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Petroleum Science and Technology
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Catalytic Dewaxing for Lube Oil Production
a

b

M. F. Menoufy , A. E. Nadia & H. S. Ahmed
a

a

Refining Division , Egyptian Petroleum Research Institute , Nasr City, Cairo, Egypt

b

Petroleum Refining Engineering Department, Faculty of Petroleum and Mining Engineering ,
Suez Canal University ,
Published online: 11 Mar 2009.

To cite this article: M. F. Menoufy , A. E. Nadia & H. S. Ahmed (2009) Catalytic Dewaxing for Lube Oil Production, Petroleum
Science and Technology, 27:6, 568-574, DOI: 10.1080/10916460802104172
To link to this article: http://dx.doi.org/10.1080/10916460802104172

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3  5. F. 27:568–574.2 and H. An increase in temperature (between 290ıC and 375ıC) increased wax conversion (percent dewaxing) on H-ZSM-5 compared with NiMo-Hmordenite catalysts due to its higher cracking activity. and the rate of normal paraffin cracking was increased due to the hydrogenolysis activity of the active metals.5  7. The reduction in dewaxed pour points (pp) was observed to be in the range of 38ı C–42ıC over H-ZSM-5. Egypt Refining Engineering Department. In other words. Nasr City. LLC ISSN: 1091-6466 print/1532-2459 online DOI: 10. high concentrations of aromatics were obtained on both catalysts.6 Å for ZSM-5). S.. and operating reactor temperatures (290ıC–475ıC) can have a great effect on cracking high pour point n-paraffins into lower ones. Refining Division. Ahmed El-Zomor St. since the waxy paraffins are converted to lower boiling products.5ıC). These results may be attributed to shape-selective discriminating behavior due to differences in zeolite pore openings (i. The influences of process parameters (temperature. Suez Canal University Downloaded by [Kungliga Tekniska Hogskola] at 16:06 16 December 2014 2 Petroleum Abstract: The selective cracking of long-chain normal paraffin’s of medium neutral raffinate. Egypt. The influences of zeolite types.0 Å for mordenite and 5. derived from a lube oil-phenol extraction unit. 2009 Copyright © Taylor & Francis Group.net. Faculty of Petroleum and Mining Engineering. and liquid hourly space velocity [LHSV]) on the relations between wax conversion to maintain maximum low pour points and maximum dewaxed oil yields or minimum yields of the least desired gases were optimized to produce dewaxed lube oils of acceptable characteristics.e. by the catalytic dewaxing technique over H-ZSM-5 and NiMo-H-mordenite catalysts was studied. and hence a reduction in pour points. On the other hand.1 A. The runs were conducted to produce lube oils with acceptable cold flow properties.Petroleum Science and Technology. mohammedfathyh@yahoo. 6. metals loading. Egyptian Petroleum Research Institute.1080/10916460802104172 Catalytic Dewaxing for Lube Oil Production M.. compared to 37ıC–40ıC over NiMo-H-mordenite at the same reaction temperature ranges (290ı C–375ıC). The addition of bimetallic components to the mordenite-catalyst enhances its activity.com 568 . Cairo. Cairo. E. The low pour point lube oils produced from catalytic dewaxing over H-ZSM-5 compared with NiMo-H-mordenite catalyst indicates that the former was more selective for removing wax components than the later. a combination of isomerization and selective cracking reactions of high nparaffins may occur during the dewaxing process using NiMo-H-mordenite catalyst. Menoufy. As a result. Address correspondence to Mohammed F Menoufy. pressure. Nasr City 11727. Nadia. This means that the bimetallic H-mordenite catalyst has the advantage over H-ZSM-5 in its refining activities (hydrodesulfurization [HDS] and hydrodenitrogenation [HDN]) under the tested operating conditions. but NiMo-H-mordenite has advantages at higher temperature ranges (above 375ıC) in pour point reduction (pp range: 41ı C–42. E-mail: Mohammed2002@link. Egyptian Petroleum Research Institute. Ahmed1 1 Refining Division. large amounts of C1 -C4 gases and C5 -170ıC naphtha were produced.

. raffinates Downloaded by [Kungliga Tekniska Hogskola] at 16:06 16 December 2014 INTRODUCTION Lubricating oil base stock is manufactured from heavy petroleum fractions through a number of steps. METHODS Two types of commercial zeolites—ZSM-5 and Na-mordenite—were used in the study. catalytic dewaxing developed by Mobil/Exxon Mobil. Chitnis et al. 1996. and produce lower pour point products than solvent dewaxing. and space velocities. This process is energy intensive. and improves their life (Sivasanker et al. 1994. Robert and Randall. and Mo) to zeolites enhances the activity. Recently. NiMo catalyst. in which the wax molecules are selectively cracked over shape-selective zeolite (ZSM-5. 2003). Mordenite.Catalytic Dewaxing for Lube Oil Production 569 Keywords: catalytic dewaxing. Recent catalytic dewaxing processes commercialized in the 1990s combine wax cracking and wax isomerization (Miller. and there is a loss of lube oil due to entrapment of oil by the wax (Sivasanker et al. 2001. Pd. 1997. H-ZSM-5. flow properties at low temperatures) have a significant impact on the end-use performance of finished lubricants (Himmat.g. The hydrocarbon components (wax/long-chain paraffins. and aromatics) that are not suitable for lube oil base stocks are removed by solvent refining/hydroprocessing or dewaxing to decrease the pour point. Thomas and David.. The catalytic dewaxing processes operate at moderate temperatures. Stephen and Russell. isomerization. pour point. The oldest dewaxing process is solvent extraction and separation of the crystallized wax. pressures. such as fractional distillation. Chevron.. The ZSM-5 sample was tested without metal loading. BP. They differ in molecular composition and physicochemical properties due to changes in crude source and the processing steps used in their manufacture. heterocyclics. from light viscosity through bright stock. A series of tests were previously performed in order to optimize the dewaxing process conditions. we investigated the use of medium and large pore size zeolites for improving the paraffinic medium neutral raffinate feed stock via catalytic dewaxing using inexpensive metal combinations for low pour point and higher viscosity index lube oil production. hydrodenitrogenation. and Akzo-Nobel. due to the bifunctional characters. paraffins. etc. 1996). The processes are applicable to the entire range of lube oil base stocks. These differences in composition/properties (e. Theo and Wilfried. Ni. As the reaction is carried out in presence of hydrogen. mordenite. but the .. has become popular. Sivasanker. the addition of metallic components (Pt. In this work. and can tolerate sulfur and nitrogen species. 2005). 1994.) catalysts. hydrodesulfurization. 2003). 2002.

The feedstock used in the dewaxing process was medium neutral raffinate. Liquid and volatile samples were separated and collected from the highpressure separator for analysis in order to complete the mass balance. F.5N NH4 Cl. and the liquid dewaxed samples were analyzed according to ASTM standard procedures. derived from a lube oil-phenol extraction unit (Alexandria Petroleum Co. ppm Viscosity index (VI) Composition. Alexandria.1 hr 1 . wt% Total paraffins Naphthenes Total aromatics 0. After each loading. RESULTS AND DISCUSSION Effect of Process Temperatures Tables 2 and 3 indicate that an increase in reaction temperature increases the conversion of the waxy molecules and lowers the pour point of the dewaxed oil (DWO).6 22. The reduction in pour point (pp) is the difference between the pour point of the feed and dewaxed product. Usually 100 mL of either ZSM-5 or NiMo-H-mordenite catalyst was used and feedstock was pumped to the reactor. respectively.e. hydrogen pressure 30 bar. with the characteristics indicated in Table 1. mixed with hydrogen under the tested operating conditions (i. and hydrogen-to-feed ratio 200 L/L). As the process is based on selective cracking of n-paraffin ..570 M. dried at 110ıC.. The finished catalyst contained 1 wt% NiO and 4 wt% MoO3 . and loaded by the successive impregnation method of the determined concentration of nickel and molybdenum salt solutions. The catalyst was presulfiding in situ before catalytic dewaxing operating runs. ı C Sulfur content. temperature range 290ıC– 475ı C.2 Na-mordenite was transformed to the H-form by cation exchange with 0.2 31.82 143 116 46. Characteristics of the feedstock Specific gravity at 60ıF Pour point. Menoufy et al. The dewaxing reactions were carried out in a continuance fixed-bed catatest unit. Egypt). Downloaded by [Kungliga Tekniska Hogskola] at 16:06 16 December 2014 Table 1.8977 36 0. Volatile samples were analyzed on a Perkin-Elmer gas chromatograph (model 910) using 20% squalane on chromosorb-W. wt% Nitrogen content. drying and calcinations were carried out at 110ıC and 510ı C overnight and for 3 hr. LHSV 2.

3 61.5 0.9 90.7 2.6 57 60.5 42.6 4.4 93 22.0 41.5 43. wt% Total aromatics.6 121 15.2 H2 pressure.1 85 14.64 21.0 46.0 0.1 hr 1.0 58.0 37.6 80. ı C Dewaxed lube oil yield.5 40.0 41. wt% HDS.0 43.7 84.0 41. % Viscosity index (VI) Total paraffins.5 23.1 8.1 92 18.5 3.1 70 51.4 62 56.8 6.9 77. wt% Naphthenes.8 39.5 9.0 42.5 1. 200 L/L. 200 L/L. % Nitrogen content.0 10.0 0. wt% Dewaxing.6 5.1 hr 1.15 81. ı C pp. wt% Light naphtha. wt% Naphthenes.8 7.6 4.76 7.4 49. % Viscosity index (VI) Total paraffins.0 98 23.9 110 23. Effect of reactor temperatures on catalytic dewaxing with NiMo-H-mordenite catalyst Reactor temperature.9 6.6 46.0 0.72 12.1 116 18.0 13.13 84. % Nitrogen content.0 H2 pressure.0 44.7 37.9 94.8 81.7 96 24.0 0.0 46. LHSV.5 37.0 38 0. wt% HDS. wt% 325 350 375 400 425 475 92.6 57.0 40.0 39.0 0.0 0.0 36.8 101 25. H2 /feed ratio. ı C Dewaxed lube oil yield.17 79.0 0.0 39.0 46.68 17.2 37.6 83.5 0.0 42.2 95 20. LHSV.Catalytic Dewaxing for Lube Oil Production 571 Table 2.8 65. ı C Sulfur content.9 4.6 5.2 70. Table 3. wt% Total aromatics. ppm HDN.1 5.7 37.0 12.2 8.2 126 11.0 15.0 59. wt% Gases (C1 -C4 ).4 6.2 6.3 132 7.0 0.0 50.1 36.3 36. 2.6 87.8 89 37. . ppm HDN.1 36.9 5.3 9.6 3.19 76.4 7. 30 bar.4 86.7 6.3 83 42.8 76.9 39.0 5.6 1.4 8. wt% Dewaxing.4 36. wt% Dewaxed lube oil properties Pour point.5 41.0 42. 30 bar. ı C Sulfur content. wt% Gases (C1 -C4 ).1 91 19. wt% Light naphtha.2 7.0 43.4 3. 2. Effect of reactor temperatures on catalytic dewaxing with ZSM-5 catalyst Downloaded by [Kungliga Tekniska Hogskola] at 16:06 16 December 2014 Reactor temperature. wt% Dewaxed lube oil properties Pour point.9 92 19.7 77 46. ı C pp.0 7.6 6.6 90 16.0 42. H2 /feed ratio.12 85.4 35.70 14.7 52. wt% 290 325 350 375 400 92.11 86.

Therefore the medium pore size (10 MR) zeolite appeared to be particularly suitable for selectively hydrocracking the n-paraffins (wax molecules) to lighter products. It was converted from the sodium form. The n-paraffin removal mostly contributes to pour point reduction and cracking of the paraffinic side chains in polycondensed molecules of the feedstock. into the active acidic form.Downloaded by [Kungliga Tekniska Hogskola] at 16:06 16 December 2014 572 M. The difference was due to their difference in pore size member ring opening (MR) (i. This means that the slightly smaller pore size zeolite. . Material balance data on catalytic dewaxing of the paraffinic feedstock and its product show that during hydrocracking some naphthenes and aromatics are converted into lower boiling products. The addition of metallic components. the greater the selective removal of the waxy n-paraffins (Tables 2 and 3). which led to a reduction in the pour point of dewaxed oil. leading to a lower VI and dewaxed lube oil yields.e. molecules present in the medium neutral raffinate. the acidic ZSM-5.5ı C) above 400ıC. deactivates rapidly. 10 MR and 12 MR for ZSM-5 and H-mordenite. which has a one-dimensional pore system. Menoufy et al. This difference was attributed to the bifunctional characteristics of the additional metal sites. The viscosity index (VI) of the dewaxed oil was also improved by mordenite catalyst compared to ZSM-5 (Tables 2 and 3). compared to 37ı C–40ıC for NiMo-H-mordenite in the same temperature range of 290ıC–375ıC. The hydrogenation function was normally incorporated to improve catalyst stability. The lower the pour point. Therefore the product qualities of the dewaxed lube oil (Tables 2 and 3). F. Effect of Metals Addition on Dewaxing Catalyst Mordenite. such as HDS and HDN. enhances its activity and reduces the deactivation rate. The reduction in dewaxed pour point (pp) was in the range of 38ı C–42ıC for ZSM-5. such as Mo or Ni instead of expensive Pt metal. by ion exchange. but also an adjustment in the Si/Al ratio.. due to the destruction of naphthenic components by ZSM-5. produce higher wax removal (percent dewaxing) than the mordenite catalyst in the temperature range 290ıC–375ıC. as in case of ZSM-5. the selectivity for producing DWO was observed to be more selective on ZSM-5 than NiMo-Hmordenite at the operating temperatures. but above 375ıC the larger pore size mordenite catalyst was more selective for wax removal. respectively) and the Si/Al ratio. The mordenite catalyst was observed to have a higher pp (42ıC–42. were enhanced more with NiMo-H-mordenite catalyst than ZSM-5. The added Ni and Mo metals impart bifunctional characteristics to mordenite and enhance the selective cracking rate of the paraffinic feedstock. The shape selectivity properties of zeolites are reported in terms of pour points of the products. which involves not only ion exchange of Na to H.

wt% ZSM-5 NiMo-H-mordenite 315 30 1. ı C pp. wt% Pour point. . % Nitrogen content. wt% Gases (C1 -C4 ). CONCLUSIONS The data obtained demonstrate the flexibility of producing dewaxed lube oil in good yield by combining catalytic dewaxing over the large-pore H-mordenite containing Ni and Mo metals as selective catalytic dewaxing catalyst with higher hydrogenation activity than the medium pore zeolite ZSM-5. The optimization condition revealed that the produced dewaxed lube oil may have better characteristics if an additional hydrogenation step or catalyst combined design is considered.69 15. bar LHSV. but the viscosity index of the produced oil differs (92 and 95.11 86.5 325 30 1. ı C Sulfur content.9 142 0.6 88 38.5 Process Optimization for Lube Oil Production Optimization of dewaxing raffinate feedstock operating conditions in order to obtain lube oil with a pour point of 7ıC are shown in Table 4. respectively). ppm HDN. hr 1 H2 /feed ratio. The reduction in pour point (pp) were reached at 43ıC for both H-ZSM-5 or NiMo-Hmordenite. wt% Light naphtha. Higher HDS and HDN activities were obtained with mordenite catalyst compared with ZSM-5 catalyst.2 200 85 8 7 7 43 0. Optimization conditions for dewaxed lube oil with a 7ı C pour point Downloaded by [Kungliga Tekniska Hogskola] at 16:06 16 December 2014 Catalyst Reaction temperature.Catalytic Dewaxing for Lube Oil Production 573 Table 4. The study showed that the production of lube oils characterized by low pour points and higher VI was feasible via shape-selective cracking of higher paraffinic distillates using loaded zeolites by Ni and Mo oxides rather than the expensive Pt metal.5 200 83 11 6 7 43 0. These results are confirmed with the Egyptian base lube oil specifications. wt% HDS.7 17 63. ı C Hydrogen pressure. % Total paraffins Dewaxing. L/L Dewaxed lube oil yield.5 17 63.

February 26–27. (2005). J.. J. D. (2002).. W. Novak.. A Gen.. Weinheim: Wiley VCH. J. Downloaded by [Kungliga Tekniska Hogskola] at 16:06 16 December 2014 REFERENCES Chitnis. Production of high quality lubricant bright stock. High quality lubricants through advanced technologies. F. Nagel. S. Helton. K. K. Lubricants and lubrication. S. 119:121–138. Macris. P. S. T. (1994). Hydrocarbon Asia 29:40–46. and Tracy. and Wilfried.S.. A Gen. J. V. F.. Thomas. S. . G. U. Theo. Miller. Catal. U. and Randall. (1994). Himmat. (2001). S. Catal.574 M. Design catalyst and process for the dewaxing of petroleum oils. T. M.. Proceedings of the 3rd European Catalyst Technology Conference. Design of catalysts for pour-point reduction of lube oil fractions. and David. Menoufy et al. A. Catalytic dewaxing of lube base stock raffinates in contact with pour point depressants. Soc. A Chem. The Netherland.. 2:439–449. M. Bull.S. and U. and Russell. (2003). W. A. Amsterdam. J. Sivasanker. India 2:100–106. Micropor.. Innovative solutions for production of low sulfur distillates using selective dewaxing and advanced hydrotreating catalyst. R. New molecular sieve process for lube dewaxing by wax isomerization. Selective hydroisomerization of long chain normal paraffins. Patent 5603822. 138:369–379. 47–53. (1997). E. Robert. J. Pappal. Appl. 125:159.. P. Stephen. Appl. and Ratnasamy. (2003). (1996). A. Mater.. Catal. Ramaswamy. pp. H. March 3. Mol.. Patent 208058000. D. R. Sivasanker. Catal.