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Catalytic Functionality of NiMo and CoMo Catalysts, Supported on US-Y Zeolite for hydrotreating processes.

K.S Rawat*, Manoj Kumar, J.K.Gupta, Rajaram Bal , G.Murali Dhar and A.Datta
Catalytic Conversion Processes Division, Indian Institute of Petroleum, Dehradun 248005, India *Email-ksrawat@iip.res.in

Abstract The Ultra stable Y zeolites were prepared by hydrothermal treatment of NH4Y zeolite in steam deactivation unit at a temperature of 600 oC in a fixed bed reactor. The prepared USY zeolite have a unit cell size (U.C.S ) of 24.41 0A and crystallinity of around 67.70%. The ultra stable Y zeolite was used as a support for preparing Mo catalysts and their Co and Ni promoter analogues. The MoS2 supported on USY catalyst was prepared by incipient wetness impregnation method. The Mo content was varied from 2 to 14 wt % and the promoter Co or Ni content varied from 1 to 5 wt %. The catalysts were characterized by B.E.T surface area, X-ray diffraction (XRD), Temperature Programmed Reduction (TPR) and Low temperature Oxygen Chemisorption . The catalytic activities were tested by using different model compound. The hydrodesulphurization (HDS) of thiophene and hydrogenation (HYD) of cyclohexane were carried out at 400 0C on a sulfided catalyst .These supported catalysts are reported to exhibit superior activities compared to commercial -Al2O3 supported catalyst. A correlation between oxygen chemisorption and catalytic activity has also been presented. A comparative study of Mo, NiMo & CoMo supported on USYzeolite with -Al2O3 also have been presented. in this paper . Keywords :CoMo catalyst, Ultra stableY zeolite, Oxygen Chemisorption and Hydrotreating catalyst. 1. Introduction In petroleum refining, hydrotreating process is playing an important role for removing the Sulfur, Nitrogen, Oxygen compounds ( S.N.O) and metals from petroleum fractions. Due to the environmental restrictions on petroleum product, the sulfur level in diesel is limited to 50 ppm or lower and in addition, for preparing fuel feeds to the fuel cell application required sulfur reduction to 1 ppm. [1-2].Therefore, there is a need of such new generation supports, which have not only higher activity but it should have different activity profiles with respect to different functionalities than the present catalyst.The catalytic activity can to achieved the above said level by several approaches, among which variation of the support is very important[ 3] The -Al2O3 supported CoMo ,NiMo and NiW catalysts have been widely studied for hydrotreating. Many other oxide supports such as TiO2, [4] ZrO2, [5}

SiO2 [6] and mixed oxides such as ZrO2-Al2O3, [7 ] ZrO2-SiO2, [8] and SiO2-Al2O3 [9] have also been used as supports.In several cases it is claimed that higher activities were obtained than those of commercial -Al2O3 supported catalysts, but they could not break into commercial application In recent years, mesoporous materials such as MCM-41[10] and SBA-15 [11] and Zeolites also have been studied with great interest as supports for hydrotreating catalysts In future, the heavier feed stock will be processes. Which contain high refractory of sulfur and nitrogen compound Therefore the attention is shifted to new generation supports such as Y, and USY zeolite These zeolites can be used as support for hydrotreating catalyst. The Mo, NiMo and NiW supports on USY supported catalyst are reported to exhibit superior activities compared to commercial - Al2O3 supported catalyst. In continuation of our work on the effect of the support on catalytic (HDS & HYD) functionalities, we are presenting our results on USY supported molybdenum catalysts with a goal of understanding the origin and variation catalytic functionalities as a function of molybdenum and Co or Ni contents and relating the activities to results on physicochemical characterization of the catalysts 2. Experimental The USY zeolite support was prepared by hydrothermal treat method of NH4Y. The molybdenum content varied from the 2 wt%Mo to 14 wt%Mo on USY support .These Mo catalysts were prepared by incipient wetness impregnation method using appropriate concentrations of ammonium hepta molybdate using USY material as the support. The Co or Ni promoted ( 1 to 5 wt% ) catalysts were also prepared by impregnating the promoter Co or Ni precursor on dried Mo supported catalysts. The impregnated catalysts were dried in air at 100 0C over night and all the catalysts were calcined at 500 0C for 5 h. The calcined catalyst , supported on USY were characterized by XRD by using D/max2500 diffractometer using Cu K radiation and Surface area and Pore size distribution analysis were measured by N2 adsorption at _196 oC using Belsorp Max (Japan).The Temperature Program reduction ( TPR ) was carried out on Micromeritics TPD/TPR2720 instrument.

The low temperature oxygen chemisorption was measured at -78 oC in conventional high static vacuum glass system on catalyst after sulfided at 400oC for 2 hr in the flow of CS2 / H2 mixture at a flow rate of 40 ml/min, according to double isotherm procedure reported by Parekh and Weller [12] for reduced molybdenum catalysts. The catalyst activity for HDS of thiophene and HYD of cyclohexene were carried out at 400 oC on a sulfided catalyst. All the catalysts were sulfided at 400oC for 2.0 hr in flow of CS2/H2 mixture, in a fixed-bed reactor operating at atmospheric pressure and interfaced with a six-way sampling valve for product analysis [13]. First order rates were evaluated according the equation x = r (W/F). where r is rate in moles per hour per gram, x is the fractional conversion, W is the weight of the catalyst in grams, and F is flow rate of the reactant in moles per hour 3.0 Results and Discussion: 3.1 BET Surface area analysis. The BET Surface area of the catalyst was evaluated as a function of Mo loading are present in Table-1 The surface area per gm of supports and per gm of catalyst are almost constant unto 10 wt % Mo .The BET Surface area per gm of catalyst continuously decreasing with increasing Mo loading. The invariance of the BET surface area per gm of support indicates the MOS 2 is the dispersed on monolayer or in very high dispersed state. 3.2 X-ray diffraction (XRD) The X-ray diffraction pattern was used to determine the crystallinity, unit cell size and MoO3 phase .It measurements have confirmed the preservation of the lattice properties The crystallinity and unit cell size decrease as Mo loading on USY zeolite are increase. The USY Supported molybdenum catalysts obtained after calcination have been examined by X-ray diffraction in oxide forms. The X-ray diffraction patterns are shown in Figure 1.

The X-ray diffraction pattern of pure USY-600 is also included in the same figure. It can be seen from the figure that the intensities of the zeolite lines decrease with the addition of Mo content on the zeolite , indicating that the crystallinity of the zeolite is decreasing with increasing Mo loading up to 10% Mo.The crystallinity drops to 35% with the addition of 6 wt % Mo and then changes to a small extent up to 10 wt % Mo, beyond this loading, there is a rapid decrease in crystallinty. The high-intensity lines of MoO3 fall in the same region (2 ) = ( 20- 25) as the strong lines of USY zeolite, therefore, it is difficult to confirm the absence of these phases at lower loading in the oxide state. The MoO3 line seems to be fall from 10 wt% Mo catalyst .The unit cell size is also continuously decreasing as a function of Mo catalyst. The X-ray diffractgram results also confirming that Mo is very well dispersed on the USY support, which is similar to the surface area result. 3.3. Low Temperature Oxygen Chemisorption. The oxygen uptake as a function of Mo loading is also presented in table-1 and figure 4.
Table 1 O2 uptake, Crystallite size, EMSA and Crystallinity as a function of Mo loading supported on USY zeolite. Catalyst BETSurfac BETSurface O2 uptake O/Mo EMSA Surface wt%Mo e area (molg-1 cat ) x100 Coverage Crystallite area(m-2g-1 ) (m-2g-1 ) Per gm (b*) Per gm of (a*) size 0A (c*) of catalyst support (m-2g-1 )

2 4 6 8 10

519 493 480.62 463.96 448.36

529.59 513.78 511.30 504.30 498.18

23.36 34.26 47.29 61.45 77.89

22.4 1 16.4 3 15.1 2 14.9 4 13.7 0

13.23 19.41 26.79 34.82 44.13

2.5 3.78 5.24 6.9 8.86

15.75 21.47 23.33 23.93 23.60

12 248.62 487.07 56.24 8.99 31.87 6.54 39.22 14 409.62 476.30 41.87 5.74 23.72 4.98 61.46 (a*)- EMSA- (Oxygen uptake) x ( O2 uptake/Surface area of pour MoS2 ) (b*)- Surface Coverage- = ( EMSA /Surface area ) x100 (c*)- Crystallite Size= 5x104xmetal/ x M.Where (density of MoS2) =4.8gm/cc and M is the EMSA per gm of MoS2. The oxygen chemisorption increases with Molybdenum loading up to 10%wt and then decreases with further loading. The oxygen chemisorption on sulfides such as MoS 2 and WS2 is well known to present the concentration of anion vacancies. It is noted from the table that the O/Mo is measured of dispersion of MoS 2, remain more or less constant upto 10 wt% and then decrease at higher Mo loading, indecating that MoS 2 is well dispersed upto 10wt%Mo.The equivalent molybdenum surface area is also increased continuously upto 10wt%Mo, further it decrease at higher loading The crystallite size data shows that it is almost constant unto 10wt% Mo loading and further onward is increasing upto 61 A0 at 14 wt% Mo.it indicts that the MoS2 is well dispersed state up to 10% Mo loading further on words decrease the dispersion at high loading. it is due to the crystal growth. The surface coverage by molybdenum increase continuously upto 10wt%Mo, indicating that the total surface is covered by molybdenum only 10%. Such a low surface coverage indicates that USY surface is not fully covered by monolayer of MoS 2 but consists of monolayer patches on the support surface. This result indicates that molybdenum selectively interacts with some portion of USY zeolite support. 3.4 Temperature Program reduction The TPR is a very useful tool for gaining knowledge about the reducibility of various species present in the hydrotreating catalysts. The MoO 3 / USY -zeolite catalysts containing different amounts of molybdenum in the range 6-14wt % Mo are subjected to TPR analysis. . The TPR results of 6 wt% Mo, 10wt%Mo and 14wt%Mo, supported on USY catalysts are shown in Fig 3. All the samples show the typical two peak reduction patterns corresponding to unsupported MoO3 is known to reduce in two steps , MoO3 to MoO2 and MoO2 to Mo [14] . The TPR pattern in figure shows that the first peak in 6 wt % Mo sample shows a single peak at 560 C, with a shoulder on the low-temperature side. The 10 wt % Mo samples show a peak at 580 C and a shoulder on the high-temperature side. While the 14 wt % Mo shows a pattern similar to that of 10% Mo, but the low-temperature peak at 570 C is more intense

It is appear that the high temperature part of TPR spectrum appears slightly hump two peaks, which is appears sharply at 10wt%Mo content. The second peak at higher temperature is increase as Mo content loading. This is may be due to the reduction of tetrahedral, polymolybdate and bulk crystalline MoO3. Thus on the basis of the above discussion, we may assign the peak in the low-temperature region to octahedral species and MoO2 and the high-temperature peak to the reduction of tetrahedral species as well as for reduction of MoO2 to Mo. 4.0 Catalyst activity The Catalytic activities for the two functionalities viz. thiophene hydrodesulfurization and cyclohexene hydrogenation, on sulfided catalysts at 400 oC for 2 hr obtained at 400 oC presented in figure 4 . It can be seen that the two functionalities (HDS &HYD) increase with Mo loading upto 10 wt % Mo and then start decreasing at higher loading. The O 2 uptake is also plotted in the same figure (figure 4 ) and varies in a similar manner to that of the activities. It is interesting to note that oxygen chemisorption and two catalytic functionalities very more or less linearly upto 10wt% molybdenum and then start to decrease. It is indicating that these properties are related to each other. Therefore, the increase and decrease of the oxygen uptake with Mo loading can be related to the
O cat) molh 2 uptake (

are

variation of anion vacancy concentration as a function of Mo loading


Rate ( mol gcat) h x10 Fig 4- Va ra tion of ca ta lytic a ctivity & O 2 upta ke a s a function of Mo conte nt.
-3

80 70 60 50 40 30 20 10 0 2

HDS HYD O2 Up Ta ke

110 100 90 80 70 60 50 40 30 20 10 0 6
W t% Mo

-1

-1

10

12

14

.It is well known that O2 uptake on MoS2 and WS2 catalyst is measured of the number of anion vacancies created is also measure of dispersion of MoS2 on USY zeolite. Therefore, the above observation suggests that the hydrogenation (HYD) and hydrodesulphurization ( HDS) take place on anion vacancies and the oxygen is also known to chemosorb on anion vacancies. 4.1 Promotional Effects. The variation in catalytic activities for HDS , HYD and oxygen uptake of sulfide catalyst as a function of promoter content of Ni & Co are presented in Fig 5.and fig-6 respectively.

-1

Fig- 5 Effect on catalytic activity & O2 uptake as a function of Nickle content 110 120 Rate ( mol h-1 g-1 catalyst ) X10-3

Fig 6- Effect on catalytic activity and O2 Up Take as a function of Cobalt ontent. 100 90 110 100 90 80 70 60 50 1%Co 3%Co Wt% Co 5%Co
-

100 90 80 70 60 1%Ni 3%Ni wt%Ni 5%Ni

110 100 90

-1 O2 uptake ( mol g cat )

80

HDS HYD O2 UpTake

80 70 60

HDS HYD O2 Up Take


70 60 50

It can be seen that the promotion effect is present and maximum at 3 wt % Co or Ni for hydrodesulphurization, hydrogenation activity and oxygen uptake further on words is decrease. The catalytic activity functionality of NiMo/USY and CoMo/USY catalyst are higher than the Mo/USY catalyst. This is due to formation of new active site and some new phase like- Ni-Mo-S and Co-Mo- S. The oxygen uptake of promoter is increased than the unprompted catalyst .It is conformed the increase the dispersion of MoS2 and increase the number of anion vacancies on USY supported catalyst. 5.0 A comparison of NaY and US-Y-zeolite-supported catalysts with - Al2O3 supported catalysts. A catalytic activities supported on NaY and USY zeolite for various functionalities with - Al2O3 and USY-zeolite-supported analogues. Such a comparison is shown in Figure 7. In the same figure, oxygen uptake on the same catalyst is also presented. It has been observed that the HYD activity of 10%Mo/NaY has two times more active and 3%Ni10%Mo/NaY is three times more active than - Al2O3 supported. The HDS activity of 10%Mo/NaY has four times more active and 3%Ni10%Mo/NaY has five times more active than - Al2O3 supported catalysts. It has been observed that the HYD activity of 10%Mo/USY has four times more active and 3%Ni10%Mo/USY is five times more active than - Al2O3 supported. The similar comparison has been observed in the case of hydrodesulphurization of thiophene. The HDS activity of 10%Mo/USY has 5-6 times more active ,while the 3%Ni10%Mo/USY has 7th times more active than the - Al2O3 supported catalysts. The Mo, CoMo, and NiMo catalyst supported on USY-zeolites showed higher activities. This is due to increasing of acid sites of MoS 2, which is also responsible for hydrogenation functionality through electron transfer.

O 2 Up Take ( mol g 1 cat)

Rate ( mol h-1 g-1 catalyst ) X10 -3

90 80

1 20

Rate (mol g ) x10 h

70 60 50

HDS HY D O2 Up Take

1 00

80

60

40 30 20
20 40

10 0
M o/ A l 2O3 N i M o/ A l 2O3 C oM o/ A l 2O3 M o/ Na Y Ni M o/ N aY C oM o/ N aY M o/ USY 3% Ni -10% M o/ USY C oM o/ USY W/ USY N i W/ USY

Support e d Catalys ts

Fig 7- A comparison of - Al2O3 with NaY and Y-Zeolite Supported Catalysts It appears that USY zeolite structure has some unique property to impacts high activities in supported MoS2 phase and its promoter analogous 6. 0- ConclusionThe Ultra stable Y zeolites were prepared by hydrothermal treatment method and have a unit cell size (U.C.S ) of 24.41 0A and crystallinity is 67.70%. The Mo, CoMo, and NiMo catalysts, supported on USY were prepared by incipient-wetness method using the USY zeolite as a support. The BET surface area as a function of the Mo loading, indicating that molybdenum oxide is present as highly dispersed monolayer in the oxide state. The oxygen uptake studies indicated that MOS2 is well dispersed even at higher loading srudied. The NiMo and CoNi catalysts have higher activity then the unprompted catalyst this due some formation of some more new acid site of MoS2 and new phase such as Ni-Mo-S and Co-Mo-S The USY zeolite supported catalyst 10%Mo/USY and 3%Ni10%Mo/USY have shown four and seven times respectively more higher for hydrodesulphurization (HDS) activity than the Al2O3 supported catalyst.. It also has been observed that the HYD activity of 10%Mo/USY has four times more active and 3%Ni10%Mo/USY is five times more active than - Al2O3 supported catalyst References [1] Song, C. Catal. Today 2003, 86, 211. [2] Fuel Processing for Fuel Cell applications, Special Issue of Catal. Today, in Saikatikaneni, A.M. Gaffrey, C. Song (Eds.), Catal. Today 77 (2002 [3] . Murali Dhar, B.N. Srinivas, M.S. Rana, M. Kumar, S.K. Maity, Catal.Today 86 (2003) 45. [4] L.C. Caero, A.R. Romero, J. Ramirez, Catal. Today 78 (14) (2003) 513. [5] M.C. Barrera, M. Viniegra, J. Escobar, M. Vrinat, J.A. de los Reyes, F. Murrieta, J. Garca, Catal. Today 98 (12) (2004) 131. [6 ] G. Murali Dhar, F.E. Massoth, J. Shabtai, J. Catal. 85 (1984) 44. [7] Damyanova, S.; Petrov, L.; Centeno, M. A.; Grange, P. Appl. Catal.,A 2002, 224 (1-2), 271. [8] Rana, M. S.; Srinivas, B. N.; Maity, S. K.; Murali Dhar, G.; Prasada Rao, T. S. R. J. Catal. 2000, 195, 31. [9] Massoth, F. E.; Murali Dhar, G.; Shabtai, J. J. Catal. 1994, 85, 52.

O ( g) mol 2 uptake

-1 -1

-3

-1

[10] Wang, A.; Wang, Y.; Kabe, T.; Chen, Y.; Ishihava, A.; Qian, W.;Yao, P. J. Catal. 2002, 210, 319. [11] Murali Dhar, G.; Muthu Kumaran, G.; Manoj, K.; Rawat, K. S.;Sharma, L. D.; David Raju, B.; Rama Rao, K. S. Catal. Today 2005, 99,309. (32) Parekh, B. S.; Weller, S. W. J. Catal. 1977, 47, 100 [12] Parekh, B. S.; Weller, S. W. J. Catal. 1977, 47, 100. [13] Wang, A.;Wang, Y.; Kabe, T.; Chen, Y;Ishihava,A.; Qian, W.;. J. Catal. 2002, 210, 19. [14] Arnoldy, P.; de Jonge, J. C. M.; Moulijin, J. A. J. Phys. Chem. 1985, 89, 4517.