Hydrotreating catalyst containing phosphorus and boron

Abstract

A catalyst having at least one Group VIB metal component, at least one Group VIII metal component, a phosphorus component, and a boron-containing carrier component. The amount of the phosphorus component is at least 1 wt %, expressed as an oxide (P.sub.2O.sub.5) and based on the total weight of the catalyst, and the amount of boron content is in the range of about 1 to about 13 wt %, expressed as an oxide (B.sub.2O.sub.3) and based on the total weight of the catalyst. In one embodiment of the invention, the boron-containing carrier component is a product of a co-extrusion of at least a carrier and a boron source. A method for producing the catalyst and its use for hydrotreating a hydrocarbon feed are also described.

Claims

1. A catalyst comprising at least one Group VIB metal component, at least one Group VIII metal component comprising nickel and/or cobalt, a phosphorus component, and a boron-containing carrier component, wherein the amount of the phosphorus component is at least about 1 wt %, expressed as an oxide (P.sub.2O.sub.5) and based on the total weight of the catalyst, and the boron content is in the range of about 1 to about 13 wt %, expressed as an oxide (B.sub.2O.sub.3) and based on the total weight of the catalyst; and wherein the formation of the catalyst involves at least co-extruding a boron compound with a carrier to form a boron-containing carrier extrudate, drying and calcining the extrudate, and impregnating the calcined extrudate with a solution comprised of a phosphorus source, at least one Group VIB metal source and/or at least one Group VIII metal source.

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

3. The catalyst according to claim 2 wherein the Group VIII metal component comprises nickel.

4. The catalyst according to claim 2 wherein the Group VIII metal component comprises cobalt.

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

6. The catalyst according claim 1 wherein the carrier comprises alumina.

7. The catalyst according to claim 1 wherein the boron compound is selected from the group consisting of meta-boric acid, ortho-boric acid, ammonium borate tetra-hydrate, sodium tetra borate, ammonium borate, ammonium tetra borate, boric oxide, mono-, di- and tri-alkyl amine borate, ammonium tetra phenyl borate, and a mixture of any two or more of the foregoing.

8. The catalyst according to claim 1, further comprising an organic additive.

9. The catalyst according to claim 8, wherein the organic additive is (i) an organic compound selected from the group consisting of (a) organic compounds comprising at least two oxygen atoms and 2-10 carbon atoms, and (b) the ethers, esters, acetals, acid chlorides, acid amides, oligomers and polymers of the organic compounds of (a), and/or (ii) an organic compound comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety.

10. A method which comprises contacting a hydrocarbon feed with a catalyst according to claim 9 under hydrotreating conditions so as to hydrotreat the hydrocarbon feed.

11. The catalyst according to claim 9 wherein the organic additive is selected from 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.

12. A method which comprises contacting a hydrocarbon feed with a catalyst according to claim 1 under hydrotreating conditions so as to hydrotreat the hydrocarbon feed.

13. The catalyst according to claim 1 wherein the components consist of at least one Group VIB metal component, at least one Group VIII metal component comprising nickel and/or cobalt, a phosphorus component, a boron-containing carrier component, and optionally an organic additive.

14. The catalyst according to claim 13 wherein the organic additive is (i) an organic compound selected from the group consisting of (a) organic compounds comprising at least two oxygen atoms and 2-10 carbon atoms, and (b) the ethers, esters, acetals, acid chlorides, acid amides, oligomers and polymers of the organic compounds of (a), and/or (ii) an organic compound comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety.

15. A method of producing a catalyst, the method comprising co-extruding a boron compound with a carrier to form a boron-containing carrier extrudate, drying and calcining the extrudate, and impregnating the calcined extrudate with a solution comprised of a phosphorus source, at least one Group VIB metal source and/or at least one Group VIII metal source comprising nickel and/or cobalt, the amount of the boron compound and the amount of the phosphorus source being sufficient so as to form a catalyst composition at least having a boron content in the range of about 1 wt % to about 13 wt %, expressed as an oxide (B.sub.2O.sub.3) and based on the total weight of the catalyst, and a phosphorus content of at least about 1 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 15, further comprising calcining an impregnated calcined extrudate formed in the impregnating step.

17. The method according to claim 15, further comprising drying an impregnated calcined extrudate formed in the impregnation step so as to form a dried impregnated calcined extrudate so as to form the catalyst.

18. The method according to claim 17 wherein the solution further comprises an organic additive.

19. The method of claim 15, further comprising drying an impregnated calcined extrudate formed in the impregnation step so as to form a dried impregnated calcined extrudate, and further calcining the dried impregnated calcined extrudate so as to form the catalyst.

20. The method according to claim 15 wherein the solution further comprises an organic additive.

21. The method according to claim 20 wherein the organic additive is (i) an organic compound selected from the group consisting of (a) organic compounds comprising at least two oxygen atoms and 2-10 carbon atoms, and (b) the ethers, esters, acetals, acid chlorides, acid amides, oligomers and polymers of the organic compounds of (a), and/or (ii) an organic compound comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety.

22. A catalyst formed by the process of claim 15.

23. The method according to claim 15 wherein the components consist of a boron compound, a carrier, and a solution comprised of a phosphorus source, at least one Group VIB metal source, at least one Group VIII metal source comprising nickel and/or cobalt, and optionally an organic additive.

24. The method according to claim 23 wherein the organic additive is (i) 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/or (ii) an organic compound comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety.

Description

EXAMPLES

(1) Activity Test

(2) The activity test was carried out in a micro flow reactor. Light Gas Oil (LGO) spiked with dimethyl disulfide (DMDS) (total S content of 3.6 wt %) was used for presulphiding, Heavy Gas Oil (HGO), having a S content of 1.6 wt. % and N content of 1050 ppm, Vacuum Gas Oil (VGO), having a S content of 1.8 wt. % and N content of 1152 ppm and Light Gas Oil (LGO), having a S content of 1.2 wt. % and a N content of 94 ppm, were used for testing. Detailed information about feed and test condition is given in Tables 1-5.

(3) The relative weight activities for the various catalysts were determined as follows. For each catalyst the reaction constant k wt was calculated from the following formula:
k wt=WHSV*1/(n?1)?(1/Sn.sup.?1?1/S.sub.0.sup.n?1)
in which the S stands for percentage of sulfur in the product and S.sub.0 for the percentage of sulfur in the feed, and n stands for the reaction order of the hydrodesulfurisation reaction. For HC-PT and FCC-PT mode a n of 1.75 was used. For ULSD a n of 1.2 was used For nitrogen the k wt was calculated from the following formula:
k wt=ln(N.sub.0/N)*WHSV
in which the N stands for the nitrogen content in the product and No for the nitrogen content in the feed.

(4) In the tables, S=sulfur, N=nitrogen, ToS=time on stream, LHSV=liquid hourly space velocity, IBP=initial boiling point, FBP=final boiling point.

(5) TABLE-US-00001 TABLE 1 Feed properties IBP FBP Feed wt % S ppm N Density (g/ml) (? C.) (? C.) HGO 1.578 1050 0.9443 (@ 15.5 C) 139 482 VGO 1.763 1152 0.9221 (@ 15.5 C) 265 600 LGO 1.167 94 0.8366 (@ 15.5 C) 114 420
Presulfiding/Testing Conditions

(6) TABLE-US-00002 TABLE 2 Test conditions HC-PT test, Feed HGO. Presulphiding Testing Temperature (? C.) 320 345 H2 pressure (bar) 45 100 LHSV 3 2.75 H2/oil 300 1000 Time (hours) 27.5 * Feed LGO spiked with DMDS (total S content of 3.6 wt %) was used for presulphiding. * Time on stream is reported in the text of the examples.

(7) TABLE-US-00003 TABLE 3 Test conditions HC-PT test, Feed VGO. Presulphiding Testing Temperature (? C.) 340 382 H2 pressure (bar) 30 120 LHSV 3 1.75 H2/oil 300 1000 Time (hours) 27.5 * Feed LGO spiked with DMDS (total S content of 3.6 wt %) was used for presulphiding. * Time on stream is reported in the text of the examples.

(8) TABLE-US-00004 TABLE 4 Test conditions FCC-PT test, Feed VGO. Presulphiding Testing Temperature (? C.) 320 360 H2 pressure (bar) 45 70 LHSV 3 1.2 H2/oil 300 400 Time (hours) 16 * Feed LGO spiked with DMDS (total S content of 3.6 wt %) was used for presulphiding. * Time on stream is reported in the text of the examples.

(9) TABLE-US-00005 TABLE 5 Test conditions ULSD test, Feed LGO. Presulphiding Testing Temperature (? C.) 320 340 H2 pressure (bar) 45 45 LHSV 3 2 H2/oil 300 300 Time (hours) 27.1 * Feed LGO spiked with DMDS (total S content of 3.6 wt %) was used for presulphiding. * Time on stream is reported in the text of the examples.
Support Preparation (0-18.75 wt % B.sub.2O.sub.3 in Support)

(10) The support was prepared by mixing an alumina hydrate cake (water content about 80%) and boric acid (H.sub.3BO.sub.3) in a kneader to form an extrudable paste. (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 1.3Q die plate, dried overnight at 120? C. and then calcined (optionally with steam) at a temperature in the range of 475-850? C. (See Table 6).

(11) Support D3 was prepared from A1 and supports B.sub.2, C3 and D4 were prepared from A6 by pore volume impregnation of the support A1 and A6, respectively, with a solution of ammonium tetra borate tetra hydrate ((NH.sub.4).sub.2B.sub.4O.sub.7.4H.sub.2O) in water. The impregnated support was heated to a temperature of 120? C., kept at this temperature for 30 minutes and subsequently calcined (optionally with steam) at a temperature in the range of 475-550? C. for 1 hour (See Table 6).

(12) TABLE-US-00006 TABLE 6 Calcination temperature of the supports A-H Calcination Support B.sub.2O.sub.3 (wt %) Temperature (? C.) A1 0 475 A2 0 600 A3 0 750 A4 0 840 A5 0 720 A6 0 550 B1 1.88 700 B2 1.88 550 C1 3.75 700 C2 3.75 680 C3 3.75 550 D1 7.5 760 D2 7.5 800 D3 7.5 475 D4 7.5 550 E1 9.8 650 E2 9.8 750 E3 9.8 550 F1 11.25 810 F2 11.25 760 G1 15 850 H1 18.75 750
Preparation and Testing of Catalysts 1-44

(13) All chemical compositions of the catalysts are calculated on basis of the amount of material used for the catalyst preparation.

Example 1

(14) NiMoP Catalyst 1

(15) The impregnation solution was prepared by mixing appropriate amounts of water, nickel carbonate [Ni(OH).sub.x(CO.sub.3).sub.Y], molybdenum trioxide (MoO.sub.3), and phosphoric acid (H.sub.3PO.sub.4). The mixture was sufficiently heated and kept at temperature while stirred until a clear solution was obtained. After the solution was cooled down, diethylene glycol (0.44 mol/mol hydrogenation metals present in the catalyst) was added. The initial amount of water was chosen in a way that the total volume of the solution after the addition of diethylene glycol was ca. 230% of the pore volume for the impregnation of the powdered support A4.

(16) Support A4 was crushed, sieved and impregnated with the impregnation solution to 230% pore volume saturation. The impregnated powder was dried 10 hours at 80? C. and subsequently for 4 hours at 120? C. The final MoO.sub.3 content was 24 wt % (dry base) of the finished catalyst. The final NiO content was 4 wt % (dry base) of the finished catalyst. The final P.sub.2O.sub.5 content was 2 wt % (dry base) of the finished catalyst.

(17) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 1026 ppm (k wt=21.05) and product N of 80 ppm (k wt=8.38) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 2

(18) NiMoPB Catalyst 2

(19) The powdered catalyst was prepared as described in Example 1, except that support D1 was used and the final B.sub.2O.sub.3 content was 5.3 wt % (dry base) of the finished catalyst.

(20) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 976 ppm (k wt=21.76) and product N of 29 ppm (k wt=11.54) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 3

(21) NiMoPB Catalyst 3

(22) The powdered catalyst was prepared as described in Example 1, except that support G1 was used and that the final B.sub.2O.sub.3 content was 10.5 wt % (dry base) of the finished catalyst.

(23) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 995 ppm (k wt=21.11) and product N of 23 ppm (k wt=12.24) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 4

(24) NiMoP Catalyst 4

(25) The powdered catalyst was prepared as described in Example 1, except that the final P.sub.2O.sub.5 content was 4.5 wt % (dry base) of the finished catalyst.

(26) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 902 ppm (k wt=23.10) and product N of 44 ppm (k wt=10.18) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 5

(27) NiMoPB Catalyst 5

(28) The powdered catalyst was prepared as described in Example 4, except that support C1 was used and that the final B.sub.2O.sub.3 content was 2.5 wt % (dry base) of the finished catalyst.

(29) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 910 ppm (k wt=21.90) and product N of 18 ppm (k wt=11.75) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 6

(30) NiMoPB Catalyst 6

(31) The powdered catalyst was prepared as described in Example 4, except that support D1 was used and that the final B.sub.2O.sub.3 content was 5.1 wt % (dry base) of the finished catalyst.

(32) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 926 ppm (k wt=22.31) and product N of 16 ppm (k wt=12.70) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 7

(33) NiMoPB Catalyst 7

(34) The powdered catalyst was prepared as described in Example 4, except that support F1 was used and that the final B.sub.2O.sub.3 content was 7.6 wt % (dry base) of the finished catalyst.

(35) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 1137 ppm (k wt=18.18) and product N of 16 ppm (k wt=12.70) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 8

(36) NiMoPB Catalyst 8

(37) The powdered catalyst was prepared as described in Example 4, except that support G1 was used and that the final B.sub.2O.sub.3 content was 10.1 wt % (dry base) of the finished catalyst.

(38) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 998 ppm (k wt=21.33) and product N of 23 ppm (k wt=12.43) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 9

(39) NiMoP Catalyst 9

(40) The powdered catalyst was prepared as described in Example 1, except that the final P.sub.2O.sub.5 content was 7 wt % (dry base) of the finished catalyst.

(41) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 1069 ppm (k wt=20.62) and product N of 34 ppm (k wt=10.57) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

(42) Catalyst 9 was also prepared as whole extrudates, following the preparation procedure as described above, except that the total volume of the impregnation solution after the addition of di ethylene glycol was ca. 110% of the pore volume for the impregnation of extrudates support A4 and that the support was impregnated with the impregnation solution to 110% pore volume saturation.

(43) Extrudates of catalyst 9 were tested in HC-PT mode with HGO feed (product S of 653 ppm (k wt=28.74) and product N of 26 ppm (k wt=11.49) after 192 hours time on stream), in HC-PT mode with VGO feed (product S of 583 ppm (k wt=19.84) and product N of 155 ppm (k wt=4.01) after 300 hours time on stream) and in FCC-PT mode with VGO feed (product S of 2022 ppm (k wt=4.72) and product N of 557 ppm (k wt=0.97) after 174 hours time on stream).

Example 10

(44) NiMoPB Catalyst 10

(45) The powdered catalyst was prepared as described in Example 9, except that support C1 was used and that the final B.sub.2O.sub.3 content was 2.4 wt % (dry base) of the finished catalyst.

(46) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 964 ppm (k wt=20.97) and product N of 18 ppm (k wt=11.21) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

(47) Catalyst 10 was also prepared as whole extrudates, following the preparation procedure as described above, except that the total volume of the impregnation solution after the addition of di ethylene glycol was ca. 110% of the pore volume for the impregnation of extrudates support C1 and that the support was impregnated with the impregnation solution to 110% pore volume saturation.

(48) Extrudates of catalyst 10 were tested in HC-PT mode with HGO feed (product S of 438 ppm (k wt=41.57) and product N of 12 ppm (k wt=14.26) after 192 hours time on stream) and in HC-PT mode with VGO feed (product S of 304 ppm (k wt=32.40) and product N of 92 ppm (k wt=4.65) after 300 hours time on stream).

Example 11

(49) NiMoPB Catalyst 11

(50) The powdered catalyst was prepared as described in Example 9, except that support D1 was used and that the final B.sub.2O.sub.3 content was 4.9 wt % (dry base) of the finished catalyst.

(51) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 799 ppm (k wt=25.59) and product N of 11 ppm (k wt=14.17) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

(52) Catalyst 11 was also prepared as whole extrudates, following the preparation procedure as described above, except that the total volume of the impregnation solution after the addition of di ethylene glycol was ca. 110% of the pore volume for the impregnation of extrudates support D1 and that the support was impregnated with the impregnation solution to 110% pore volume saturation.

(53) Extrudates of catalyst 11 were tested in HC-PT mode with HGO feed (product S of 349 ppm (k wt=47.72) and product N of 8 ppm (k wt=14.93) after 192 hours time on stream), in HC-PT mode with VGO feed (product S of 300 ppm (k wt=31.84) and product N of 80 ppm (k wt=4.82) after 300 hours time on stream) and in FCC-PT mode with VGO feed (product S of 1805 ppm (k wt=5.46) and product N of 463 ppm (k wt=1.26) after 174 hours time on stream).

Example 12

(54) NiMoPB Catalyst 12

(55) The powdered catalyst was prepared as described in Example 9, except that support F1 was used and that the final B.sub.2O.sub.3 content was 7.3 wt % (dry base) of the finished catalyst.

(56) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 1190 ppm (k wt=17.52) and product N of 21 ppm (k wt=11.35) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 13

(57) NiMoPB Catalyst 13

(58) The powdered catalyst was prepared as described in Example 9, except that support G1 was used and that the final B.sub.2O.sub.3 content was 9.8 wt % (dry base) of the finished catalyst.

(59) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 1043 ppm (k wt=20.21) and product N of 26 ppm (k wt=11.81) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 14

(60) NiMoPB Catalyst 14

(61) The powdered catalyst was prepared as described in Example 1, except that support F1 was used and that the final P.sub.2O.sub.5 content was 9.5 wt % (dry base) and the final B.sub.2O.sub.3 content was 7.0 wt % (dry base) of the finished catalyst.

(62) The catalyst was tested in HC-PT mode with HGO feed and reached a product S of 1370 ppm (k wt=15.59) and product N of 30 ppm (k wt=11.48) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 15

(63) NiMoPB Catalyst 15

(64) The catalyst was prepared as whole extrudates as described in Example 9, except that support B.sub.1 was used and that the final P.sub.2O.sub.5 content was 1.5 wt % (dry base) and the final B.sub.2O.sub.3 content was 1.3 wt % (dry base) of the finished catalyst.

(65) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1220 ppm (k wt=8.06) and product N of 509 ppm (k wt=1.18) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 16

(66) NiMoPB Catalyst 16

(67) The powdered catalyst was prepared as described in Example 1, except that support C2 was used and that the final MoO.sub.3 content was 19 wt % (dry base), the final P.sub.2O.sub.5 content was 4 wt % (dry base) and the final B.sub.2O.sub.3 content was 2.7 wt % (dry base) of the finished catalyst.

(68) The catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1481 ppm (k wt=6.48) and product N of 545 ppm (k wt=1.03) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 17

(69) NiMoPB Catalyst 17

(70) The powdered catalyst was prepared as described in Example 16, except that support F2 was used and that the final B.sub.2O.sub.3 content was 8.2 wt % (dry base) of the finished catalyst.

(71) The catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1616 ppm (k wt=6.06) and product N of 521 ppm (k wt=1.11) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 18

(72) NiMoP Catalyst 18

(73) The catalyst was prepared as whole extrudates as described in Example 9, except that support A1 was used and that the final P.sub.2O.sub.5 content was 4.5 wt % (dry base) of the finished catalyst.

(74) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1216 ppm (k wt=7.03) and product N of 455 ppm (k wt=1.16) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 19

(75) NiMoPB Catalyst 19

(76) The catalyst was prepared as whole extrudates as described in Example 18, except that support B.sub.1 was used and that the final B.sub.2O.sub.3 content was 1.3 wt % (dry base) of the finished catalyst.

(77) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1230 ppm (k wt=7.85) and product N of 473 ppm (k wt=1.26) after 120 hours time on stream.

Example 20

(78) NiMoPB Catalyst 20

(79) The catalyst was prepared as whole extrudates as described in Example 18, except that support B.sub.2 was used and that the final B.sub.2O.sub.3 content was 1.3 wt % (dry base) of the finished catalyst.

(80) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1115 ppm (k wt=7.33) and product N of 413 ppm (k wt=1.25) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 21

(81) NiMoPB Catalyst 21

(82) The catalyst was prepared as whole extrudates as described in Example 9, except that support C1 was used and that the final MoO.sub.3 content was 26 wt % (dry base), the final NiO content was 5 wt % (dry base), the final P.sub.2O.sub.5 content was 4.5 wt % (dry base) and the final B.sub.2O.sub.3 content was 2.4 wt % (dry base) of the finished catalyst.

(83) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1407 ppm (k wt=6.63) and product N of 452 ppm (k wt=1.26) after 120 hours time on stream.

Example 22

(84) NiMoPB Catalyst 22

(85) The catalyst was prepared as whole extrudates as described in Example 9, except that support C1 was used and that the final MoO.sub.3 content was 22 wt % (dry base), the final NiO content was 3 wt % (dry base), the final P.sub.2O.sub.5 content was 4.5 wt % (dry base) and the final B.sub.2O.sub.3 content was 2.6 wt % (dry base) of the finished catalyst.

(86) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1664 ppm (k wt=6.14) and product N of 507 ppm (k wt=1.19) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 23

(87) NiMoPB Catalyst 23

(88) The catalyst was prepared as whole extrudates as described in Example 22, except that support C1 was used and that the final NiO content was 5 wt % (dry base) of the finished catalyst.

(89) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1282 ppm (k wt=7.87) and product N of 455 ppm (k wt=1.37) after 120 hours time on stream.

Example 24

(90) NiMoPB Catalyst 24

(91) The catalyst was prepared as whole extrudates as described in Example 23, except that support C3 was used.

(92) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1231 ppm (k wt=7.08) and product N of 429 ppm (k wt=1.26) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 25

(93) NiMoPB Catalyst 25

(94) The catalyst was prepared as whole extrudates as described in Example 18, except that support D3 was used and that the final B.sub.2O.sub.3 content was 5.1 wt % (dry base) of the finished catalyst.

(95) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1488 ppm (k wt=5.62) and product N of 406 ppm (k wt=1.25) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 26

(96) NiMoPB Catalyst 26

(97) The catalyst was prepared as whole extrudates as described in Example 25, except that support D2 was used.

(98) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1429 ppm (k wt=6.60) and product N of 419 ppm (k wt=1.37) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 27

(99) NiMoPB Catalyst 27

(100) The catalyst was prepared as whole extrudates as described in Example 25, except that support H1 was used and that the final B.sub.2O.sub.3 content was 12.7 wt % (dry base) of the finished catalyst.

(101) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1646 ppm (k wt=5.66) and product N of 436 ppm (k wt=1.28) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 28

(102) NiMoPB Catalyst 28

(103) The powdered catalyst was prepared as described in Example 1, except that support D1 was used and that the final MoO.sub.3 content was 19 wt % (dry base), the final P.sub.2O.sub.5 content was 6.5 wt % (dry base) and the final B.sub.2O.sub.3 content was 5.3 wt % (dry base) of the finished catalyst.

(104) The catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1473 ppm (k wt=6.09) and product N of 520 ppm (k wt=1.02) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 29

(105) NiMoPB Catalyst 29

(106) The powdered catalyst was prepared as described in Example 28, except that support F2 was used and that the final B.sub.2O.sub.3 content was 7.9 wt % (dry base) of the finished catalyst

(107) The catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1659 ppm (k wt=5.51) and product N of 486 ppm (k wt=0.94) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 30

(108) NiMoP Catalyst 30

(109) The catalyst was prepared as whole extrudates as described in Example 9, except that support A3 was used.

(110) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1597 ppm (k wt=5.50) and product N of 483 ppm (k wt=1.09) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 31

(111) NiMoPB Catalyst 31

(112) The catalyst was prepared as whole extrudates as described in Example 9, except that support C1 was used and that the final MoO.sub.3 content was 22 wt % (dry base), the final NiO content was 5 wt % (dry base), the final P.sub.2O.sub.5 content was 7 wt % (dry base) and the final B.sub.2O.sub.3 content was 2.5 wt % (dry base) of the finished catalyst.

(113) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1206 ppm (k wt=7.81) and product N of 415 ppm (k wt=1.41) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 32

(114) NiMoPB Catalyst 32

(115) The catalyst was prepared as whole extrudates as described in Example 31, except that support C3 was used.

(116) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1272 ppm (k wt=6.70) and product N of 416 ppm (k wt=1.27) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 33

(117) NiMoPB Catalyst 33

(118) The catalyst was prepared as whole extrudates as described in Example 9, except that support D2 was used and that the final B.sub.2O.sub.3 content was 4.9 wt % (dry base) of the finished catalyst.

(119) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1313 ppm (k wt=6.56) and product N of 408 ppm (k wt=1.42) after 120 hours time on stream.

Example 34

(120) NiMoPB Catalyst 34

(121) The catalyst was prepared as whole extrudates as described in Example 33, except that support D4 was used.

(122) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1275 ppm (k wt=6.44) and product N of 391 ppm (k wt=1.30) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 35

(123) NiMoPB Catalyst 35

(124) The catalyst was prepared as whole extrudates as described in Example 34, except that support H1 was used and that the final B.sub.2O.sub.3 content was 12.2 wt % (dry base) of the finished catalyst.

(125) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1592 ppm (k wt=5.62) and product N of 430 ppm (k wt=1.25) after 120 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 36

(126) NiMoPB Catalyst 36

(127) The powdered catalyst was prepared as described in Example 1, except that support C2 was used and that the final MoO.sub.3 content was 19 wt % (dry base), the final P.sub.2O.sub.5 content was 9 wt % (dry base) and the final B.sub.2O.sub.3 content was 2.6 wt % (dry base) of the finished catalyst.

(128) The catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1575 ppm (k wt=5.85) and product N of 533 ppm (k wt=1.01) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 37

(129) NiMoPB Catalyst 37

(130) The powdered catalyst was prepared as described in Example 36, except that support D1 was used and that the final B.sub.2O.sub.3 content was 5.1 wt % (dry base) of the finished catalyst.

(131) The catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1607 ppm (k wt=5.62) and product N of 559 ppm (k wt=0.93) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 38

(132) NiMoPB Catalyst 38

(133) The impregnation solution was prepared by mixing appropriate amounts of water, nickel carbonate [Ni(OH).sub.x(CO.sub.3).sub.Y], molybdenum trioxide (MoO.sub.3), and phosphoric acid (H.sub.3PO.sub.4). The mixture was sufficiently heated and kept at temperature while stirred until a clear solution was obtained. The initial amount of water was chosen in a way that the total volume of the solution was ca. 230% of the pore volume for the impregnation of the powdered support C2.

(134) Support C2 was crushed, sieved and impregnated with the impregnation solution to 230% pore volume saturation. The impregnated powder was dried for 10 hours at 80? C. and subsequently 4 hours at 120? C. Next, the dried catalyst was calcined for 1 hour at 480? C. The final MoO.sub.3 content was 19 wt % (dry base) of the finished catalyst. The final NiO content was 4 wt % (dry base) of the finished catalyst. The final P.sub.2O.sub.5 content was 4 wt % (dry base) of the finished catalyst. The final B.sub.2O.sub.3 content was 2.7 wt % (dry base) of the finished catalyst.

(135) The catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1396 ppm (k wt=6.33) and product N of 448 ppm (k wt=1.20) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 39

(136) NiMoP Catalyst 39

(137) The powdered catalyst was prepared as described in Example 38, except that support A5 was used and that the final P.sub.2O.sub.5 content was 6.5 wt % (dry base) of the finished catalyst.

(138) The catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1191 ppm (k wt=8.18) and product N of 556 ppm (k wt=1.05) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 40

(139) NiMoPB Catalyst 40

(140) The powdered catalyst was prepared as described in Example 38, except that support C2 was used and that the final P.sub.2O.sub.5 content was 6.5 wt % (dry base) of the finished catalyst.

(141) The catalyst was tested in FCC-PT mode with VGO feed and reached a product S of 1576 ppm (k wt=5.52) and product N of 468 ppm (k wt=1.12) after 144 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 41

(142) CoMoP Catalyst 41

(143) The extrudate catalyst was prepared as described in Example 9, except that nickel carbonate was replaced by cobalt carbonate (CoCO.sub.3) and that support A2 was used. The final MoO.sub.3 content was 24 wt % (dry base) of the finished catalyst. The final CoO content was 4.4 wt % (dry base) of the finished catalyst. The final P.sub.2O.sub.5 content was 2.1 wt % (dry base) of the finished catalyst.

(144) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in ULSD mode with LGO feed and reached a product S of 28.1 ppm (k wt=22.07) and product N of 1.15 ppm (k wt=10.18) after 216 hours time on stream. Results are on basis of averaged duplicate measurements.

Example 42

(145) CoMoPB Catalyst 42

(146) The extrudate catalyst was prepared as described in Example 41, except that support E3 was used and that the final MoO.sub.3 content was 25 wt % (dry base), the final CoO content was 6 wt % (dry base) and the final B.sub.2O.sub.3 content was 6 wt % (dry base) of the finished catalyst.

(147) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in ULSD mode with LGO feed and reached a product S of 11.9 ppm (k wt=24.97) and product N of 0.3 ppm (k wt=12.18) after 216 hours time on stream.

Example 43

(148) CoMoPB Catalyst 43

(149) The extrudate catalyst was prepared as described in Example 41, except that support E2 was used and that the final MoO.sub.3 content was 25 wt % (dry base) and the final B.sub.2O.sub.3 content was 6.1 wt % (dry base) of the finished catalyst.

(150) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in ULSD mode with LGO feed and reached a product S of 11.3 ppm (k wt=24.30) and product N of 0.3 ppm (k wt=11.71) after 216 hours time on stream.

Example 44

(151) CoMoPB Catalyst 44

(152) The extrudate catalyst was prepared as described in Example 41, except that support E1 was used and that the final CoO content was 5 wt % (dry base), the final P.sub.2O.sub.5 content was 7.9 wt % (dry base) and the final B.sub.2O.sub.3 content was 5.8 wt % (dry base) of the finished catalyst.

(153) The catalyst was crushed and sieved, prior to the activity test. The powdered catalyst was tested in ULSD mode with LGO feed and reached a product S of 11.7 ppm (k wt=25.09) and product N of 0.3 ppm (k wt=12.19) after 216 hours time on stream.

(154) 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.

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

(156) 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.

(157) 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.

(158) 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.

(159) 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.