HYDROTREATING CATALYST CONTAINING METAL ORGANIC SULFIDES ON DOPED SUPPORTS

Abstract

A catalyst comprising: a catalyst support; at least one Group VIB metal component; at least one Group VIII metal component; at least one mercapto-carboxylic acid; wherein the catalyst support contains at least one dopant comprising either boron, and/or silicon, and/or phosphorusin the range of about 1 to about 13 wt %, expressed as an oxide and based on the total weight of the catalyst for each dopant added; and wherein the amount of the at least one mercapto-carboxylic acid is in the amount from about 0.4 to about 3 equivalents to the sulfur amount necessary for forming sulfides of the Group VI and VIII components.

Claims

1. A catalyst comprising: a catalyst support; at least one Group VIB metal component; at least one Group VIII metal component; at least one mercapto-carboxylic acid; wherein the catalyst support contains at least one dopant comprising either boron, and/or silicon, and/or phosphorus in the range of about 1 to about 13 wt %, expressed as an oxide and based on the total weight of the catalyst for each dopant added; and wherein the amount of the at least one mercapto-carboxylic acid is in the amount from about 0.4 to about 3 equivalents to the sulfur amount necessary for forming sulfides of the Group VI and VIII components.

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

3. The catalyst according to claim 1 or 2 wherein the Group VIII metal component comprises nickel and/or cobalt.

4. The catalyst according to any one of claims 1-3 wherein the mercapto-carboxylic acid is thioglycolic acid, thiolactic acid, mercapto succinic acid, cysteine or thio propionic acid.

5. The catalyst according to claim 4 further comprising an additional carboxylic acid.

6. The catalyst according to any one of claims 1-5, wherein the dopant is boron in the range of about 2 wt % to about 8 wt %, expressed as an oxide (B.sub.2O.sub.3) and based on the total weight of the catalyst.

7. The catalyst according to any one of claims 1-5, wherein the dopant is phosphorus in the range of about 2 wt % to about 10 wt %, expressed as an oxide (P.sub.2O.sub.5) and based on the total weight of the catalyst.

8. The catalyst according to claims any one of 1-5, wherein the dopant is silicon in the range of about 1 wt % to about 9 wt %, expressed as an oxide (SiO.sub.2) and based on the total weight of the catalyst.

9. The catalyst according to claim 6, 7, or 8 wherein the catalyst support is impregnated with the Group VIB metal component, the Group VIII metal component, and the mercapto-carboxylic acid.

10. The catalyst according to claim 9 wherein the catalyst support is further impregnated with a phosphorous component.

11. The catalyst according to any of the preceding claims, wherein the catalyst support comprises alumina.

12. A method of producing a catalyst, the method comprising: forming a doped catalyst support having a boron, and/or silicon and/or phosphorus content in the range of about 1 wt % to about 13 wt % for each dopant added, expressed as an oxide and based on the total weight of the catalyst; drying and calcining the catalyst support; impregnating the calcined catalyst support with a solution comprised of a mercapto-carboxylic acid, at least one Group VIB metal source and/or at least one Group VIII metal source, wherein the amount of the mercapto-carboxylic acid is at least 0.4 to 3 equivalents to the sulfur amount necessary for forming sulfides of the Group VI and VIII components; and ageing the impregnated catalyst support for a period of time between 60 and 160? C.

13. A method of producing a catalyst, the method comprising forming a doped catalyst support having a boron, and/or silicon and/or phosphorus content in the range of about 1 wt % to about 13 wt % for each dopant added, expressed as an oxide and based on the total weight of the catalyst; drying and calcining the catalyst support; impregnating the calcined catalyst support with a solution comprised of at least one Group VIB metal source and/or at least one Group VIII metal source; drying the impregnated catalyst support at 80-150? C.; further impregnating the dried impregnated catalyst support with an amount of a mercapto-carboxylic acid wherein the amount of the mercapto-carboxylic acid is at least 0.4 to 3 equivalents to the sulfur amount necessary for forming sulfides of the Group VI and VIII components; and ageing the impregnated catalyst support for a period of time between 60 and 160? C.

14. The method according to claim 12 or 13, wherein the amount of the boron component source is sufficient so that the boron content of the catalyst produced is in the range of about 2 wt % to about 8 wt %, expressed as an oxide (B.sub.2O.sub.3) and based on the total weight of the catalyst.

15. The method according to claim 12 or 13, wherein the phosphorus component source is sufficient so that the phosphorus content in the catalyst produced is in the range of about 2 wt % to about 10 wt %, expressed as an oxide (P.sub.2O.sub.5) and based on the total weight of the catalyst.

16. The method according to claim 12 or 13, wherein the silicon component source is sufficient so that the silicon content in the catalyst produced is in the range of about 2 wt % to about 9 wt %, expressed as an oxide (SiO.sub.2) and based on the total weight of the catalyst.

17. The method according to any one of claims 12-16 wherein the mercapto-carboxylic acid is thioglycolic acid, thiolactic acid, mercapto succinic acid, cysteine or thio propionic acid.

18. The method according to any one of claims 12-16 further comprising impregnating the extrudate with a carboxylic acid.

19. A catalyst formed in accordance with any one of claims 12-18.

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.

21. 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, wherein the catalyst is activated without the addition of additional sulfur compounds.

Description

EXAMPLES

Preparation of the Support

[0033] The support was prepared by mixing an alumina hydrate (water content about 80%) in a kneader to form an extrudable paste. When desired, boric acid and/or phosphoric acid were added to the mix. Additionally, other acids such as nitric acid, can be used in the mixing step, the preceding precipitation step, or as peptizing agents. A person skilled in the art knows when such precipitation and peptizing agents are required. For the preparation of the silicon-containing support, sodium silicate was added in the precipitation process prior to the mixing and kneading steps. (In some cases, the water content of the extrusion mix had to be adjusted by evaporation or by adding additional water in order to obtain a paste suitable for extrusion. A person skilled in the art knows how to adjust the water content in order to obtain an extrudable paste). The resulting mixture was extruded through a die plate (of desired shapes and diameters), dried, and then calcined (optionally with steam) at a temperature in the range of 475-900? C. See Table 1 for details of the support properties. PV is pore volume. MPD is median pore diameter as determined by mercury intrusion.

TABLE-US-00001 TABLE 1 Weight % (of dopant as oxides) based on the total weight of the PV MPD Support Material Dopant support (ml/g) (nm) S1 ?-alumina 0.77 9.3 S2 ?-alumina Boron 4.1 0.75 10.0 S3 ?-alumina Boron 3.8 0.81 10.5 S4 ?-alumina Boron 6.7 0.76 10.6 S5 ?-alumina Phosphorus 3.4 0.72 8.7 S6 ?-alumina Boron 8.3 0.78 10.6 S7 ?-alumina Boron 5.5 0.84 11.3 S8 ?-alumina Silica 11.8 0.78 10.1 S9 ?-alumina Boron 3.8 0.78 11

Activity Test

[0034] The activity tests were carried out in microflow reactors using two types of extrudates. Under the first method, the catalyst extrudates were crushed and a sieve fraction between 125-310 ?m was used. Under the second method, the extrudates were sized to a length of 1.4-1.8 mm. Light gas oil (LGO) spiked with dimethyl disulfide (DMDS) (total S content of 2.5 wt %) was used for pre-sulfiding the as-prepared catalysts. Vacuum gas oil (VGO) with a density of 0.93 g/ml @ 15? C., a sulfur content of 2.0 wt %, and a nitrogen content of 1600 mg/kg was used for the FCC-PT and HC-PT testing conditions. Heavy gas oil (HGO) with a density of 0.90 @ 15? C., a S content of 1.5 wt % and a N content of 542 mg/kg, was used for testing under high pressure ULSD conditions. For moderate pressure ULSD testing, a Straight Run Gas Oil (SRGO) with a density of 0.85 g/ml @ 15? C., a sulfur content of 1.31 wt. % and a nitrogen content of 121 mg/kg was used. Detailed information about test conditions is given in Tables 2, 4, and 6 and 8.

Examples FCC-PT Application

[0035] Table 2 presents the pre-sulfiding and testing conditions for the catalysts in the different units. Table 3 lists the relative HDS and HDN activity per volume basis (RVA) and compared to the benchmark (set at 100%) for both hydrodenitrification (HDN) and hydrodesulphurization (HDS). The relative volume activities (RVA) for the various catalysts were determined as follows. For each catalyst the reaction constant kvol was calculated from the following equation: k.sub.vol=LHSV?(1/(n?1))?(1/S.sup.n-1?1/S.sub.0.sup.n-1); in which the S stands for percentage of sulfur in the product and S.sub.0 stands for the percentage of sulfur in the feed, and n stands for the reaction order of the hydrodesulfurization reaction (n.sub.HDS). For nitrogen the kvol was calculated from the following equation: k.sub.vol=ln(N.sub.0/N)?LHSV; in which the N stands for the nitrogen content in the product and N.sub.0 for the nitrogen content in the feed. RVA is the ratio of k.sub.vol of the catalyst and k.sub.vol of the benchmark, and is expressed as a percentage. In the tables, P=pressure, LHSV=liquid hourly space velocity. Actual extrudate loading densities were used to determine LHSV. The calculations are performed in the same way regardless of the application.

[0036] The catalysts were tested in FCC-PT mode to obtain S and N-levels as low as 500 mg/kg and 600 mg/kg (for the benchmark catalyst) respectively in the condition mentioned in table 2. For the sake of comparison in FCC-PT, we use CoMo grades. We also further compare the effect of the addition of boron or silicon or phosphorus to the support in the absence of the mercapto-carboxylic acid and the effect of the addition of the mercapto-carboxylic acid in the absence of boron or silicon or phosphorus to highlight the synergistic effect of the presence of both components in this particular case. Samples (inventions) prepared on a boron doped support are compared to a benchmark prepared on a boron doped support and samples prepared on a phosphorus doped support are compared to a benchmark prepared on a phosphorus containing support.

TABLE-US-00002 TABLE 2 Pre-sulfiding and FCC-PT test format Pre-sulfiding LHSV H.sub.2/oil Temperature Feed P (bar) (1/hr) (Nl/l) (? C.) Time (hours) Spiked LGO 45 3 300 320 24 Test condition LHSV Temperature Time Feed P (bar) (1/hr) H.sub.2/oil (Nl/l) (? C.) (days) nHDS VGO 70 1.20 400 360 12 1.65

Example 1: Comparative A1

[0037] An impregnation solution was prepared by mixing appropriate amounts of Cobalt carbonate (CoCO.sub.3, 46% purity), molybdenum trioxide (MoO.sub.3) and phosphoric acid (H.sub.3PO.sub.4) in deionized water. The mixture was constantly stirred and kept at an appropriate temperature such as to obtain a clear solution with minimal loss of water. The initial amount of water is chosen in such a way that the resulting metal solution would have sufficient metals as compared to that desired in the final product such that no further evaporation of water is required. Having an additional amount of water is not seen as a problem, since this can be evaporated in a subsequent step.

[0038] Support S2 was impregnated with the above mentioned impregnation solution to 115% of its pore volume saturation. The thus impregnated catalyst extrudates were aged in the rotating pan for 30 minutes at room temperature. After this, the extrudates were dried by blowing hot air (120? C., inlet) for another 30-60 minutes until free flowing extrudates are obtained. Thus, a metal impregnated dried catalysts is obtained, which is labelled as A1. The final metal content of the catalyst (dry base) was found to be 23.8 wt. % MoO.sub.3, 4.9 wt. % CoO, 2.5 wt. % P.sub.2O.sub.5 and 2.9% B.sub.2O.sub.3.

Example 2: Comparative A2

[0039] The catalyst was prepared in the same way as described in example 1, except that support S1 was used. The metal impregnated dried catalyst was found to have 23.0 wt. % MoO.sub.3, 4.5 wt. % CoO and 2.1 wt. % P.sub.2O.sub.5. To the resulting sample, enough 2,2-dithioethanol was added such that it would fill up 80% of the available volume of the pores. The impregnated catalyst was further aged for 1 hour, while rotating. The extrudates were then poured out into a petri dish and placed in an oven at 80? C. for 16 hours. The thus obtained catalyst is labelled as A2.

Example 3: Comparative A3

[0040] The catalyst was prepared in the same way as described in example 1 except that support S1 (without any dopant) was used in the preparation. The metal impregnated dried catalyst (dry base) was found to have 24.7 wt. % MoO.sub.3, 4.4 wt. % CoO and 2.2 wt. % P.sub.2O.sub.5. The dried intermediate was further modified by adding thiolactic acid (3.5 mol/mol molybdenum present in the catalyst) in a rotating pan. Subsequently, the additive containing intermediate was further aged under blowing hot air for 1 hour, while rotating. The extrudates were then poured out into a petri dish and placed in an oven at 80? C. for 16 hours. The resulting sample was labelled A3.

Example 4: Comparative A4

[0041] The catalyst was prepared in the same way as described in example 1 except that support S1 (without any dopant) was used in the preparation. The metal impregnated dried catalyst (dry base) was found to have 24.1 wt. % MoO.sub.3, 4.3 wt. % CoO and 2.1 wt. % P.sub.2O.sub.5. The intermediate was further modified by adding thioglycolic acid (3.5 mol/mol molybdenum present in the catalyst) in a rotating pan. The additive containing intermediate was further aged under blowing hot air for 1 hour, while rotating. The extrudates were then poured out into a petri dish and placed in an oven at 80? C. for 16 hours. The resulting sample was labelled A4.

Example 5: Comparative A5

[0042] The catalyst was prepared in the same way as described in example 1 and on the same support (S2) except that diethylene glycol (0.44 mol/mol of hydrogenation metal (Co+Mo) metals present), was added to the metal solution prior to impregnation. The resulting sample was found to have (excluding the organic additive) had 23.8 wt. % MoO.sub.3, 4.9 wt. % CoO, 2.5 wt. % P.sub.2O.sub.5 and 2.9% B.sub.2O.sub.3. The resulting sample was labelled A5.

Example 6: Invention A6

[0043] The catalyst was prepared in the same way as described in example 1 except that support S3 was used in the preparation. The metal impregnated dried catalyst (dry base) had 24.8 wt. % MoO.sub.3, 4.3 wt. % CoO, 2.2 wt. % P.sub.2O.sub.5 and 2.9% B.sub.2O.sub.3, and was further modified by adding thioglycolic acid (3.5 mol/mol molybdenum present in the catalyst) in a rotating pan. The intermediate was further aged under blowing hot air for 1 hour, while rotating. The extrudates were then poured out into a petri dish and placed in an oven at 80? C. for 16 hours. The resulting sample was labelled A6.

Example 7: Invention A7

[0044] The catalyst was prepared in the same way as described in example 1 except that support S3 was used in the preparation. The metal impregnated dried catalyst (dry base) had 24.8 wt. % MoO.sub.3, 4.3 wt. % CoO, 2.2 wt. % P.sub.2O.sub.5 and 2.9% B.sub.2O.sub.3, and was further modified by adding thiolactic acid (3.5 mol/mol molybdenum present in the catalyst) in a rotating pan. The intermediate was further aged for 1 hour under blowing hot air, while rotating. The extrudates were then poured out into a petri dish and placed in an oven at 80? C. for 16 hours. The resulting sample was labelled A7.

Example 8: Invention A8

[0045] The catalyst was prepared in the same way as illustrated in example 1, except for two differences: support S5 was used; diethylene glycol (0.44 mol/mol of hydrogenation (Co+Mo) metals present), was added to the metal solution prior to impregnation. The resulting sample (excluding the organic additive) was found to have 18.7 wt. % MoO.sub.3, 3.4 wt. % CoO and 4.2 wt. % P.sub.2O.sub.5. This is labelled as A8.

Example 9: Invention A9

[0046] The catalyst was prepared in the same way as described in example 1 except that support S5 was used in the preparation. The metal impregnated dried catalyst (dry base) was found to have 22.4 wt. % MoO.sub.3, 4 wt. % CoO and 4.3 wt. % P.sub.2O.sub.5, and was further modified by adding thioglycolic acid (3.5 mol/mol molybdenum present in the catalyst) in a rotating pan. The intermediate was further aged for 1 hour, while rotating. The extrudates were then poured out into a petri dish and placed in an oven at 80? C. for 16 hours. The resulting sample was labelled A9.

Example 10: Invention A10

[0047] The catalyst was prepared in the same way as described in example 1 except that support S5 was used in the preparation. The metal impregnated dried catalyst (dry base) was found to have 22.4 wt. % MoO.sub.3, 4 wt. % CoO and 4.3 wt. % P.sub.2O.sub.5, and was further modified by adding thiolactic acid (3.5 mol/mol molybdenum present in the catalyst) in a rotating pan. The intermediate was further aged for 1 hour, while rotating. The extrudates were then poured out into a petri dish and placed in an oven at 80? C. for 16 hours. The resulting sample was labelled A10.

TABLE-US-00003 TABLE 3 The effect of the addition of a support dopant and further a mercapto-carboxylic acids in the activity of supported CoMo catalysts in the FCC-PT application. RVA RVA Example Support Additive Test HDN HDS Benchmark Comparative S2 None crushed 100% 100% A1 A1 Comparative S1 2.2-dithioethanol crushed 119% 141% A1 A2 Comparative S1 Thiolactic acid crushed 127% 146% A1 A3 Comparative S1 Thioglycolic acid crushed 134% 151% A1 A4 Comparative S2 Di ethylene glycol crushed 124% 132% A1 A5 Invention A6 S3 Thioglycolic acid crushed 141% 156% A1 Invention A7 S3 Thiolactic acid crushed 149% 165% A1 Comparative S5 Di ethylene glycol extrudates 100% 100% A8 A8 Invention A9 S5 Thioglycolic acid crushed 146% 119% A8 Invention A10 S5 Thiolactic acid crushed 131% 119% A8

Examples HC-PT Application

[0048] Table 4 presents the pre-sulfiding and testing conditions. For the sake of comparison in HC-PT, we use NiMo grades. The benchmark contains a boron-containing support. Comparison is made between samples with similar metal loadings. The catalyst comparison is presented at nitrogen and sulfur levels of 60 mg/kg N and 190 mg/kg S (for the reference catalyst). Table 5 lists the relative HDS and HDN activity per volume basis (RVA) and compared to the benchmark (set at 100%) for both hydrodenitrification (HDN) and hydrodesulphurization (HDS).

TABLE-US-00004 TABLE 4 Pre-sulfiding and HC-PT test format of Standard Extrudate runs. Pre-sulfiding LHSV H.sub.2/oil Temperature Feed P (bar) (1/hr) (Nl/l) (? C.) Time (hours) Spiked LGO 45 3 300 320 29 Test condition Time on LHSV Temperature stream Feed P (bar) (1/hr) H.sub.2/oil (Nl/l) (? C.) (days) nHDS VGO 120 1.7 1000 380 35 1.1

Example 11: Comparative B1

[0049] An impregnation solution was prepared by mixing appropriate amounts of Nickel carbonate (NiCO.sub.3, 49% purity), molybdenum trioxide (MoO.sub.3) and phosphoric acid (H.sub.3PO.sub.4) in deionized water. The mixture was constantly stirred and kept at an appropriate temperature such as to obtain a clear solution with minimal loss of water. The initial amount of water is chosen in such a way that the resulting metal solution would have sufficient metals as compared to that desired in the final product such that no further evaporation of water is required. To this metal solution diethylene glycol (0.44 mol/mol of hydrogenation metals present), was added.

[0050] Support S4 was impregnated with the above mentioned impregnation solution to 115% of its pore volume saturation. The thus impregnated catalyst extrudates were aged in the rotating pan for 30 minutes at room temperature. After this, the extrudates were dried by blowing hot air (120? C., inlet) for another 30-60 minutes until free flowing extrudates are obtained. Thus, a metal impregnated dried catalyst is obtained, which is labelled as B1. The final metal content of the catalyst (dry base, excluding organics) was found to be 24 wt. % MoO.sub.3, 3.8 wt. % NiO, 6.8 wt. % P.sub.2O.sub.5 and 4.5 wt. % B.sub.2O.sub.3.

Example 12: Invention B2

[0051] Catalyst B2 was made in the same way as described in example 11, except that no diethylene glycol was added to the metal solution and support S6 was used. The metal impregnated catalyst (dry base) was found to have 24 wt. % MoO.sub.3, 3.8 wt. % NiO, 7.1 wt. % P.sub.2O.sub.5 and 5.6 wt. % B.sub.2O.sub.3 and was further modified by adding thioglycolic acid (3.5 mol/mol molybdenum present in the catalyst) in a rotating pan. The intermediate was further aged for 1 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 resulting sample was labelled B2.

Example 13: Comparative B3

[0052] The catalyst was prepared in the same way as described in example 11, however to end up with a higher metal content. The metal impregnated dried catalyst (excluding organics) was found to have 25.9 wt. % MoO.sub.3, 4.1 wt. % NiO, 7.2 wt. % P.sub.2O.sub.5 and 4.4% B.sub.2O.sub.3. The resulting sample was labelled B3.

Example 14: Invention B4

[0053] Catalyst B4 was made in the same way as described in example 12, however with lower amount of TGA (1.75 mol/mol molybdenum present in the catalyst) and to end up with a higher metal content. The metal impregnated catalyst (dry base) was found to have 26 wt. % MoO.sub.3, 4.1 wt. % NiO, 7.6 wt. % P.sub.2O.sub.5 and 4.9 wt. % B.sub.2O.sub.3. The resulting sample was labelled B4.

Example 15: Invention B5

[0054] The catalyst was prepared in the same way as described in example 11, except that citric acid (instead of diethylene glycol) was added to the metal solution (0.14 mol/mol of hydrogenation metals present) and support S7 was used for impregnation of the said solution. The metal impregnated catalyst (dry base) was found to have 25.9 wt. % MoO.sub.3, 4.3 wt. % NiO, 7.1 wt. % P.sub.2O.sub.5 and 3.5 wt. % B.sub.2O.sub.3 and was further modified by adding thioglycolic acid (1 mol/mol molybdenum present in the catalyst) in a rotating pan. The intermediate was further aged for 1 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 resulting sample was labelled B5.

Example 16: Invention B6

[0055] The catalyst was prepared in the same way as described in example 11, except that citric acid was also added to the metal solution (0.14 mol/mol of hydrogenation metals present) and support S9 was used for impregnation of the said solution. The metal impregnated catalyst (dry base) was found to have 26.2 wt. % MoO.sub.3, 4.1 wt. % NiO, 7.2 wt. % P.sub.2O.sub.5 and 2.6 wt. % B.sub.2O.sub.3 and was further modified by adding thioglycolic acid (1 mol/mol molybdenum present in the catalyst) in a rotating pan. The intermediate was further aged for 1 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 resulting sample was labelled B6.

TABLE-US-00005 TABLE 5 The effect of the addition of a support dopant and further a mercapto-carboxylic acids in the activity of supported NiMo catalysts in the HC-PT application. RVA RVA Example Support Additive Test HDN HDS Benchmark Comparative S4 Di ethylene glycol extrudates 100% 100% B1 B1 Invention B2 S6 Thio glycolic acid extrudates 123% 113% B1 Comparative S4 Di ethylene glycol extrudates 100% 100% B3 B3 Invention B4 S6 Thio glycolic acid extrudates 133% 118% B3 Invention B5 S7 Citric acid + thio extrudates 125% 118% B3 glycolic acid Invention B6 S9 Diethylene glycol + crushed 108% 111% B3 citric acid + thio glycolic acid

Examples High-Pressure ULSD Application

[0056] The catalysts were tested in a multi-test unit under ultra-low sulfur diesel conditions. Table 6 lists the pre-sulfidation and testing condition used for the comparison. The four catalysts presented are NiMo grades with comparable metal loadings and are based on two different supports. Table 7 shows the activity results.

TABLE-US-00006 TABLE 6 Pre-sulfiding and high pressure ULSD test format of Standard Extrudate runs. Pre-sulfiding LHSV H.sub.2/oil Temperature Feed P (bar) (1/hr) (Nl/l) (? C.) Time (hours) Spiked LGO 45 3 300 320 24 Test condition Time on LHSV Temperature stream Feed P (bar) (1/hr) H.sub.2/oil (Nl/l) (? C.) (days) nHDS HGO 80 1.75 500 341 14 1.05

Example 17: Comparative C1

[0057] Comparative C1 was prepared on support S4 in the same way as described in example 11, except a higher amount of diethylene glycol (1 mol/mol of hydrogenation metals) and metals were used. The final metal composition of the catalyst (dry base, excluding organics) was 28.9 wt. % MoO.sub.3, 4.7 wt. % NiO, 3.2 wt. % P.sub.2O.sub.5 and 4.7% B.sub.2O.sub.3.

Example 18: Invention C2

[0058] Invention C2 was prepared on support S4 in the same way as illustrated in example 17, except no diethylene glycol was added to the metal solution. The composition of the metal impregnated dried catalyst (dry base) was 28.9 wt. % MoO.sub.3, 4.6 wt. % NiO, 3.2 wt. % P.sub.2O.sub.5 and 4.7% B.sub.2O.sub.3 and was further modified by adding thioglycolic acid (1 mol/mol total hydrogenation metals in the catalyst) in a rotating pan. The intermediate was further aged for 1 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 resulting sample was labelled C2.

Example 19: Comparative C3

[0059] Comparative C3 was prepared in the same way as illustrated in example 17, except support S8 was used instead. The final metal composition of the catalyst (dry base, excluding organics) was 28.5 wt. % MoO.sub.3, 4.5 wt. % NiO, 3 wt. % P.sub.2O.sub.5 and 8 wt. % SiO.sub.2.

Example 20: Invention C4

[0060] The catalyst was produced in the same way as illustrated in example 18, except support S8 was used instead. The final metal composition of the catalyst (dry base, excluding organics) was 28.8 wt. % MoO.sub.3, 4.5 wt. % NiO, 2.8 wt. % P.sub.2O.sub.5 and 7.7 wt. % SiO.sub.2.

TABLE-US-00007 TABLE 7 The effect of the addition of a dopant and further a mercapto-carboxylic acids in the activity of supported NiMo catalysts in the HP-ULSD application. RVA RVA Bench- Example Support Additive Test HDN HDS mark Comparative S4 Diethylene Extrudates 100% 100% C1 C1 glycol Invention C2 S4 Thioglycolic Extrudates 113% 125% C1 acid Comparative S8 Diethylene Extrudates 100% 100% C3 C3 glycol Invention C4 S8 Thioglycolic Extrudates 113% 132% C3 acid

Examples Moderate Pressure ULSD Application

[0061] The catalysts were tested in a multi-test unit under medium pressure ultra-low sulfur diesel conditions. The four catalysts presented are CoMo grades with comparable metal loadings and are based on two different supports. Table 8 shows the pre-sulfidation and activity results and Table 9 shows the activity results.

TABLE-US-00008 TABLE 8 Pre-sulfiding and MP-ULSD test format of Standard Extrudate runs. Pre-sulfiding LHSV H.sub.2/oil Temperature Feed P (bar) (1/hr) (Nl/l) (? C.) Time (hours) Spiked LGO 45 3 300 320 24 Conditions H.sub.2/ Tem- Time on P LHSV oil perature stream Condition Feed (bar) (1/hr) (Nl/l) (? C.) (days) nHDS 1 SRGO 45 4 200 350 6 1

Example 21: Comparative D1

[0062] Comparative D1 was prepared in the same way as described in example 5, except that Support S1 was used in the preparation, and an additional amount of citric acid was included in the metal solution (0.07 mol/mol of hydrogenation metals). The final metal composition of the catalyst (dry base, excluding organics) was 24.1 wt. % MoO.sub.3, 4.2 wt. % CoO and 2.1 wt. % P.sub.2O.sub.5.

Example 22: Comparative D2

[0063] Comparative D2 was prepared in the same way and on the same support as example 21, except no diethylene glycol was added to the metal solution. The composition of the metal impregnated dried catalyst (dry base) was 24.1 wt. % MoO.sub.3, 4.2 wt. % CoO and 2.1 wt. % P.sub.2O.sub.5 and was further modified by adding thioglycolic acid (1 mol/mol total hydrogenation metals in the catalyst) in a rotating pan. The intermediate was further aged for 1 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 resulting sample was labelled D2.

Example 23: Comparative D3

[0064] Comparative D3 was prepared in the same way as described in example 21, except that Support S2 was used in the preparation, and no citric acid was included in the metal solution. The final metal composition of the catalyst (dry base, excluding organics) was 24.1 wt. % MoO.sub.3, 4.1 wt. % CoO, 2 wt. % P.sub.2O.sub.5 and 3 wt. % B.sub.2O.sub.3. The resulting catalyst was labelled D3.

Example 24: Invention D4

[0065] Invention D4 was in the same way and on the same support as example 23, except no diethylene glycol was added to the metal solution. The composition of the metal impregnated dried catalyst (dry base) was 24.1 wt. % MoO.sub.3, 4.1 wt. % CoO, 2 wt. % P.sub.2O.sub.5 and 3 wt. % B.sub.2O.sub.3 and was further modified by adding thioglycolic acid (1 mol/mol total hydrogenation metals in the catalyst) in a rotating pan. The intermediate was further aged for 1 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 resulting sample was labelled D4.

TABLE-US-00009 TABLE 9 The effect of the addition of a dopant and further a mercapto-carboxylic acids in the activity of supported NiMo catalysts in the MP-ULSD application RVA RVA Bench- Example Support Additive Test HDN HDS mark Comparative S1 Diethylene Extrudates 100% 100% D1 D1 glycol + citric acid Invention D2 S1 Thioglycolic Extrudates 121% 106% D1 acid + citric acid Comparative S2 Diethylene Extrudates 103% 85% D1 D3 glycol Invention D4 S2 Thioglycolic Extrudates 206% 143% D1 acid

[0066] 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.

[0067] The invention may comprise, consist, or consist essentially of the materials and/or procedures recited herein.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.