Hydrotreating catalyst with a titanium containing carrier and organic additive

Abstract

Disclosed is a catalyst for use in hydrotreating hydrocarbon feedstocks and methods of making the same catalyst. Specifically, a catalyst is disclosed comprises at least one Group VIB metal component, at least one Group VIII metal component, an organic additive resulting in a C-content of the final catalysts of 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 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 AI.sub.2O.sub.3 precursor to form a porous support material primarily comprising AI.sub.2O.sub.3 or by impregnating a titanium source onto a porous support material primarily comprising AI.sub.2O.sub.3. Special preference is given to alumina and alumina containing up to and no more than 1 wt % of silica, preferably no more than 0.5 wt % based on the total weight of the support (dry base).

Claims

1. 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 an 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 to about 60 wt. %, expressed as an oxide (TiO.sub.2) based on the total weight of the catalyst and has less than 1.0 wt. % silica expressed as an oxide (SiO.sub.2) and based on the total weight of the catalyst; wherein the precipitation comprises the steps of (a) simultaneous dosing of sodium aluminate and aluminum sulfate to water at a fixed pH (b) re-slurrying the formed alumina filter cake in water (c) adding to this slurry TiOSO.sub.4 or titanium sulfate at a fixed pH>7 controlled by an alkaline solution.

2. 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 an 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 to about 60 wt. %, expressed as an oxide (TiO.sub.2) based on the total weight of the catalyst and has less than 1.0 wt. % silica expressed as an oxide (SiO.sub.2) and based on the total weight of the catalyst; wherein the aluminum source and the titanium source are mixed in one stream and sodium aluminate are dosed either simultaneously or subsequently to water at a pH>7.

3. The method of claim 1 or 2 wherein the organic additive is an organic compound selected from the group consisting of organic compounds comprising at least two oxygen atoms and 2-10 carbon atoms, and the ethers, esters, acetals, acid chlorides, acid amides, oligomers or polymers thereof and the impregnation is performed in a single step with a solution comprising an organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source.

4. The method of claim 1 or 2 wherein the organic additive is an organic compound selected from the group consisting of organic compounds comprising at least two oxygen atoms and 2-10 carbon atoms, and the ethers, esters, acetals, acid chlorides, acid amides, oligomers or polymers thereof and the impregnation is 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 an organic additive.

5. The method of claim 1 or 2 further comprising the titanium source being selected from the group consisting of titanyl sulfate, titanium sulfate, titanium alkoxide, or Titanium(IV)bis(ammonium lactato)dihydroxide.

Description

EXAMPLES

(1) Activity Test

(2) The activity tests were carried out in a micro flow reactor. 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 240-200 ppm, was used for medium pressure ULSD testing in Examples A-F. A Vacuum Gas Oil (VGO) feed with S content of 2.1 wt. % S and 1760 ppmN was used for HC-PT testing in Example G. Catalysts were evaluated at equal volume, unless stated otherwise. The relative volumetric activities for the various catalysts were determined as follows. For each catalyst the volumetric reaction constant k.sub.vol 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. 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 isotherm, S is sulfur, N is nitrogen, P is pressure, g.sub.cat is the amount of catalyst in the reactor, LHSV is liquid hourly space velocity and r.o. is reaction order.

(3) Support Preparation

(4) The following supports were made in accordance with the procedures described below. One support was prepared as a reference (S1, Al.sub.2O.sub.3). A summary of the properties for each support can be found in Table 1.

Example S1: Comparative S1

(5) 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.

Example S2: Support S2

(6) 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 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.

Example S3: Support S3

(7) 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.

Example S4: Support S4

(8) 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.

Example S5: Support S5

(9) The support S5 was prepared by consecutive precipitation of alumina and titania. Firstly alumina (boehmite) was precipitated according to the procedure as described in Example S1 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 using water or ammonium bi-carbonate solution 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.

Example S6: Support S6

(10) 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 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.

Example S7: Support S7

(11) 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 Example 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 is placed outside of the atmosbag for hydrolysis overnight (at RT). Finally the sample is dried at 120° C. overnight. The sample was 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.

Example S8: Support S8

(12) 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 Example S7. The procedure as described in Example 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.

Example S9: Comparative S9

(13) 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 minutes 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 is re-slurried with water, brought to pH 10 with ammonia and aged at 95° C. for 1 hour while stirring. Then, the slurry is 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.

Example S10: Support S10

(14) The support S10 was prepared by strike-precipitation of alumina, titania and silica in the same way as S9 using different amounts of the raw materials. The final composition of the support (dry base) was found to be 21.3 wt. % TiO.sub.2, 0.6 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example S11: Comparative S11

(15) The support S11 was prepared by strike-precipitation of alumina, titania and silica in the same way as S9 using different amounts of the raw materials. In this case, the extrudates were calcined at 750° 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 21.0 wt. % TiO.sub.2, 9.9 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example S12: Support S12

(16) The support S12 was prepared by strike-precipitation of alumina, titania and silica in the same way as S9 using different amounts of the raw materials. The final composition of the support (dry base) was found to be 20.9 wt. % TiO.sub.2, 0.02 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example S13: Support S13

(17) The support S13 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 TiO.sub.2 wt. %, 0.5 SiO.sub.2 wt. % and 88.7 Al.sub.2O.sub.3 wt. %.

Example S14: Support S14

(18) The support S14 was prepared via a co-precipitation process. Aluminum sulfate (Alum) in one stream and sodium aluminate (Natal) were dosed simultaneously to a heel of water and waterglass at 50° C. and pH 8.7. 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 0.5 hour and the final solid concentration in the reactor was approximately 3.5% on weight basis. The slurry was filtered over a filter cloth and washed with water. The cake was dried, extruded and calcined at 650° C. with steam (25%) for 1 hour under airflow of ca. 10 nL/min. The final composition of the support (dry base) was found to be 1.0 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example S15: Support S15

(19) The support S15 was prepared by co-extrusion/kneading of Al.sub.2O.sub.3 cake (S14) and a titanium source. The Titanium(IV)isopropoxide 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 710° C. The final composition of the support (dry base) was found to be 10.6 wt. % TiO.sub.2, 0.82 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example S16: Support S16

(20) The support S16 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 5.4 TiO.sub.2 wt. %, 0.57 SiO.sub.2 wt. % and the rest Al.sub.2O.sub.3 wt. %.

Example S17: Support S17

(21) The support S17 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 10.6 TiO.sub.2 wt. %, 0.73 SiO.sub.2 wt. % and the rest Al.sub.2O.sub.3 wt. %.

Example S18: Support S18

(22) The support S18 was prepared in the same way as S9, but lower SiO.sub.2 sources were used. The final composition of the support (dry base) was found to be 21.6 TiO.sub.2 wt. %, 0.51 SiO.sub.2 wt. % and the rest Al.sub.2O.sub.3 wt. %.

(23) 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.

(24) TABLE-US-00001 TABLE 1 Summary of supports used during examples. Sup- Weight % Weight % SA PV DMPD port Procedure TiO.sub.2 (*) SiO.sub.2 (*) (m.sup.2/g) (ml/g) (nm) S1 ref. — — 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 0.6 236 0.59 8.1 S11 strike-precipitation 21.0 9.9 270 0.61 7.1 S12 strike-precipitation 20.9 0.02 172 0.40 7.2 S13 strike-precipitation 10.8 0.53 240 0.65 9.0 S14 ref. — 1.0 257 0.60 7.2 S15 co-extrusion 10.6 0.82 225 0.54 7.4 S16 strike-precipitation 5.4 0.57 216 0.63 9.0 S17 strike-precipitation 10.6 0.73 225 065 9.0 S18 strike-precipitation 21.6 0.51 219 0.59 8.5 * 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

(25) The following examples illustrate the positive effect of TiO.sub.2 addition in the support on the activity of NiMo catalysts when combined with organics in the catalyst preparation. The catalysts were prepared as described in examples A1-A11 using the same method to apply metals and organic additives to the catalysts and have a comparable volume loading of metals in the reactor. Approximately 0.9 ml of each of the catalysts was tested in a multi-reactor unit under medium pressure ultra-low sulfur diesel conditions. Table 2 shows the pre-sulfidation and test conditions and Table 3 shows the activity results.

(26) TABLE-US-00002 TABLE 2 Pre-sulfiding and test (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

Example A1: Comparative A1

(27) Comparative A1 was prepared by consecutive impregnation of support Comparative A1 with (i) a NiMoP aqueous solution and, after drying, (ii) with thioglycolic acid. 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 MoO3 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 at ambient temperature. 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. Both impregnations were performed in a rotating pan. 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.

Example A2: Invention A2

(28) Invention A2 was prepared using support S2 and the same preparation process as 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.

Example A3: Invention A3

(29) 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.

Example A4: Invention A4

(30) 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.

Example A5: Invention A5

(31) 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.

Example A6: Invention A6

(32) 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.

Example A7: Invention A7

(33) 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.

Example A8: Invention A8

(34) 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.

Example A9: Comparative A9

(35) Comparative A9 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.

Example A10: Invention A10

(36) Invention A10 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.

Example A11: Invention A11

(37) Invention A11 was prepared using support S13 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.

(38) TABLE-US-00003 TABLE 3 The effect of the addition of TiO.sub.2 in combination with an 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% Comparative A9 S1 0.719 198 58 100% 2.7 144 100% Invention A10 S10 0.855 209 9 246% 24 177% Invention A11 S13 0.820 215 19 190% 29 169%

(39) 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 and impregnation method. 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.

(40) The prior art teaches that it is critical to obtain a good dispersion of the TiO.sub.2 phase in TiO.sub.2/Al.sub.2O.sub.3 based hydroprocessing catalysts enable to observe the most positive effect of TiO.sub.2 addition on catalyst activity. This is for example expressed in [U.S. Pat. No. 9,061,265B2] in a claim regarding the relative intensity of the anatase and rutile TiO.sub.2 peaks vs. the intensity of the γ-Al.sub.2O.sub.3 peak at ° 2 theta in the XRD pattern. In FIG. 1, the XRD patterns of the catalysts of the invention are presented. It can be observed that the intensity of the anatase TiO.sub.2 (101) peak (around 26° 2 theta) vs the γ-Al.sub.2O.sub.3 (400) peak (around 46° 2 theta) ratio varies greatly between the different catalysts of the invention, with a number of catalysts exhibiting a anatase/γ-Al.sub.2O.sub.3 peak ratio that is much higher than what is claimed to be advantageous in the prior art. Also, there seems to be no obvious link between TiO.sub.2 dispersion and catalyst activity, when applying the preparation method of the invention. For example, Invention A5 shows a relative anatase TiO.sub.2 peak vs γ-Al.sub.2O.sub.3 peak intensity that is much higher than what is observed for Invention A4, which is likewise prepared via precipitation and roughly contains the same wt. % of TiO.sub.2. To our surprise, and in contrast to what is taught in the art, the activity of Invention A5 is significantly higher than that of Invention A4. Apparently the preparation method used and the organics applied removes the need for a very good TiO.sub.2 dispersion in preparation of a highly active TiO.sub.2/Al.sub.2O.sub.3 based hydroprocessing catalyst.

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

(41) These examples illustrate the positive effect of addition of TiO.sub.2 in the support on the activity of CoMo catalysts when combined with organics in the preparation in a wide range of TiO.sub.2 contents. Catalysts B1-B8 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.

(42) TABLE-US-00004 TABLE 4 Pre-sulfiding and test (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 with 1.09 wt. % 45 300 350 4 S and 200 ppmN

Example B1: Comparative B1

(43) 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 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 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.

Example B2: Invention B2

(44) 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.

Example B3: Invention B3

(45) 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.

Example B4: Inventive B4

(46) 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 Al.sub.2O.sub.3.

Example B5: Invention B5

(47) 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.

Example B6: Comparative B6

(48) 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 26.1 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.

Example B7: Invention B7

(49) Invention B7 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.

Example B8: Invention B8

(50) Invention B8 was prepared using support S13 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.

(51) 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. mg RVA g.sub.CAT db MoO.sub.3 LHSV N 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 0.701 203 4.0 88 100% Invention B7 S10 0.893 232 19 259% Invention B8 S13 0.812 226 40 186%

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

Examples C: The Effect of Organics Addition on Activity and the Limited Effect of SiO.SUB.2.-Content on Activity of TiO.SUB.2.—Al.SUB.2.O.SUB.3 .Supported CoMo Catalysts

(53) In the following examples it is illustrated that the inclusion of SiO.sub.2 in the catalyst composition has only a very modest, if any effect on catalyst activity. Supports with a variation in SiO.sub.2 content were prepared using a co-precipitation method and these were used to make CoMo catalysts according to the preparation method of the invention and comparable metal loadings per reactor volume. The catalysts were tested in a multi-reactor unit under medium pressure hydrotreating of a SRGO. Table 6 shows the pre-sulfidation and test conditions that were used for testing and Tables 7 shows the activity results that were obtained.

(54) TABLE-US-00006 TABLE 6 Pre-sulfiding and test (medium P ULSD) format used for activity testing of CoMo 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 with 1.4 wt. % 45 300 350 3 S and 200 ppmN

Example C1: Comparative C1

(55) Comparative C1 was prepared using support S1 and impregnated with CoMoP aqueous solution without organics. Preparation of the CoMoP solution and impregantion was done according to the procedure described in Example B1. The composition of the metal impregnated dried catalyst (dry base) was 26.4 wt. % MoO.sub.3 and 4.8 wt. % CoO, 4.2 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

Example C2: Comparative C2

(56) Comparative C2 was prepared using support S9 and impregnated, as C1, with a CoMoP aqueous solution without organics. The composition of the metal impregnated dried catalyst (dry base) was 24.1 wt. % MoO.sub.3 and 3.6 wt. % CoO, 3.9 wt. % P.sub.2O.sub.5, 15.3 wt. % TiO.sub.2.

Example C3: Comparative C3

(57) Comparative C3 was prepared using support S9. Firstly, it was impregnated with CoMoP aqueous solution as Example C1 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 hours, 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 24.2 wt. % MoO.sub.3 and 4.5 wt. % CoO, 4.1 wt. % P.sub.2O.sub.5, 13.9 wt. % TiO.sub.2, 1.8 wt. % SiO.sub.2 wt % and the rest is Al.sub.2O.sub.3.

Example C4: Comparative C4

(58) Invention C5 was prepared using support S10 and the same impregnation procedure as Example C3. The composition of the metal impregnated dried catalyst (dry base) was 26.1 wt. % MoO.sub.3 and 4.8 wt. % CoO, 4.3 wt. % P.sub.2O.sub.5, 13.5 wt. % TiO.sub.2, 6.4 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example C5: Invention C5

(59) Invention C4 was prepared using support S11 and the same impregnation procedure as Example C3. The composition of the metal impregnated dried catalyst (dry base) was 22.3 wt. % MoO.sub.3 and 4.3 wt. % CoO, 3.8 wt. % P.sub.2O.sub.5, 14.5 wt. % TiO.sub.2, 0.4 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example C6: Invention C6

(60) Invention C6 was prepared using support S12 and the same impregnation procedure as in Example C3. The composition of the metal impregnated dried catalyst (dry base) was 24.4 wt. % MoO.sub.3 and 4.5 wt. % CoO, 4.1 wt. % P.sub.2O.sub.5, 13.7 wt. % TiO.sub.2, 0.1 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

(61) TABLE-US-00007 TABLE 7 The effect of the addition of an organic in combination with TiO.sub.2-containing support in the activity of CoMo catalysts in medium P ULSD activity testing and the limited effect of SiO.sub.2 addition. RVA mg RVA HDS SiO.sub.2 g.sub.CAT db MoO.sub.3 LHSV N HDN LHSV S r.o. Example Support wt. % Additive Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) 1.2 Comparative C1 S1 — No organic 0.732 211 3.7 86 100% 2.6 211 100% Comparative C2 S9 3.2 No organic 0.778 220 56 145% 150 111% Comparative C3 S9 3.2 Thioglycolic acid 0.798 222 7 345% 23 186% Comparative C4 S11 9.9 Thioglycolic acid 0.703 219 16 271% 38 165% Invention C5 S10 0.6 Thioglycolic acid 0.774 218 10 319% 26 182% Invention C6 S12 — Thioglycolic acid 0.912 216 19 258% 35 171%

(62) From the test results in Table 7, it can be observed that regardless of the SiO.sub.2 in the support, a large activity benefit is observed for the catalysts based on a TiO.sub.2/Al.sub.2O.sub.3 support in combination with the preparation method that involves the use of organics. The effect of the organic additive on activity (delta C3 vs C2) is much larger than the effect of the SiO.sub.2 content (differences between C3, C4, C5 and C6). Apparently, the preparation method based on the use of organic additives removes the need of SiO.sub.2 addition for the preparation of efficient TiO.sub.2/Al.sub.2O.sub.3 based hydroprocessing catalysts.

(63) It can be concluded that, in contrast to what is described in the prior art, using the preparation method disclosed in which organics are used in the preparation, the dispersion of the TiO.sub.2 phase within the TiO.sub.2/Al.sub.2O.sub.3 support does not have an obvious effect on catalyst activity. Likewise, the addition of SiO.sub.2 to the catalyst composition does not result in a higher activity. Hence, the preparation method based on the use of organic additives as disclosed offers the advantage that allows greater flexibility in the design of a manufacturing process. For example, co-extrusion of Ti-precursors could be used, which would remove the need for cumbersome washing steps that are required when Ti is added during precipitation. Also a higher calcination temperature could be applied to obtain a certain required pore diameter without a negative effect of this procedure resulting in a decrease of the TiO.sub.2 dispersion.

Examples D: The Effect of a Wide Variation of Organics Additives on the Activity of TiO.SUB.2./Al.SUB.2.O.SUB.3.Supported NiMo and CoMo Catalysts

(64) In the following examples it is illustrated that the use of different organic additives has a positive effect on the catalyst activity. A fixed TiO.sub.2/Al.sub.2O.sub.3 support with a variation in the organic additive and comparable metal loading catalysts were prepared. The catalysts were tested in a multi-reactor unit under medium pressure hydrotreating of a SRGO. Table 8 shows the pre-sulfidation and test conditions that were used for testing and Tables 9 (NiMo) and 10 (CoMo) shows the activity results that were obtained.

(65) TABLE-US-00008 TABLE 8 Pre-sulfiding and test (medium P ULSD) format used for activity testing of NiMo and CoMo 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 with 1.09 wt. % 45 300 350 4 S and 200 ppmN

Example D1: Comparative D1

(66) Comparative D1 was prepared using support Sand impregnated with NiMoP aqueous solution without organics. An amount of aqueous NiMoP solution equivalent to fill 105% of the pore volume was used for impregnation, 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 composition of the metal impregnated dried catalyst (dry base) was 22.1 wt. % MoO.sub.3 and 3.6 wt. % NiO, 3.8 wt. % P.sub.2O.sub.5, 0.38 wt. % SiO.sub.2, 15.0 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example D2: Invention D2

(67) Invention D2 was prepared using Comparative D1 and a subsequent impregnation with Glyoxilic acid to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D1.

Example D3: Invention D3

(68) Invention D3 was prepared using Comparative D1 and a subsequent impregnation with Resorcinol to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D1.

Example D4: Invention D4

(69) Invention D4 was prepared using Comparative D1 and a subsequent impregnation with Triethylene glycol to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D1.

Example D5: Comparative D5

(70) Comparative D5 was prepared in the same way as Comparative D1. The composition of the metal impregnated dried catalyst (dry base) was 23.6 wt. % MoO.sub.3 and 4.1 wt. % NiO, 4.1 wt. % P.sub.2O.sub.5, 0.39 wt. % SiO.sub.2, 14.4 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example D6: Invention D6

(71) Invention D6 was prepared using Comparative D5 and a subsequent impregnation with Itaconic acid to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D5.

Example D7: Invention D7

(72) Invention D6 was prepared using Comparative D5 and a subsequent impregnation with Diethylene Glycol Butyl Ether to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D5.

Example D8: Invention D8

(73) Invention D8 was prepared using Comparative D5 and a subsequent impregnation with Glucose to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D5.

Example D9: Invention D9

(74) Invention D9 was prepared using Comparative D5 and a subsequent impregnation with Ribose to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D5.

(75) TABLE-US-00009 TABLE 9 The effect of the addition of an organic in combination with TiO.sub.2-containing support in the activity of NiMo catalysts in medium P ULSD activity testing. mg RWA RWA g.sub.CAT db MoO.sub.3 LHSV N HDN LHSV S HDS Example Support Additive Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) r.o. 1.2 Comparative D1 S10 No organic 0.841 207 4.0 46 100% 2.7 61 100% Invention D2 Glyoxilic acid 0.857 211 27 129% 26 125% Invention D3 Resorcinol 0.830 204 22 149% 27 130% Invention D4 Triethylene glycol 0.847 208 19 150% 50 104% Invention D6 Itaconic acid 0.886 233 14 161% 3.0 44 133% Invention D7 DiethyleneGlycol 0.873 219 11 178% 28 156% Butyl Ether Invention D8 Glucose 0.907 238 2 257% 21 158% Invention D9 Ribose 0.918 230 3 256% 21 165%

(76) As can be observed in Table 9, there is a difference in catalyst intake, and MoO.sub.3 loading in the reactor between the set of catalysts D1-D4 (based in D1) and D6-D9 (based on D5). To be able to compare the activity of the different catalysts, it was decided to determine catalyst activities on a wt-basis and compare the relative weight based activity (RWA) of all catalysts to Comparative D1. It becomes quite clear that the addition of a wide variety of different organic additives to NiMo catalysts based on a TiO.sub.2—Al.sub.2O.sub.3(S10) support increases significantly the HDN and HDS activity of these catalysts.

Example D10: Comparative D10

(77) Comparative D10 was prepared using support S10 and impregnated with CoMoP aqueous solution without organics. 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 composition of the metal impregnated dried catalyst (dry base) was 22.2 wt. % MoO.sub.3 and 3.8 wt. % CoO, 3.9 wt. % P.sub.2O.sub.5, 0.37 wt. % SiO.sub.2, 15.0 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example D11: Invention D11

(78) Invention D11 was prepared using Comparative D10 and a subsequent impregnation with Glucose to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D10.

Example D12: Invention D12

(79) Invention D12 was prepared using Comparative D10 and a subsequent impregnation with 3-hydroxybutyric acid to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D10.

Example D13: Invention D13

(80) Invention D13 was prepared using Comparative D10 and a subsequent impregnation with Ribose to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D10.

Example D14: Invention D14

(81) Invention D14 was prepared using Comparative D10 and a subsequent impregnation with Triethylene glycol to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D10.

Example D15: Invention D15

(82) Invention D15 was prepared using Comparative D10 and a subsequent impregnation with 1,2-propanediol to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as D10.

(83) TABLE-US-00010 TABLE 10 The effect of the addition of an organic in combination with TiO.sub.2-containing support in the activity of CoMo catalysts in medium P ULSD activity testing. mg RVA RVA g.sub.CAT db MoO.sub.3 LHSV N HDN LHSV S HDS Example Support Additive Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) r.o. 1.2 Comparative D10 S10 No organic 0.845 209 4.0 66 100% 2.7 105 100% Invention D11 Glucose 0.848 209 46 129% 48 128% Invention D12 3-hydroxybutyric 0.842 208 50 129% 54 127% acid Invention D13 Ribose 0.847 209 49 128% 57 124% Invention D14 Triethylene glycol 0.853 211 53 116% 54 122% Invention D15 1,2-propanediol 0.853 211 56 113% 66 116%

(84) As observed in Table 10, the addition of an organic additive (wide variation) on CoMo catalysts based on a TiO.sub.2—Al.sub.2O.sub.3(S10) support increases significantly the HDN and HDS activity of these catalysts. Activity of all catalysts has been related to Comparative Don a relative volumetric activity (RVA) basis, as in this case all catalysts were based on the same intermediate catalyst (D10) and catalyst intake and MoO.sub.3 loading per reactor were almost identical for all catalysts.

Examples E: Synergistic Effect of the Use of Organics Additives in Combination with Ti—Al.SUB.2.O.SUB.3 .Supports on the Activity of NiMo Catalysts

(85) In the following examples, it is illustrated that the use of a TiO.sub.2/Al.sub.2O.sub.3 support in combination with organic additives results in a synergetic effect. The activity benefit of applying a TiO.sub.2/Al.sub.2O.sub.3 support in combination with 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 organics as determined in separate experiments and can therefore be regarded as surprising. The catalysts presented are NiMo grades with comparable metal loadings and are based on the same TiO.sub.2—Al.sub.2O.sub.3 support and the Al.sub.2O.sub.3 counterpart. The catalysts were tested in a multi-reactor unit under medium pressure ultra-low sulfur diesel conditions. Table 11 shows the experimental settings for the pre-sulfidation and test conditions and Tables 12, 13 and 14 shows the amount of catalyst that was loaded in the different reactors and the activity results.

(86) TABLE-US-00011 TABLE 11 Pre-sulfiding and test (medium P ULSD) format used for activity testing of NiMo catalysts from example 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 with 1.09 wt. % 45 300 350 4 S and 200 ppmN

Example E1: Comparative E1

(87) Comparative E1 was prepared using support S1 and impregnated with NiMoP aqueous solution without organics. An amount of aqueous NiMoP solution equivalent to fill 105% of the pore volume was used for impregnation, 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 composition of the metal impregnated dried catalyst (dry base) was 23.8 wt. % MoO.sub.3 and 4.5 wt. % NiO, 4.1 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

Example E2: Comparative E2

(88) Comparative E2 was prepared using S10 and the same impregnation method as E1. The composition of the metal impregnated dried catalyst (dry base) was 21.3 wt. % MoO.sub.3 and 4.0 wt. % NiO, 3.6 wt. % P.sub.2O.sub.5, 0.48 wt. % SiO.sub.2, 15.3 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example E3: Comparative E3

(89) Comparative E3 was prepared using S1 and the same impregnation procedure as E1, but with the addition of Gluconic acid with 0.42 mol/mol Mo in the metal impregnation solution. The composition of the metal impregnated dried catalyst (dry base) based on theoretical loading was 24.1 wt. % MoO.sub.3 and 4.0 wt. % NiO, 4.0 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

Example E4: Invention E4

(90) Invention E4 was prepared using S10 and impregnated as E3. The composition of the metal impregnated dried catalyst (dry base) based on theoretical loading was 21.0 wt. % MoO.sub.3 and 3.5 wt. % NiO, 3.5 wt. % P.sub.2O.sub.5, 0.42 wt. % SiO.sub.2, 15.3 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

(91) TABLE-US-00012 TABLE 12 The effect of the addition of gluconic acid in combination with TiO.sub.2-containing support in the activity of NiMo catalysts in medium P ULSD activity testing. mg RVA RVA g.sub.CAT db MoO.sub.3 LHSV N HDN LHSV S HDS Example Support Additive Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) r.o. 1.2 Comparative E1 S1 No organic 0.746 200 4.0 76 100% 3.0 280 100% Comparative E2 S10 No organic 0.876 204 41 154% 120 134% Comparative E3 S1 Gluconic Acid 0.744 199 61 131% 224 117% Invention E4 S10 Gluconic Acid 0.880 205 15 241% 47 179% S.sub.xy 56 28

(92) As can be observed in Table 12, the activity of catalyst of the Invention E4 is larger than could be expected based on the added benefits of Ti-containing support (E2 without gluconic acid) and the use of gluconic acid as organic additive (E3 without Ti-support). To our surprise, the combination of a Ti-containing support and the use of gluconic acid as organic additive (Invention E4) show greater activity improvement than individual effects of support (E2) or organic (E3) relative to Comparative E1.

(93) 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]

Example E5: Comparative E5

(94) Comparative E5 was prepared using support S1 and impregnated with NiMoP aqueous solution without organics. An amount of aqueous NiMoP solution equivalent to fill 105% of the pore volume was used for impregnation, 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 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.

Example E6: Comparative E6

(95) Comparative E6 was prepared using S10 and the same impregnation method as E5. The composition of the metal impregnated dried catalyst (dry base) was 22.0 wt. % MoO.sub.3 and 3.8 wt. % NiO, 3.8 wt. % P.sub.2O.sub.5, 0.37 wt. % SiO.sub.2, 15.0 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example E7: Comparative E7

(96) Comparative E7 was prepared using S1 and impregnated as E5. Then a subsequent impregnation was performed with 1,2-propanediol to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was 25.9 wt. % MoO.sub.3 and 4.3 wt. % NiO, 4.4 wt. % P.sub.2O.sub.5 and the rest is Al.sub.2O.sub.3.

Example E8: Invention E8

(97) Invention E8 was prepared using S10 and impregnated as E5. Then a subsequent impregnation was performed with 1,2-propanediol to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was 23.6 wt. % MoO.sub.3 and 4.1 wt. % NiO, 4.1 wt. % P.sub.2O.sub.5, 0.39 wt. % SiO.sub.2, 14.4 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

(98) TABLE-US-00013 TABLE 13 The effect of the addition of an organic in combination with TiO.sub.2-containing support in the activity of NiMo catalysts in medium P ULSD activity testing. mg RVA g.sub.CAT db MoO.sub.3 LHSV N HDN Example Support Additive Reactor Reactor HDN (ppm) r.o. 1 Comparative E1 S1 No organic 0.746 200 4.0 76 100% Comparative E5 S1 No organic 0.715 197 76 100% Comparative E2 S10 No organic 0.876 204 41 154% Comparative E6 S10 No organic 0.854 209 47 146% Comparative E7 S1 1,2-propanediol 0.709 204 51 135% Invention E8 S10 1,2-propanediol 0.876 230 7 307% S.sub.xy 122

(99) As can be observed in Table 13, the activity of Invention E8 is larger than what can be expected based on the individual benefits of Ti-containing support (E2 and E6 without organic) and the use of 1,2-propanediol as organic additive (E7 without Ti-support). To our surprise, the combination of Ti-containing support and the use of 1,2-propanediol as organic additive (Invention E8) show greater activity improvement than individual effects of support (E2 and E6) or organic (E7), resulting in a very significant synergy factor (S.sub.xy). Since data from different tests have been used, RVA HDN is calculated according to a different reference: E2 and E8 are relative to Comparative E1, while E6 and E7 are relative to Comparative E5.

Example E9: Comparative E9

(100) Comparative E9 was prepared using S1 and impregnated as E5. Then a subsequent impregnation was performed with 3-hydroxybutyric acid to reach 15 wt. % in the final catalyst. The composition of the metal impregnated dried catalyst (dry base) was as E5.

Example E10: Invention E10

(101) Invention E10 was prepared using S10 and impregnated as E9. The composition of the metal impregnated dried catalyst (dry base) was 23.6 wt. % MoO.sub.3 and 4.1 wt. % NiO, 4.1 wt. % P.sub.2O.sub.5, 0.39 wt. % SiO.sub.2, 14.4 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

(102) 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 NiMo catalysts in medium P ULSD activity testing. mg RVA g.sub.CAT db MoO.sub.3 LHSV N HDN Example Support Additive Reactor Reactor HDN (ppm) r.o. 1 Comparative E1 S1 No organic 0.746 200 40 76 100% Comparative E5 S1 No organic 0.715 197 76 100% Comparative E2 S10 No organic 0.876 204 41 154% Comparative E6 S10 No organic 0.854 209 47 146% Comparative E9 S1 3-hydroxybutiric acid 0.731 211 49 144% Invention E10 S10 3-hydroxybutiric acid 0.898 236 6 334% S.sub.xy 140

(103) As can be observed in Table 14, the activity of Invention E10 is larger than the individual benefits of Ti-containing support (E2 and E6 without organic) and the use of 1,2-propanediol as organic additive (E9 without Ti-support). To our surprise, the combination of Ti-containing support and the use of 3-hydroxybutiric acid as organic additive (Invention E10) show greater activity improvement than individual effects of support (E2 and E6) or organic (E9). Since different LHSV have been used, RVA HDS is calculated according to a different reference: E2 and E10 are relative to Comparative E1, while E6 and E9 are relative to Comparative E5.

(104) In ULSD applications, the removal of S to very low S-levels (<10 ppm) is the main objective. As a result, HDS-activity at high conversion is the most important activity parameter. However, it is well known that N-compounds inhibit the HDS reaction and removal of these molecules will greatly enhance the HDS reaction rate towards 10 ppm S. Moreover, HDS kinetics are highly complex and the reaction order is a function of conversion. HDN, on the other hand, is an apparent 1.sup.st order reaction across a large conversion range. For these reasons, we have chosen to use HDN activity as the most activity to determine the synergetic effect.

Examples F: Effect of Co-Extruded Alumina Supports on the Activity of NiMo Catalysts for ULSD Applications

(105) The following examples illustrate the positive effect of TiO.sub.2 addition in different ways as co-extruded supports on the activity of NiMo catalysts. The catalysts were prepared as described in examples F1-F3 using the same method to apply metals and organic additives to the catalysts and have a comparable volume loading of metals in the reactor. Approximately 0.9 ml of each of the catalysts was tested in a multi-reactor unit under medium pressure ultra-low sulfur diesel conditions. Table 15 shows the pre-sulfidation and test conditions and Table 16 shows the activity results.

(106) TABLE-US-00015 TABLE 15 Pre-sulfiding and test (medium P ULSD) format used for activity testing of NiMo catalysts from 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) SRGO with 1.1 wt. % 45 300 350 5 S and 240 ppmN

Example F1: Comparative F1

(107) Comparative F1 was prepared using support Sand impregnated with NiMoP aqueous solution and diethylene glycol. 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. Then, 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 cooling down, an amount of diethylene glycol to achieve 0.44 mol DEG per mol of metals (Mo+Ni) was added to the solution. An amount of the final solution equivalent to fill 105% of the pore volume was used for impregnation, 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. 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 composition of the metal impregnated dried catalyst (dry base) was 22.8 wt. % MoO.sub.3 and 3.9 wt. % NiO, 6.8 wt. % P.sub.2O.sub.5, 0.66 wt. % SiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example F2: Invention F2

(108) Invention F2 was prepared using S15 and the same impregnation method as F1. The composition of the metal impregnated dried catalyst (dry base) was 22.7 wt. % MoO.sub.3 and 3.8 wt. % NiO, 6.8 wt. % P.sub.2O.sub.5, 0.59 wt. % SiO.sub.2, 7.1 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example F3: Invention F3

(109) Invention F4 was prepared using S13 and the same impregnation method as F1. The composition of the metal impregnated dried catalyst (dry base) was 23.2 wt. % MoO.sub.3 and 3.9 wt. % NiO, 6.9 wt. % P.sub.2O.sub.5, 0.35 wt. % SiO.sub.2, 7.1 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

(110) 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 medium P ULSD activity. RVA mg RVA HDS g.sub.CAT db MoO.sub.3 LHSV N HDN LHSV S r.o. Example Support Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) 1.2 Comparative F1 S14 0.847 193 4.0 28 100% 2.5 35 100% Invention F2 S15 0.928 211 14 132% 25 109% Invention F3 S13 0.795 185 18 120% 24 111%

(111) As can be observed in Table 16, the catalysts with titania present in the support show higher activity than Comparative catalyst F1 without titania when using the same metal preparation procedure and similar metal loadings. The co-extruded titania and alumina support F2 shows very similar activity as the precipitated sample (F3) shown in previous examples when using diethylene glycol as organic additive.

Examples G: HC-PT Activity Data of NiMo Catalysts with Ribose as Organic Additive and TiO.SUB.2.-Containing Supports

(112) The following examples illustrate the positive effect of TiO.sub.2 addition in the support and Ribose as organic additive on the activity of NiMo catalysts in HC-PT application. The catalysts were prepared as described in examples G1-G4 using the same method to apply metals and organic additives to the catalysts and have a comparable volume loading of metals in the reactor. Approximately 0.9 ml of each of the catalysts was tested in a multi-reactor unit under medium pressure ultra-low sulfur diesel conditions. Table 17 shows the pre-sulfidation and test conditions and Table 18 shows the activity results.

(113) TABLE-US-00017 TABLE 17 Pre-sulfiding and HC-PT test format used for activity testing of NiMo catalysts from examples G. Pre-sulfiding conditions P LHSV H.sub.2/oil Temperature Time Feed (bar) (1/hr) (Nl/l) (° C.) (hours) Spiked LGO 45 3 300 320 24 Testing conditions P LHSV H.sub.2/oil Temperature Time @ Feed (bar) (1/hr) (Nl/l) (° C.) condition (days) VGO with 120 1.7 1000 380 3 2.1 wt. % S and 1760 ppmN

Example G1: Comparative G1

(114) Comparative G1 was a commercial NiMo catalyst with no titania in the support and no Ribose additive.

Example G2: Invention G2

(115) Comparative G1 was prepared using support S16 and impregnated with NiMoP aqueous solution without organics. After that, 0.44 mol Ribose/mol Metals were dissolved in water and impregnated in the previous sample allowed to age for 2 hours. The final catalyst was dried in a static oven at 100° C. overnight. The composition of the metal impregnated dried catalyst (dry base) was 27.7 wt. % MoO.sub.3 and 5.0 wt. % NiO, 4.2 wt. % P.sub.2O.sub.5, 0.37 wt. % SiO.sub.2, 3.5 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example G3: Invention G3

(116) Invention G3 was prepared using S17 and the same impregnation method as G2. The composition of the metal impregnated dried catalyst (dry base) was 27.9 wt. % MoO.sub.3 and 5.1 wt. % NiO, 4.2 wt. % P.sub.2O.sub.5, 0.39 wt. % SiO.sub.2, 6.8 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

Example G4: Invention G4

(117) Invention G4 was prepared using S18 and the same impregnation method as G2. The composition of the metal impregnated dried catalyst (dry base) was 26.0 wt. % MoO.sub.3 and 4.4 wt. % NiO, 3.9 wt. % P.sub.2O.sub.5, 0.40 wt. % SiO.sub.2, 13.6 wt. % TiO.sub.2 and the rest is Al.sub.2O.sub.3.

(118) TABLE-US-00018 TABLE 18 The NiMo catalysts activity in HC-PT testing for TiO.sub.2 supported Ribose/NiMo catalysts from examples G (vs a commercial NiMo catalyst). g.sub.CAT mg RVA db MoO.sub.3 RVA HDS Re- Re- N HDN S r.o. Example Support actor actor (ppm) r.o. 1 (ppm) 1.2 Comparative NiMo 0.748 232 72 100% 198 100% G1 commercial catalyst Invention G2 S16 0.896 266 55 109% 153 109% Invention G3 S17 0.886 265 27 131% 94 127% Invention G4 S18 0.899 257 29 129% 103 123%

(119) As can be observed in Table 16, the Invention examples with Ti-addition in the catalyst support (G2-G4) show significantly higher performance than the Comparative G1 (no titania) example. It is clear that the samples with 10 and 20 wt. % TiO.sub.2 are better than the sample with 5 wt. % TiO.sub.2 at similar metal loading.

(120) 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.

(121) The invention may comprise, consist, or consist essentially of the materials and/or procedures recited herein.

(122) 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.

(123) 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.

(124) 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.

(125) 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.