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PERFORMANCE STUDY OF CERTAIN COMMERCIAL CATALYSTS IN HYDRODESULFURIZATION OF DIESEL OILS

V. Ramesh Kumar , K. S. Balaraman , V. S. Ramachandra Rao & M. S. Ananth
a b a b c c

University College of Technology, Osmania University, Hyderabad, 500 007, India

Research and Development Centre, Madras Refineries Limited, Manali, Chennai, 600 068, India
c

Department of Chemical Engineering, Indian Institute of Technology, Madras, Chennai, 600 036, India Version of record first published: 14 Feb 2007.

To cite this article: V. Ramesh Kumar , K. S. Balaraman , V. S. Ramachandra Rao & M. S. Ananth (2001): PERFORMANCE STUDY OF CERTAIN COMMERCIAL CATALYSTS IN HYDRODESULFURIZATION OF DIESEL OILS, Petroleum Science and Technology, 19:9-10, 1029-1038 To link to this article: http://dx.doi.org/10.1081/LFT-100108292

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PETROLEUM SCIENCE AND TECHNOLOGY, 19(9&10), 10291038 (2001)

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PERFORMANCE STUDY OF CERTAIN COMMERCIAL CATALYSTS IN HYDRODESULFURIZATION OF DIESEL OILS

V. Ramesh Kumar,1,* K. S. Balaraman,2 V. S. Ramachandra Rao,1 and M. S. Ananth1 Department of Chemical Engineering, Indian Institute of Technology, Madras, Chennai 600 036, India 2 Research and Development Centre, Madras Reneries Limited, Manali, Chennai 600 068, India
1

ABSTRACT Hydrodesulfurization experiments have been carried out in a cocurrent down-ow trickle-bed reactor over two commercially available high activity Co-Mo/Al2O3 catalysts (A & B) using diesel oil as feed stock. Similar drying and presulding procedures are followed for both the catalysts. The eciency of these catalysts is evaluated based on catalyst activity and compared at typical operating conditions. It is found that the catalyst-A exhibits higher activity than the catalyst-B.

*Corresponding author. Current address: University College of Technology, Osmania University, Hyderabad 500 007, India. 1029
Copyright & 2001 by Marcel Dekker, Inc. www.dekker.com

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INTRODUCTION Catalytic hydrodesulfurization is widely used in petroleum reneries to reduce sulfur content from the feedstocks. Because of stringent environmental regulations and demand for high quality products, this process is gaining signicant attention throughout the world. Trickle-bed reactors are usually employed for carrying out hydrodesulfurization reactions. These reactors are often preferred because of their simple and stable mode of operation, ease of control and exibility of application to a wide range of feedstocks. It is common practice to test the catalysts and evaluate process conditions through laboratory experiments. These experiments help in understanding the catalyst eciency and chemical kinetics and enable us in predicting the behaviour of industrial reactor. The problems associated with laboratory reactors, for example, axial dispersion and partial wetting are discussed by de Bruijn, 1976; Van Klinken and Van Dongen, 1980; Carruthers and Dicamillo, 1988; Sie, 1991; Tsamatsoulis and Papayannakos, 1994. Laboratory as well as pilot scale trickle-bed reactors deviate from plug ow due to axial dispersion, channeling eects and poor catalyst wetting. Several authors (Mears, 1971; Doraiswamy and Tajbl, 1974; Sattereld, 1975) have proposed dierent criteria, in order to ensure the kinetic data free from transport, channeling and wall eects. Mears criterion (Mears, 1971) is useful in determining the axial dispersion or back mixing. If the L/dp (L is the length of the reactor and dp is the diameter of the particle) ratio is greater than 350, axial dispersion or back mixing is minimum. Doraiswamy and Tajbl (1974) suggested that if the radial aspect ratio dt/dp (dt is the diameter of the reactor tube and dp is the particle diameter) is greater than 4, it can be assumed that the liquid distribution is good enough and there is no adverse channeling and heat transfer eects at the reactor wall. Incomplete wetting of the catalyst bed prevails in the operation of laboratory trickle-bed reactors. By diluting the catalyst bed with an equal volume of inert material, the wetting eciency can be increased. The inert nes dispersed among the catalyst particles provide more solidsolid contact points and areas over which the liquid ows (Aldahhan et al, 1995). Several types of sulfur compounds are present in diesel fuels: mercaptants R-SH, suldes R-S-R0 , disuldes R-S-S-R0 , polysuldes R-Sn-R0 , thiophene, benzothiophene (BT), dibenzothiophene (DBT) and their alkyl derivatives. The specication on diesel fuel for both technical and environmental reasons are getting more stringent. For example, the sulfur specications for diesel fuel in the USA were reduced from 2000 ppm to 500 ppm by the Clean Air Act (CAA) as of October 1, 1993. Canada is adopting the same US regulations and the European countries are limiting the sulfur level

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in diesel fuel to 500 ppm (maximum) by 1996 inline with EC directives (Qabazard et al, 1995). In Japan, the maximum permissible level of 0.05 wt% S is implemented from 1997. The Bureau of Indian Standards (BIS) proposes to reduce the sulfur content to 0.20 to 0.25 wt% by 2000 AD. The selection of active catalyst plays important role in sulfur removal operation. The role of the hydrodesulfurization catalyst is to activate C-S bond on the sulfur compounds and to hydrogenate the hydrocarbons, from which sulfur has been removed. In general Co-Mo catalysts have higher desulfurization activity. In this study, the main objective is to evaluate the eciency of certain commercial catalysts and compare.

EXPERIMENTAL The ow diagram of the experimental unit used for the investigations is shown in Figure 1. The unit consists of a cocurrent down-ow xed bed reactor of internal dia 28 mm and length of 830 mm. The reactor is heated by 4 heating shells. Each shell is controlled independently by temperature controllers to maintain essentially isothermal conditions within the reactor. A 150 ml sample of catalyst diluted with an equal amount of inerts (carborundum particles 2 mm size) is loaded inside the reactor. The entrance and exit eects are avoided using small inert beds at both the ends of the catalyst bed. The properties of the diesel fuel used in the investigation is presented in Table 1 and properties of the commercial catalysts are given in Table 2. The catalysts are manufactured in the oxide form. Prior to use they are sulded in reducing environment. Presulng is carried out to obtain high and stable activity, when the catalyst is loaded in the reactor. The details of sulding procedure carried out are given in the Appendix. The hydrodesulfurization reactions are carried out under steady-state operation at 3.0, 3.6, 4.2 and 4.8 MPa. Temperatures of 593, 613 and 633 K, hydrogen to oil ratio of 200 vol/vol abd 3.24 LHSVs are made use of. The following sets of experimental data are obtained using both the catalysts separately. (i) The reaction temperature is varied at constant pressure (3.6 MPa) and constant LHSVs (3.2 and 4 1/h) (ii) The total pressure is varied at constant temperature (633 K) and constant LHSVs (3 and 4 1/h). The H2/oil ratio is maintained constant in all the experimental runs.

KINETICS The interpretation of kinetic results of hydrotreating reactions in trickle-bed reactors is a dicult task due to various complexities. The

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Figure 1.

Flow diagram of experimental setup.

Table 1. Density Aniline point Viscosity at 40 C (Cst) Pour point ( C) Sulfur (wt%) Simulated distillation IBP 10 wt% 30 wt% 50 wt% 70 wt% 90 wt%

Properties of the Feedstock ASTM ASTM ASTM ASTM Antek ASTM D-1298 D-611 D-445 D-97 D-2887 205 270 288 304 329 347 0.8548 76.0 5.12 3 1.65

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HYDRODESULFURIZATION OF DIESEL OILS Table 2. Catalyst Chemical properties: (wt% dry basis) CoO MoO3 Alumina Physical properties: Shape Size, mm Bulk density, kg/m3 Avg. Crush strength, kg/mm Surface area, m2/gm Pore volume, ml/gm Typical Catalyst Properties A B

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110 < 25 Balance Quadralobe extrudates 1.6 550900 3.2 237 0.43

34 10.2 Balance Quadralobe extrudates 1.6 690 1.1 224 0.56

models reported earlier are generally based on several assumptions. The models assume plug-ow pattern and isothermality of bed. The chemical complexity of the reaction has been empirically taken into account by assuming nonlinear kinetic laws of the power law form. The rate of reaction including temperature and pressure terms is expressed as dC ko expE =RT Pm Cn dt 1

Since several compounds with dierent chemical structures and molecular weights react simultaneously with dierent rates, the apparent reaction resulting from several parallel reactions may behave like nth order reaction, with n >1. Therefore for a given reaction the outlet concentration is calculated using Eq. (1) at dierent values of n between 1 and 2 and m between 0 and 1. For each value of n and m Arrhenius rate constant and activation energy are determined using exponential regression analysis. From this procedure the best values of n and m corresponding kinetic parameters are arrived at. COMPARISON OF PERFORMANCE OF COMMERCIAL CATALYSTS Catalysts are generally compared with respect to activity, selectivity, life, mechanical properties and costs. The commonly used measures of activity are (i) temperature required for a specied conversion (ii) conversion

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achieved at desired temperatures (iii) space velocities required for a given conversion at given temperature and (iv) overall reaction rate at given conditions. In the present study, the catalysts comparison is made based on catalyst activity using procedure (iv) assuming the ratio of catalyst activities equal to the ratio of observed rates.

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Activity Calculation The activities of the catalysts are expressed in terms of reaction rates using experimentally evaluated reaction kinetics. The relative activities (RA) are calculated from the reaction rates of the sample and the standard catalyst using the following equations:   LHSV 1 1 1 k 2 n1 n 1 n 1 Pm Csf Csi RAsample ksample RAstandard kstandard 3

where k is the reaction rate constant, LHSV is liquid hourly space velocity, P is reaction pressure, Csi is sulfur content in the product and Csf is the sulfur content in feed.

RESULTS AND DISCUSSION Using Mears criterion (Mears, 1971), the L/dp ratio is calculated for both the commercial catalysts and found to be greater than 350. It shows that there is no signicant axial dispersion or back mixing. The radial aspect ratio calculated shows that the liquid distribution is good and there is no adverse channeling eects. It is found that 1.3 order dependence with respect to sulfur content at m 0.8 gave the best t data for catalyst-A. The reaction orders m and n are found as 1.0 and 1.4 for catalyst-B. The kinetic results for catalyst-A and catalyst-B are presented in Table 3. The experimental and calculated results are shown in Figures 2 and 3. The catalyst B is considered as the standard catalyst with a Relative Activity (RA) of 100. The hydrodesulfurization rate of each catalyst at 613 K is used in the above equation to calculate RA. The results indicate that the catalyst A shows 1.25 times higher activity than catalyst B. A possible explanation for the superior performance of catalyst A is due to its high molybdenum content. The catalyst activity is due to presence of MoO4 molecules, which have the property of combining in pairs.

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HYDRODESULFURIZATION OF DIESEL OILS Table 3. M Catalyst-A HDS Catalyst-B HDS 0.8 1.0 Kinetic Results n 1.3 1.4 K 1.40E05 5.071E06

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E 12104.67 16808.20

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Figure 2. Performance of Catalyst-A for sulfur removal. Comparison between experimental and calculated values (m 0.8; n 1.3).

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Figure 3. Performance of Catalyst-B for sulfur removal. Comparison between experimental and calculated values (m 1.0; n 1.4).

In reducing atmosphere, two oxygen atoms are readily reduced by hydrogen and split o, forming lattice defects which become active sites. The number of active sites per unit surface of the catalyst can increase with increasing Mo and Co loading (Qabazard et al., 1995). Thus the catalyst with high molybdenum content can exhibit higher activity.

CONCLUSIONS The hydrotreatment of diesel oil is investigated over two commercially available catalysts (A and B) in a trickle-bed reactor at temperatures

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593633 K, pressures 34.8 MPa and 3.24 LHSVs. The kinetic parameters are evaluated for both the catalysts using power law approach. The catalysts are compared in terms of their hydrodesulfurization activity. Catalyst-A is found to be superior to catalyst-B.

APPENDIX

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The sulding is done with 11.47 gms of DMDS per litre of kerosine. Initially the catalyst bed is purged with 50 litre/h of N2 for 2 h at atmospheric pressure and temperature. The temperature is increased to 643 K at the rate of 50 K/h and maintained for 6 h. Then the temperature is gradually reduced to 373K. At 373 K the reactor pressure is raised to 10 kg/cm2 at a H2 ow rate of 50 litre/h. Kerosine with DMDS at a rate of 250 ml/h is introduced and maintained for 4 h. Then the following temperature programming is maintained. The temperature is increased to 433 K at a rate of 50 K/h and kept for 16 h; thereafter the temperature is increased to 477 K at a rate of 50 K/h and retained for 16 h and then increased to 533 K at the same rate and maintained for 16 h; the temperature is again increased to 589 K at a rate of 50 K/h and held for 16 h.

ACKNOWLEDGMENTS One of the authors (VRK) is grateful to Madras Reneries Limited, Manali, Chennai-600 068, India for nancial support.

REFERENCES Aldahhan, M.H., Wu, Y. and Dudukovic, M.P. 1995. Ind. Eng. Chem. Res. 34: 741. Caruthers, J.C. and Dicamillo, D.J. 1988. Appl. Catal. 43: 253. Doraiswamy, L.K. and Tajbl, D.G. 1974. Catal. Rev. Sci. Eng. 10: 177. De Bruijn, A. 1976. Testing of HDS Catalysts in Small Trickle Phase Reactors. 6th International Congress on Catalysis., London, UK, paper B34. Mears, D.E. 1971. The Role of Axial Dispersion in Trickle-Flow Laboratory Reactors. Chem. Eng. Sci. 26: 1361. Qabazard, H., Abu-Seedo, F., Stanislaus, A., Andari, M. and Absi-Halabi, M. 1995. Fuel Sci. & Tech. Intl. 13(9): 1135.

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Sattereld, C.N. 1975. A.I.Ch.E. 21(2): 209. Sie, S.T. 1991. Revue de Institut Francais du Petrole. 45: 501. Tsamatsoulis, D. and Papayannakos, N. 1994. Chem. Eng. Sci. 49: 523. Van Klinken, J. and Van Dongen, R.H. 1980. Chem. Eng. Sci. 35: 59. Received June 15, 2000 Accepted May 7, 2001

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