on the activity of NiMo catalysts when combined with sulfur-containing organics in the catalyst preparation. The catalysts were prepared as described in examples A1-A12 using the same method to apply metals and S-organic additives to the catalysts and have a comparable volume loading of metals in the reactor. The catalysts were tested in a multi-reactor unit under medium pressure ultra-low sulfur diesel conditions at equal catalyst volume. Table 2 shows the pre-sulfidation and test conditions and Table 3 shows the activity results.

TABLE-US-00002 TABLE 2 Pre-sulfiding and testing (medium P ULSD) format used for activity testing of NiMo examples A. Pre-sulfiding conditions LHSV P H.sub.2/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45 300 320 24 Testing conditions P H.sub.2/oil Temperature Time @ Feed (bar) (Nl/l) (° C.) condition (days) SRGO 1.09 wt. % S 45 300 350 4 and 200 ppmN

[0060] Example A1: Comparative A1. Comparative A1 was prepared by consecutive impregnation of support Comparative A1 with (i) a NiMoP aqueous solution and, after drying, (ii) with thioglycolic acid. Both impregnations were performed in a rotating pan. The metal loaded intermediate was prepared from support S1 using impregnation with an amount of aqueous NiMoP solution equivalent to fill 105% of the pore volume, as is known for a person skilled in the art. The pore volume of the support was determined by a so-called water PV measurement in which the point of incipient wetness was determined by addition of water to the carrier extrudates. The NiMoP solution was prepared by dispersing of the required amount of NiCO.sub.3 in water. The solution was then heated to 60° C. while stirring. Half of the required H.sub.3PO.sub.4 was added carefully to the solution and subsequently MoO.sub.3 was added in small portions. The solution was heated up to 92° C. to obtain a clear solution. Finally, the rest of the H.sub.3PO.sub.4 was added to the solution and water was added to reach the concentration required for the desired metal loading. After impregnation, the extrudates were allowed to age for 1 hour in a closed vessel, after which drying was carried out at 120° C. for at least one hour. Subsequently, impregnation of the thus formed metal loaded intermediate with thioglycolic acid was carried out with neat thioglycolic acid to reach a loading of this compound on the catalysts of 3.5 mol/mol metals (Mo+Ni) in the catalyst. The thus formed composite was further aged for 2 hour, while rotating. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was 23.0 wt. % MoO.sub.3, 4.5 wt. % NiO, 4.0 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

[0061] Example A2: Invention A2. Invention A2 was prepared using support S2 and the same preparation process as in A1. The composition of the metal impregnated dried catalyst (dry base) was 17.2 wt. % MoO.sub.3 and 3.3 wt. % NiO, 3.1 wt. % P.sub.2O.sub.5, 38.6 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0062] Example A3: Invention A3. Invention A3 was prepared using support S3 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 19.4 wt. % MoO.sub.3 and 3.8 wt. % NiO, 3.5 wt. % P.sub.2O.sub.5, 37.4 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0063] Example A4: Invention A4. Invention A4 was prepared using support S4 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 23.7 wt. % MoO.sub.3 and 4.5 wt. % NiO, 4.1 wt. % P.sub.2O.sub.5, 13.0 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0064] Example A5: Invention A5. Invention A5 was prepared using support S5 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 24.4 wt. % MoO.sub.3 and 4.7 wt. % NiO, 4.3 wt. % P.sub.2O.sub.5, 13.5 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0065] Example A6: Invention A6. Invention A6 was prepared using support S6 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 18.0 wt. % MoO.sub.3 and 3.4 wt. % NiO, 3.1 wt. % P.sub.2O.sub.5, 21.2 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0066] Example A7: Invention A7. Invention A7 was prepared using support S7 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 20.1 wt. % MoO.sub.3 and 4.0 wt. % NiO, 3.5 wt. % P.sub.2O.sub.5, 12.6 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0067] Example A8: Invention A8. Invention A8 was prepared using support S8 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 18.7 wt. % MoO.sub.3 and 3.7 wt. % NiO, 3.4 wt. % P.sub.2O.sub.5, 25.9 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0068] Example A9: Invention A9. Invention A9 was prepared using support S9 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 18.0 wt. % MoO.sub.3 and 3.5 wt. % NiO, 3.3 wt. % P.sub.2O.sub.5, 15.7 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0069] Example A10: Comparative A10. Comparative A10 was prepared using support S1 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 24.8 wt. % MoO.sub.3 and 4.4 wt. % NiO, 4.3 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

[0070] Example A11: Invention A11. Invention A11 was prepared using support S10 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 22.0 wt. % MoO.sub.3 and 3.7 wt. % NiO, 3.8 wt. % P.sub.2O.sub.5, 0.37 wt. % SiO.sub.2, 15.0 TiO.sub.2 wt. % and the rest is Al.sub.2O.sub.3.

[0071] Example A12: Invention A12. Invention A12 was prepared using support S11 and the same preparation process as A1. The composition of the metal impregnated dried catalyst (dry base) was 23.6 wt. % MoO.sub.3 and 4.1 wt. % NiO, 4.0 wt. % P.sub.2O.sub.5, 0.36 wt. % SiO.sub.2, 7.4 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

TABLE-US-00003 TABLE 3 The effect of the addition of TiO.sub.2 in combination with a sulfur containing organic on the activity of supported NiMo catalysts in medium P ULSD activity testing. RVA RVA g.sub.CAT db mg MoO.sub.3 LHSV N HDN LHSV S HDS Example Support Reactor Reactor HDN (ppm) r.o. 1.0 HDS (ppm) r.o. 1.2 Comparative A1 S1 0.720 184 4.0 49 100% 2.5 151 100% Invention A2 S2 0.881 168 40 108% 99 113% Invention A3 S3 0.794 171 22 152% 42 151% Invention A4 S4 0.647 170 44 105% 119 107% Invention A5 S5 0.640 173 35 123% 65 130% Invention A6 S6 0.990 189  9 211% 24 170% Invention A7 S7 0.844 184 19 165% 33 169% Invention A8 S8 0.936 195 11 197% 28 171% Invention A9 S9 0.856 171 17 175% 38 155% Comparative A10 S1 0.719 198 58 100% 2.7 144 100% Invention A11 S10 0.855 209  9 246% 24 177% Invention A12 S11 0.820 215 19 190% 29 169%

[0072] As can be seen in Table 3, the catalysts that were prepared using a Ti-containing support are significantly more active in HDN and HDS than the comparative catalyst without any Ti (A1, A10) using the same S-containing organic additive, impregnation method and amount of metals in the reactor. Since different LHSV have been used, RVAs of Inventions A2-A9 are relative to the activity of Comparative A1 and RVAs of Inventions A11-A12 are relative to Comparative A10.

Examples B: Positive Effect of TiO.SUB.2 .Addition in Different Amounts and Via Different Preparation Methods on the Activity of CoMo Catalysts

[0073] These examples illustrate the positive effect of addition of TiO.sub.2 in the support on the activity of CoMo catalysts when combined with sulfur-containing organics in the preparation in a wide range of TiO.sub.2 contents. Catalysts B1-B10 were all prepared using the same method to apply metals and thioglycolic acid to the catalyst and have a comparable volume loading of metals in the reactor. The catalysts were tested in a multi-reactor unit under medium pressure ultra-low sulfur diesel conditions. Table 4 shows the pre-sulfidation and Table 5 shows the activity results.

TABLE-US-00004 TABLE 4 Pre-sulfiding and testing (medium P ULSD) format used for activity testing of CoMo examples B. Pre-sulfiding conditions LHSV P H.sub.2/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45 300 320 24 Testing conditions P H.sub.2/oil Temperature Time @ Feed (bar) (Nl/l) (° C.) condition (days) SRGO 1.09 wt. % S 45 300 350 4 and 200 ppmN

[0074] Example B1: Comparative B1. Comparative B1 was prepared by consecutive impregnation of support Comparative A1 with (i) a CoMoP aqueous solution and, after drying, (ii) with thioglycolic acid. Both impregnations were performed in a rotating pan. The metal loaded intermediate was prepared from support S1 using impregnation with an amount of aqueous CoMoP solution equivalent to fill 105% of the pore volume, as is known for a person skilled in the art. The pore volume of the support was determined by a so-called water PV measurement in which the point of incipient wetness was determined by addition of water to the carrier extrudates. The CoMoP solution was prepared by dispersing of the required amount of CoCO.sub.3 in water. The solution was then heated to 60° C. while stirring. Half of the required H.sub.3PO.sub.4 was added carefully to the solution and subsequently MoO.sub.3 was added in small portions. The solution was heated up to 92° C. to obtain a clear solution. Finally, the rest of the H.sub.3PO.sub.4 was added to the solution and water was added to reach the concentration required for the desired metal loading. After impregnation, the extrudates were allowed to age for 1 hour in a closed vessel, after which drying was carried out at 120° C. for at least one hour. Subsequently, impregnation of the thus formed metal loaded intermediate with thioglycolic acid was carried out with neat thioglycolic acid to reach a loading of this compound on the catalysts of 3.5 mol/mol metals (Mo+Co) in the catalyst. The thus formed composite was further aged for 2 hours, while rotating. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was 24.0 wt. % MoO.sub.3 and 4.6 wt. % CoO, 4.2 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

[0075] Example B2: Invention B2. Invention B2 was prepared using support S3 and the same preparation process as B1. The composition of the metal impregnated dried catalyst (dry base) was 19.1 wt. % MoO.sub.3 and 3.6 wt. % CoO, 3.3 wt. % P.sub.2O.sub.5, 37.2 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0076] Example B3: Invention B3. Invention B3 was prepared using support S5 and the same preparation process as B1. The composition of the metal impregnated dried catalyst (dry base) was 19.8 wt. % MoO.sub.3 and 3.8 wt. % CoO, 3.3 wt. % P.sub.2O.sub.5, 12.4 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0077] Example B4: Inventive B4. Invention B4 was prepared using support S6 and the same preparation process as B1. The composition of the metal impregnated dried catalyst (dry base) was 19.1 wt. % MoO.sub.3 and 3.6 wt. % CoO, 3.3 wt. % P.sub.2O.sub.5, 20.7 wt. % TiO.sub.2 and the rest is

[0078] Example B5: Invention B5. Invention B5 was prepared using support S7 and the same preparation process as B1. The composition of the metal impregnated dried catalyst (dry base) was 19.8 wt. % MoO.sub.3 and 3.8 wt. % CoO, 3.5 wt. % P.sub.2O.sub.5, 20.1 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0079] Example B6: Comparative B6. Comparative B6 was prepared using support S1 and the same preparation process as B1. The composition of the metal impregnated dried catalyst (dry base) was 26.5 wt. % MoO.sub.3 and 4.8 wt. % CoO, 4.4 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

[0080] Example B7: Invention B7. Invention B7 was prepared using support S9 and the same preparation process as B1. The composition of the metal impregnated dried catalyst (dry base) was 24.2 wt. % MoO.sub.3 and 4.5 wt. % CoO, 4.1 wt. % P.sub.2O.sub.5, 1.8 wt. % SiO.sub.2, 13.9 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0081] Example B8: Comparative B8. Comparative B8 was prepared using support S1 and the same preparation process as B1. The composition of the metal impregnated dried catalyst (dry base) was 26.1 wt. % MoO.sub.3 and 4.8 wt. % CoO, 4.4 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

[0082] Example B9: Invention B9. Invention B9 was prepared using support S10 and the same preparation process as B1. The composition of the metal impregnated dried catalyst (dry base) was 23.4 wt. % MoO.sub.3 and 3.9 wt. % CoO, 4.0 wt. % P.sub.2O.sub.5, 0.36 wt. % SiO.sub.2, 14.7 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0083] Example B10: Invention B10. Invention B10 was prepared using support S11 and the same preparation process as B1. The composition of the metal impregnated dried catalyst (dry base) was 20.5 wt. % MoO.sub.3 and 4.3 wt. % CoO, 4.3 wt. % P.sub.2O.sub.5, 0.36 wt %. SiO.sub.2, 7.2 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

TABLE-US-00005 TABLE 5 The effect of the addition of a sulfur containing organic in combination with TiO.sub.2-containing support in the activity of CoMo catalysts in medium P ULSD activity testing. g.sub.CAT db mg MoO.sub.3 LHSV N RVA HDN Example Support Reactor Reactor HDN (ppm) r.o. 1 Comparative B1 S1 0.730 194 3.5 50 100% Invention B2 S3 0.837 180 26 158% Invention B3 S5 0.829 182 34 131% Invention B4 S6 0.919 187 21 160% Invention B5 S7 0.891 196 20 174% Comparative B6 S1 0.731 215 3.2 34 100% Invention B7 S9 0.789 212  4 224% Comparative B8 S1 0.701 203 4.0 88 100% Invention B9 S10 0.893 232 19 259% Invention B10 S11 0.812 226 40 186%

[0084] As can be seen in Table 5, the catalysts that were prepared on a Ti-containing supports (B2-B5, B7 and B9-B10) are significantly more active in HDN than the comparative catalysts without any Ti (B1, B6 and B8) using the same S-organic additive and impregnation method. Since different LHSV have been used, RVAs of Inventions B2-B5 are relative to the activity of Comparative B1, RVA of Inventions B7 is relative to Comparative B6 and RVAs of Inventions B9-B10 are relative to Comparative B8.

[0085] Examples C: Positive effect of a wide variation of S-organic additives on the activity of NiMo and CoMo catalysts

[0086] These examples illustrate the positive effect of S-organic additives on the activity of NiMo and CoMo catalysts when combined with TiO.sub.2-containing. The catalyst examples are 4 NiMo and 4 CoMo grades based on the same Ti—Al support and different sulfur-organic additives. They were prepared using the same method to apply metals and have a comparable volume loading of metals in the reactor. The catalysts were tested in a multi-reactor unit under medium pressure ultra-low sulfur diesel conditions. Table 6 shows the pre-sulfidation and test conditions used for both NiMo and CoMo catalysts and Table 7 and 8 shows the activity results.

TABLE-US-00006 TABLE 6 Pre-sulfiding and testing (medium P ULSD) format used for activity testing of NiMo and CoMo catalysts from examples C. Pre-sulfiding conditions LHSV P H.sub.2/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45 300 320 24 Testing conditions P H.sub.2/oil Temperature Time @ Feed (bar) (Nl/l) (° C.) condition (days) SRGO 1.09 wt. % 45 300 350 4 and 200 ppmN

[0087] Example C1: Comparative C1. Comparative C1 was prepared by impregnation of a NiMoP aqueous solution (no S-organic additive) on support S11. The impregnation was performed in a rotating pan with an amount of aqueous NiMoP solution equivalent to fill 105% of the pore volume, as is known for a person skilled in the art. The pore volume of the support was determined by a so-called water PV measurement in which the point of incipient wetness was determined by addition of water to the carrier extrudates. The NiMoP solution was prepared by dispersing of the required amount of NiCO.sub.3 in water. The solution was then heated to 60° C. while stirring. Half of the required H.sub.3PO.sub.4 was added carefully to the solution and subsequently MoO.sub.3 was added in small portions. The solution was heated up to 92° C. to obtain a clear solution. Finally, the rest of the H.sub.3PO.sub.4 was added to the solution and water was added to reach the concentration required for the desired metal loading. After impregnation, the extrudates were allowed to age for 1 hour in a closed vessel, after which drying was carried out at 120° C. for at least one hour. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was 23.6 wt. % MoO.sub.3 and 4.1 wt. % NiO, 4.0 wt. % P.sub.2O.sub.5, 0.36 wt. % SiO.sub.2, 7.4 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0088] Example C2: Invention C2. Invention C2 was prepared using Comparative C1. A second impregnation with thiolactic acid at 95% PV saturation was performed without the use of H.sub.2O, and aged for 2 hours at 80° C. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was the same as Comparative C1.

[0089] Example C3: Invention C3. Invention C3 was prepared using Comparative C1. A second impregnation with 3-mercaptopropionic acid was performed with a fixed amount reaching 15 wt. % carbon of the total catalyst, and aged for 2 hour at 80° C. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was the same as Comparative C1.

[0090] Example C4: Invention C4. Invention C4 was prepared Comparative C1. A second impregnation with mercaptosuccinic acid was performed with a fixed amount reaching 15 wt. % carbon of the total catalyst, and aged for 2 hours at 80° C. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was the same as Comparative C1.

TABLE-US-00007 TABLE 7 The effect of the addition of a sulfur-containing organic in combination with TiO.sub.2- containing support in the activity of NiMo catalysts in medium P ULSD activity testing. g.sub.CAT db mg MoO.sub.3 LHSV N RVA HDN LHSV S RVA HDS Example Support Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) r.o. 1.2 Comparative C1 S11 0.787 206 4.0 66 100% 2.7 175 100% Invention C2 S11 0.770 202 40 153%  65 147% Invention C3 S11 0.768 201 56 116% 104 120% Invention C4 S11 0.780 205 46 124%  74 128%

[0091] As observed in Table 7, the NiMo catalysts with different types of S-containing organic additives (C2-C4) show higher HDN and HDS activities than the comparative (C1) example without organic additives using the same support (S11) and similar metal loadings (ca. 200 gMoO.sub.3/Reactor).

[0092] Example C5: Comparative C5. Comparative C5 was prepared from support S11 using impregnation with an amount of aqueous CoMoP solution equivalent to fill 105% of the pore volume, as is known for a person skilled in the art. The CoMoP solution was prepared by dispersing of the required amount of CoCO.sub.3 in water. The solution was then heated to 60° C. while stirring. Half of the required H.sub.3PO.sub.4 was added carefully to the solution and subsequently MoO.sub.3 was added in small portions. The solution was heated up to 92° C. to obtain a clear solution. Finally, the rest of the H.sub.3PO.sub.4 was added to the solution and water was added to reach the concentration required for the desired metal loading. After impregnation, the extrudates were allowed to age for 1 hour in a closed vessel, after which drying was carried out at 120° C. for at least one hour. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was 23.2 wt. % MoO.sub.3, 3.9 wt. % CoO, 2.4 wt. % P.sub.2O.sub.5, 0.37 wt. % SiO.sub.2, 7.5 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

[0093] Example C6: Invention C6. Invention C6 was prepared using Comparative C5. A second impregnation with thiolactic acid at 95% PV saturation was performed without the use of H.sub.2O, and aged for 2 hours at 80° C. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was the same as Comparative C5.

[0094] Example C7: Invention C7. Invention C7 was prepared using Comparative C5. A second impregnation with 3-mercaptopropionic acid was performed with a fixed amount reaching 15 wt. % carbon of the total dried base catalyst, and aged for 2 hours at 80° C. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was the same as Comparative C5.

[0095] Example C8: Invention C8. Invention C8 was prepared using Comparative C5. A second impregnation with mercaptosuccinic acid was performed with a fixed amount reaching 15 wt. % carbon of the total dried base catalyst, and aged for 2 hours at 80° C. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was the same as Comparative C5.

TABLE-US-00008 TABLE 8 The effect of the addition of a sulfur-containing organic in combination with TiO.sub.2- containing support in the activity of CoMo catalysts in medium P ULSD activity testing. g.sub.CAT mg RVA db MoO.sub.3 LHSV N HDN Example Support Reactor Reactor HDN (ppm) r.o. 1 Comparative C5 S11 0.77 197 4.0 89 100% Invention C6 S11 0.79 203 52 158% Invention C7 S11 0.8 223 63 137% Invention C8 S11 0.77 197 74 116%

[0096] As observed in Table 8, the CoMo catalysts with different types of S-containing organic additives (C6-C8) show higher HDN activity than the comparative (C5) example without organic additives using the same support (S11) and similar metal loadings (ca. 200 gMoO.sub.3/Reactor).

Examples D: The Synergetic Effect of Sulfur-Containing Organics & Ti—Al.SUB.2.O.SUB.3 .Support for NiMo Catalysts

[0097] In the following examples, it is illustrated that the use of a TiO.sub.2/Al.sub.2O.sub.3 support in combination with S-organics results in a synergetic effect for NiMo catalysts. The activity benefit of applying a TiO.sub.2/Al.sub.2O.sub.3 support in combination with S-organics is higher than can be expected based on the separate contributions of the (i) TiO.sub.2/Al.sub.2O.sub.3 support and (ii) the S-organics as determined in separate experiments and can therefore be regarded as surprising. The NiMo catalyst examples presented have comparable metal loadings and were tested in a multi-reactor unit under medium pressure ultra-low sulfur diesel conditions. Table 9 shows the experimental settings for the pre-sulfidation and test conditions and Table 10 shows the amount of catalyst that was loaded in the different reactors and the activity results.

TABLE-US-00009 TABLE 9 Pre-sulfiding and test (medium P ULSD) format used for activity testing of NiMo catalysts from examples D. Pre-sulfiding conditions LHSV P H.sub.2/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45 300 320 24 Testing conditions P H.sub.2/oil Temperature Time @ Feed (bar) (Nl/l) (° C.) condition (days) SRGO 1.09 wt. % 45 300 350 4 and 200 ppmN

[0098] Example D1: Comparative D1. Comparative D1 was prepared using support S1 and impregnated with NiMoP aqueous solution and no organic additive. The method used for preparation of the impregnation solution is the same as the method described in Example C1. The composition of the metal impregnated dried catalyst (dry base) was 24.8 wt. % MoO.sub.3, 4.2 wt. % NiO, 2.7 wt. % P.sub.2O.sub.5 and the rest Al.sub.2O.sub.3.

[0099] Example D2: Comparative D2. Comparative D2 was prepared using support S1 and impregnated with NiMoP aqueous solution and thioglycolic acid additive. The method used for preparation of the impregnation solution, and the amount of S-organics applied (relative to the metals) is the same as the method described in Example A1. The composition of the metal impregnated dried catalyst (dry base) was the same as D1.

[0100] Example D3: Comparative D3. Comparative D3 was prepared using support S10 and impregnated with NiMoP aqueous solution and no organic additive. The method used for preparation of the impregnation solution is the same as the method described in Example C1. The composition of the metal impregnated dried catalyst (dry base) was 21.8 wt. % MoO.sub.3, 3.6 wt. % NiO, 2.4 wt. % P.sub.2O.sub.5, 0.38 wt. % SiO.sub.2, 15.4 wt. % TiO.sub.2 and the rest Al.sub.2O.sub.3.

[0101] Example D4: Invention D4. Invention D4 was prepared using support S10 and impregnated with NiMoP aqueous solution and thioglycolic acid additive. The method used for preparation of the impregnation solution, and the amount of S-organics applied (relative to the metals) is the same as the method described in Example A1. The composition of the metal impregnated dried catalyst (dry base) was the same as Example D3.

[0102] Example D5: Comparative D5. Comparative D5 was prepared using support S11 and impregnated with NiMoP aqueous solution and no organic additive. The method used for preparation of the impregnation solution is the same as the method described in Example C1.

[0103] The composition of the metal impregnated dried catalyst (dry base) was 23.3 wt. % MoO.sub.3, 3.7 wt. % NiO, 2.5 wt. % P.sub.2O.sub.5, 0.38 wt. % SiO.sub.2, 7.6 wt. % TiO.sub.2 and the rest Al.sub.2O.sub.3.

[0104] Example D6: Invention D6. Invention D6 was prepared using support S11 and impregnated with NiMoP aqueous solution and thioglycolic acid additive. The method used for preparation of the impregnation solution, and the amount of S-organics applied (relative to the metals) is the same as the method described in Example A1. The composition of the metal impregnated dried catalyst (dry base) was the same as Example D5.

TABLE-US-00010 TABLE 10 The effect of the addition of a sulfur containing organic in combination with TiO.sub.2-containing support in the activity of NiMo catalysts in medium P ULSD activity testing. RVA mg RVA HDS g.sub.CAT db MoO.sub.3 LHSV N HDN Sxy LHSV S r.o. Sxy Example Support Reactor Reactor HDN (ppm) r.o. 1 HDN HDS (ppm) 1.2 HDS Comparative D1 S1 0.710 196 4.0 87 100% 2.7 261 100% Comparative D2 S1 0.713 197 67 121% 183 110% Comparative D3 S10 0.829 201 53 141%  94 135% Invention D4 S10 0.847 205  6 370% 208  20 221% 76 Comparative D5 S11 0.762 197 73 114% 211 106% Invention D6 S11 0.793 205 23 218%  83  29 192% 76

[0105] As observed in Table 10, the activity benefit of the catalysts of the invention (D4 and D6), containing TiO.sub.2 in the support and S-containing organics are larger than expected from the individual benefits of titania addition (D3 and D5, without S-organic additive) or use of S-organic additive (D2, without titania). Both inventions are ultimately compared with Comparative D1 (no organic and no titania) at similar metal loadings.

[0106] To determine the extent of the synergy between the effect of (i) TiO.sub.2 addition to the support and (ii) addition of S-containing organics on catalyst activity, we determined Synergy factor Sxy as defined in Equation 1. RVA.sub.0,0 is the relative activity of the reference catalyst (without Ti (x) or organics (y)) Values for ax and by were determined from the RVA of the comparative catalyst that is based on the Al.sub.2O.sub.3 support with the same organics (RVA.sub.x,0=RVA.sub.0,0+ax) and the RVA of the comparative catalyst based on the TiO.sub.2—Al.sub.2O.sub.3 support without organics (RVA.sub.0,y=RVA.sub.0,0+by). A positive value of Sxy signifies that the activity of catalysts of the invention is higher than could be expected based on the individual contributions of the support and the organics on catalyst activity.

RVA.sub.x,y=RVA.sub.0,0+ax+by+Sxy  [Eq. 1]

Examples E: The Synergetic Effect of Sulfur-Containing Organics & Ti—Al.SUB.2.O.SUB.3 .Support for CoMo Catalysts

[0107] In the following examples, it is illustrated that the use of a TiO.sub.2/Al.sub.2O.sub.3 support in combination with S-organics results in a synergetic effect for CoMo catalysts for a wide range of metal loadings. The activity benefit of applying a TiO.sub.2/Al.sub.2O.sub.3 support in combination with S-organics is higher than can be expected based on the separate contributions of the (i) TiO.sub.2/Al.sub.2O.sub.3 support and (ii) the S-organics as determined in separate experiments and can therefore be regarded as surprising. The CoMo catalyst examples presented have been tested in a multi-reactor unit under medium pressure ultra-low sulfur diesel conditions. The set of examples have been tested at a comparable volumetric metal loading. A first set at high metal loading (Examples E1-E4) and a second set at low metal loading (Examples E5-E8). Tables 11 and 13 show the experimental settings for the pre-sulfidation and test conditions and Tables 12 and 14 show the amount of catalyst that was loaded in the different reactors and the activity results.

[0108] Example E1: Comparative E1. Comparative E1 was prepared using support S1 and impregnated with CoMoP aqueous solution and no organic additive. The method used for preparation of the impregnation solution is the same as the method described in Example C5. The composition of the metal impregnated dried catalyst (dry base) was 24.6 wt. % MoO.sub.3, 4.3 wt. % CoO, 2.6 wt. % P.sub.2O.sub.5 and the rest Al.sub.2O.sub.3.

[0109] Example E2: Comparative E2. Comparative E2 was prepared using support S1 and impregnated with CoMoP aqueous solution and thioglycolic acid additive. The method used for preparation of the impregnation solution is the same as the method described in Example B1. The composition of the metal impregnated dried catalyst (dry base) was the same as E1.

[0110] Example E3: Comparative E3. Comparative E3 was prepared using support S11 and impregnated as the method described in Example E1. The composition of the metal impregnated dried catalyst (dry base) was 21.8 wt. % MoO.sub.3, 3.7 wt. % CoO, 2.3 wt. % P.sub.2O.sub.5, 0.38 wt. % SiO.sub.2, 15.2 wt. % TiO.sub.2 and the rest Al.sub.2O.sub.3.

[0111] Example E4: Invention E4. Invention E4 was prepared using support S11 and impregnated as the method described in Example E1. The composition of the metal impregnated dried catalyst (dry base) was the same as Example E3.

TABLE-US-00011 TABLE 11 Pre-sulfiding and test (medium P ULSD) format used for activity testing of the high metal loading CoMo catalysts from examples E. Pre-sulfiding conditions LHSV P H.sub.2/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45 300 320 24 Testing conditions P H.sub.2/oil Temperature Time @ Feed (bar) (Nl/l) (° C.) condition (days) SRGO 1.09 wt. % 45 300 350 4 and 200 ppmN

TABLE-US-00012 TABLE 12 The effect of the addition of a sulfur containing organic in combination with TiO.sub.2-containing support in the activity of high metal loading CoMo catalysts in medium P ULSD activity testing. g.sub.CAT db mg MoO.sub.3 LHSV N RVA HDN Sxy Example Support Reactor Reactor HDN (ppm) r.o. 1 HDN Comparative E1 S1 0.682 186 4.0 100 100% Comparative E2 S1 0.701 192  81 132% Comparative E3 S10 0.829 201  67 145% Invention E4 S10 0.83 201  37 226% 49

[0112] As observed in Table 12, the activity benefit of the invention (E4) is larger than expected from the individual benefits of titania addition (E3, without S-organic additive) or use of S-organic additive (E2, without titania). The activity of all catalysts is ultimately compared with Comparative E1 (no organic and no titania) at similar metal loadings.

[0113] Example E5: Comparative E5. Comparative E5 was prepared using support S1 and impregnated, as E1, with CoMoP aqueous solution without organics. The composition of the metal impregnated dried catalyst (dry base) was 19.3 wt. % MoO.sub.3 and 3.6 wt. % CoO, 3.2 P.sub.2O.sub.5 wt. % and the rest is Al.sub.2O.sub.3.

[0114] Example E6: Comparative E6. Comparative E6 was prepared using support S9 and impregnated as E5. The composition of the metal impregnated dried catalyst (dry base) was 17.5 wt. % MoO.sub.3 and 3.2 wt. % CoO, 2.9 P.sub.2O.sub.5 wt. %, 15.8 TiO.sub.2 wt. %, 2.0 SiO.sub.2 wt. % and the rest is Al.sub.2O.sub.3.

[0115] Example E7: Comparative E7. Comparative E7 was prepared using support S1. Firstly, it was impregnated with CoMoP aqueous solution as E1 and after drying a second impregnation with thioglycolic acid (3.5 mol/mol metals in the catalyst) in a rotating pan was performed. The intermediate was further aged for 2 hour, while rotating, and then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was 19.3 wt. % MoO.sub.3 and 3.6 wt. % CoO, 3.2 P.sub.2O.sub.5 wt. % and the rest is Al.sub.2O.sub.3.

[0116] Example E8: Invention E8. Invention E8 was prepared using support S9 and impregnated as E7. The composition of the metal impregnated dried catalyst (dry base) was 17.5 wt. % MoO.sub.3 and 3.2 wt. % CoO, 2.9 P.sub.2O.sub.5 wt. %, 15.7 TiO.sub.2 wt. % and 2.1 SiO.sub.2 wt. %.

TABLE-US-00013 TABLE 13 Pre-sulfiding and test (medium P ULSD) format used for activity testing of low metal loading CoMo examples E. Pre-sulfiding conditions LHSV P H.sub.2/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45 300 320 24 Testing conditions P H.sub.2/oil Temperature Time @ Feed (bar) (Nl/l) (° C.) condition (days) SRGO 1.4 wt. % S 45 300 350 3 and 200 ppmN

TABLE-US-00014 TABLE 14 The effect of the addition of an organic in combination with TiO.sub.2-containing support in the activity of CoMo catalysts low metal loading in medium P ULSD activity testing. Mg RVA RVA g.sub.CAT db MoO.sub.3 LHSV N HDN Sxy LHSV S HDS Sxy Example Support Reactor Reactor HDN (ppm) r.o. 1 HDN HDS (ppm) r.o. 1.2 HDS Comparative E5 S1 0.634 136 2.6 86 100% 2.0 244 100% Comparative E6 S9 0.736 143 2.6 38 192% 119 126% Comparative E7 S1 0.611 131 2.8 68 129% 143 108% Invention E8 S9 0.714 139 2.8  7 362% 141  24 172% 38 CoMo commercial catalyst 0.731 196 2.6 27 235%  50 161% CoMo commercial catalyst 0.742 196 2.8 28 235%  41 161%

[0117] In the case of low metal loading catalysts a synergetic effect between the support and the organics is also observed. This was surprising since neither TiO.sub.2 nor the organics applied in the preparation will contribute directly to the activity of the catalysts. This effect can be clearly observed for a wide range of metal loadings (high ca. 220 gMoO.sub.3/L and low around 140 gMoO.sub.3/L) and most easily observed in the HDN activities. Finally, the activity of the low metal loading catalyst of the invention (E8) can be compared to that of a CoMo commercial catalyst that was included in the same test.

Examples F: The Benefit of TiO.SUB.2.—Al.SUB.2.O.SUB.3 .Co-Extruded Support in Combination with S-Organic Additives for NiMo Catalysts in HC-PT Application

[0118] The following examples illustrate the positive effect of TiO.sub.2 addition in the support on the activity of NiMo catalysts when combined with S-containing organics in the catalyst preparation. The catalysts were prepared as described in examples F1-F2 using the same method to apply metals to the catalysts and have a comparable volume loading of metals in the reactor. The catalysts were tested in a multi-reactor unit HC-PT conditions. Table 15 shows the pre-sulfidation and test conditions and Table 16 shows the activity results.

TABLE-US-00015 TABLE 15 Pre-sulfiding and test (HC-PT) format used for activity testing of low metal loading NiMo examples F. Pre-sulfiding conditions LHSV P H.sub.2/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45 300 320 24 Testing conditions P H.sub.2/oil Temperature Time @ Feed (bar) (Nl/l) (° C.) condition (days) VGO 2.1 wt. % S 120 1000 380 3 and 1760 ppmN

[0119] Example F1: Comparative F1. Comparative F1 was prepared using support S1 and a NiMoP aqueous solution. The catalyst was prepared from support S1 impregnated with an amount of aqueous NiMoP solution equivalent to fill 105% of the pore volume, as is known for a person skilled in the art. The pore volume of the support was determined by a so-called water PV measurement in which the point of incipient wetness was determined by addition of water to the carrier extrudates. The NiMoP solution was prepared by dispersing of the required amount of NiCO.sub.3 in water. The solution was then heated to 60° C. while stirring. Half of the required H.sub.3PO.sub.4 was added carefully to the solution and subsequently MoO.sub.3 was added in small portions. The solution was heated up to 92° C. to obtain a clear solution. Finally, the rest of the H.sub.3PO.sub.4 was added to the solution and water was added to reach the concentration required for the desired metal loading. After impregnation, the extrudates were allowed to age for 1 hour in a closed vessel, after which drying was carried out at 120° C. for at least one hour. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (dry base) was 25.9 wt. % MoO.sub.3, 4.1 wt. % NiO, 4.4 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

[0120] Example F2: Invention F2. Invention F2 was prepared using support S12 and impregnated with an amount of aqueous NiMoP solution equivalent to fill 105% of the pore volume, as is known for a person skilled in the art. The pore volume of the support was determined by a so-called water PV measurement in which the point of incipient wetness was determined by addition of water to the carrier extrudates. The NiMoP solution was prepared by dispersing of the required amount of NiCO.sub.3 in water. The solution was then heated to 60° C. while stirring. Half of the required H.sub.3PO.sub.4 was added carefully to the solution and subsequently MoO.sub.3 was added in small portions. The solution was heated up to 92° C. to obtain a clear solution. Finally, the rest of the H.sub.3PO.sub.4 was added to the solution and water was added to reach the concentration required for the desired metal loading. After impregnation, the extrudates were allowed to age for 1 hour in a closed vessel, after which drying was carried out at 120° C. for at least one hour. The extrudates were then poured out into a petri dish and placed in a static oven at 80° C. for 16 hours. Subsequently, impregnation of the thus formed metal loaded intermediate with thioglycolic acid was carried out with neat thioglycolic acid to reach a loading of this compound on the catalysts of 3.5 mol/mol metals (Mo+Ni) in the catalyst. The thus formed composite was further aged for 2 hours, while rotating. The composition of the metal impregnated dried catalyst (dry base) was 24.1 wt. % MoO.sub.3, 4.0 wt. % NiO, 4.1 P.sub.2O.sub.5 wt. %, 7.2 wt. % TiO.sub.2, 0.59 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

TABLE-US-00016 TABLE 16 The effect of the addition of an organic in combination with TiO.sub.2-containing support in the activity of NiMo catalysts in HC-PT activity testing. g.sub.CAT Mg RVA db MoO.sub.3 LHSV N HDN Example Support Reactor Reactor HDN (ppm) r.o. 1 Comparative F1 S1 0.719 186 1.70 182 100 Invention F2 S12 0.940 226  57 156

[0121] As can be observed in table 16, Invention F2 containing S-organic additives and titanium in the support show higher benefits in both HDN and HDS than the Comparative F1 example. The benefit of combining a S-organic additive and a Ti-containing support is visible also for HC-PT applications.

[0122] Components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another component, a solvent, or etc.). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution as such changes, transformations, and/or reactions are the natural result of bringing the specified components together under the conditions called for pursuant to this disclosure. Thus the components are identified as ingredients to be brought together in connection with performing a desired operation or in forming a desired composition.

[0123] The invention may comprise, consist, or consist essentially of the materials and/or procedures recited herein.

[0124] As used herein, the term “about” modifying the quantity of an ingredient in the compositions of the invention or employed in the methods of the invention refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like. The term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about”, the claims include equivalents to the quantities.

[0125] Except as may be expressly otherwise indicated, the article “a” or “an” if and as used herein is not intended to limit, and should not be construed as limiting, the description or a claim to a single element to which the article refers. Rather, the article “a” or “an” if and as used herein is intended to cover one or more such elements, unless the text expressly indicates otherwise.

[0126] Each and every patent or other publication or published document referred to in any portion of this specification is incorporated in toto into this disclosure by reference, as if fully set forth herein.

[0127] This invention is susceptible to considerable variation in its practice. Therefore the foregoing description is not intended to limit, and should not be construed as limiting, the invention to the particular exemplifications presented hereinabove.