Design of catalysts for pour .... by S.

Sivasanker Bulletin of the Catalysis Society of India 2 (2003) 100-106

Design of catalysts for pour-point reduction of lube oil fractions S. Sivasanker National Chemical laboratory, Pune - 411 008.

Abstract The discovery of new micro-porous materials has resulted in interesting applications in petroleum refining in recent times. An example is the use of molecular sieve based catalysts for pour-point (pp) reduction of petroleum oils used for lubricating oil production. Two different catalytic processes are available for the reduction of pp of petroleum oils. These are based on shape selective cracking of the n-paraffins and wax-isomerization. The requirements of the micro-porous materials for the two catalysts are different; these are discussed. The optimization of the catalyst parameters to design good catalysts for the two processes is described. Keywords: Dewaxing; shape-selective cracking; wax isomerization; lube oil base stocks; petroleum refining; zeolites ___________________________________________________________________________ solvent by distillation. The overall process 1. Introduction is energy intensive, besides loss of LOBS can occur due to entrapment of oil by the Lubricating oil base stocks (LOBS) wax. are manufactured from heavy petroleum In recent times, catalytic dewaxing (atmospheric and vacuum gas oil) fractions developed by Mobil (and BP) in which the through a number of steps. First of all, the wax molecules are selectively cracked over fraction that is suitable for producing the shape selective zeolite catalysts has become desired lube oil with the required viscosity popular. The Mobil process [2] is popular is cut through fractional distillation. The due to higher yields and wider range of various hydrocarbon components present in feeds that can be handled. In catalytic these fractions and their properties are dewaxing, the long chain alkanes (waxes presented in Table 1 [1]. The hydrocarbon possessing high melting points), which are components (aromatics, heterocyclics and narrow molecules (4.1 dia), are selectivity waxes - long chain alkanes) that are not cracked inside the pores (~5.5 dia) of suitable for LOBS manufacture are removed ZSM-5; the larger branched alkanes (which from the lube cuts by 1) dearomatization to possess lower pour points) and the remove aromatics and most of the N and S naphthenic molecules (which posses good compounds, 2) dewaxing to decrease the lubricity) are not cracked. As oil loss due to pour point and 3) hydrofinishing to improve entrapment in wax is not possible, the stability and colour. The dearomatization is LOBS yields are larger. Also, due to the usually done by extraction with a solvent near total removal of the waxes, lower pour such as N-methyl 2-pyrrolidone (or oils can be obtained (compared to solvent sometimes by deep hydrogenation). dewaxing). Other advantages of catalytic The oldest dewaxing process is dewaxing are lower investment and solvent extraction, which consists of operational costs. However, catalytically dissolving the oil in a solvent and the dewaxed oil is often slightly lower in VI subsequent cooling of the solution to than the solvent dewaxed oil. crystallize the wax which is separated by filtration. The oil is recovered from the

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Design of catalysts for pour .... by S. Sivasanker Bulletin of the Catalysis Society of India 2 (2003) 100-106

The major limitation of the solvent and catalytic (shape-selective) dewaxing processes is the loss of yield due to the removal of the wax molecules. Chervon has commercialized a dewaxing process called isodewaxing in which the wax molecules are isomerized into low pour iso-paraffins without cracking them [3]. A typical example of how the melting point of a long chain paraffin (wax) decreases dramatically

on isomerization is shown in Table 2. It is also seen from the table that the VI decrease is not as marked [4]. The benefits of this process are higher LOBS yields, lower pour points than possible in solvent dewaxing and higher VI of the product. This process uses Pt/SAPO-11 as the catalyst [3] and is suitable for feeds low in S and N such as hydrocracked oils and hydrogen refined oils and waxes.

Table 1. Properties of lube base oil components [1] Compound Viscosity Viscosity Pour Point type Index (VI) n-paraffins Low High High (wax) Iso-paraffins Medium High/ Medium Medium Alicyclics High Low Medium/ low (naphthenes) Aromatics High Low Low

Stability High Medium Medium/ low Low

Value as lube component Very low High/ Medium Low/ medium Very low

Table 2. Isomerization of a long chain hydrocarbon (wax) decreases its melting point [4]. Formula Structure Melting point (K) Viscosity Index n-C26H54 Long chain, no branching +331 ~150 C26H54 C10-C-C10 +292 125 [C-C-C-C-C] C26H54 C10-C -C10 [C2-C-C2] -233 119

Table 3. Comparison of dewaxing processes . Solvent Catalytic dewaxing Wax removal Physical Shape selective cracking of wax Min. P.P. of DWO (K) 258 223 VI of DWO Base Lower than base DWO yield Base Generally about same Main byproducts Wax Gas, naphtha

Isodewaxing Wax isomerization 223 Higher than base Generally higher Mostly middle distillates

Table 4. Important catalyst characteristics for the two dewaxing processes Properties Catalytic dewaxing Wax-isomerization Acidity Strong Moderate to weak Pore-characteristics Right dimensions for reactant shape Right pore-separation at selectivity for n-paraffins surface of crystallite Cracking activity Very high to crack n-paraffins Not desired Catalysis at surface Not desired Pore-mouth catalysis Al (Si) content Large (Al) content for high activity Large (Si) content uniform distribution Crystallite size Small for less diffusion effects Size may not be critical

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Design of catalysts for pour .... by S. Sivasanker Bulletin of the Catalysis Society of India 2 (2003) 100-106

A comparison of the three processes used for pour point reduction is presented in Table 3. The two processes, shape-selective cracking and wax isomerization are based on catalysts containing molecular sieves as their active component. However, the properties of the molecular sieves required for the two processes are different (Table 4). A brief description of the optimization of the catalyst properties to prepare good catalysts for the two processes is presented in this paper. 2. Experimental ZSM-5 samples with different SiO2/Al2O3 ratios (Al-contents) and crystallite sizes were prepared following established procedures [5]. The SAPO-11 samples were prepared both by a published method [6] and by new improved synthesis procedures [7,8]. All the synthesized samples were converted into the H-form and loaded with the metals by known procedures. The reactions were carried out in a commercial high-pressure reactor (220 ml volume) supplied by Geomcanique, France. The product samples were analyzed by a variety of techniques used in characterizing petroleum fractions including GC methods. 3. Results and discussion 3.1 Pour point reduction by shape-selective cracking The process is based on the selective cracking of the n-paraffin molecules present in the feed (reactant shape selectivity). The two primary considerations for the choice of the zeolite are i) reactant shape-selective properties for the conversion of the desired molecules (n-paraffins), ii) high cracking activity for n-paraffins and iii) low coke deposition rate. An examination of the properties of all the available zeolites reveals that ZSM-5 (MFI) possesses all the required characteristics. Besides, the material possesses a low H-transfer activity

producing soft-coke (large H/C ratio) making it easy to reactivate by flushing with H2 at high temperatures. Also, its high thermal stability permits repeated coke-burn off in O2 permitting a long overall life. In order to obtain a good catalyst, the properties of the zeolite component need to be optimized. Two important characteristics are SiO2/Al2O3 ratio (Alcontent) and crystallite size. Zeolites are acid catalysts and owe their acidity to the H+ ions present to compensate the negative charge created due to the presence of Al3+ ions in the silicate lattice. As a result, the number of acid sites present (and acidcatalytic activity) is a function of the Al3+ content of the zeolite. The results of dewaxing a heavy neutral raffinate over Ni/H-ZSM-5 with SiO2/Al2O3 ratios of 32, 84 and 347 are presented in Table 5. The shape selective cracking activities of the catalysts are reported in terms of the pour point (pp) of the product, the lower the pp, the greater the selective removal of the waxy components (n-paraffins). As expected, the catalyst with the highest SiO2/Al2O3 ratio (lowest Al-content) is the least active (pp = 279 K). It also deactivates faster, necessitating an increase in temperature of 75 K in 33h to maintain the same pp. The catalysts with SiO2/Al2O3 ratio of 32 and 84 have higher activities and lower deactivation rates. As the performance of both the catalysts are similar, it appears that, beyond a certain limit, higher Al-contents do not further improve dewaxing rates presumably due to diffusion limitations. The pore dimensions of ZSM-5 (0.54 0.57 nm) are just adequate for the entry of the normal and slightly branched paraffins. However, in the case of heavy feedstocks (C20 C60), such as those used in the dewaxing of lube base stocks, the diffusion of even n-paraffins is expected to become rate limiting. Therefore, smaller crystallites with shorter diffusion paths should be more active than larger crystallites in the dewaxing reaction. The results of the studies carried out on the influence of

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Design of catalysts for pour .... by S. Sivasanker Bulletin of the Catalysis Society of India 2 (2003) 100-106

crystallite size on the reaction are presented in Table 6. To obtain a dewaxed product of nearly the same pour point (263 2 K), the smaller crystallites (0.1 m) are able to operate at 28 K lower temperature than the larger crystallites (5 m). Another disadvantage of larger crystallites is that, due to the higher temperatures of operation and longer residence of the cracked products inside the pores, the yield of light gases arising by secondary cracking reactions tend to be higher. For example, the temperatures required to dewax an inter neutral feed (pp = 321 K) to a pp of 263 K were 619 and 602 K when the crystallites were 5 and 0.5 m in size, respectively and the C1 C4 gas yield over the two catalysts were 14.2 and 10.1 wt %, respectively. Small crystallites, however, expose a larger external surface area and are less shapeselective than large crystallites. They also

catalyze the cracking unwanted cracking (of branched paraffins and cyclic alkanes) causing lower yield of the dewaxed oil (DWO) and also lowering the viscosity index of the product. Therefore the external surface needs to be passivated with silicious materials to increase DWO yield and VI. It is possible to synthesize ZSM-5 with either Al3+ or Fe3+ in the lattice, the Alions produce a more acidic catalyst than the Fe-ions. The effect of isomorphous substitution of ZSM-5 on acid strength of the zeolite and dewaxing activity are presented in Table 7. The Fe-isomorph desorbs NH3 earlier (628 K) than the Alanalogue (698 K) and is less acidic. It is seen from Table 7 that the more acidic Alisomorph is more active; it dewaxes the gas oil to the same pp at a lower temperature (623 K) than the Fe-isomorph (641 K).

Table 5. Influence of SiO2/Al2O3 ratio Time On Stream ReactionTemp. (K) Crystallite SiO2/Al2O3 ratio (h) size (m) 32 76 563 ~ 0.5m 32 208 573 ~ 0.5m 84 76 562 ~ 0.5m 84 208 569 ~ 0.5m 347 13 596 ~ 0.5m 347 46 671 ~ 0.5m Feed: Heavy neutral; catalyst: Ni-ZSM-5; press: 3.0 MPa; WHSV (h-1): 0.8; 400. Table 6. Influence of zeolite crystallite size on catalytic activity Product yield(wt %) Reaction Crystallite C5 IBP Wt % DWO Temp. (K) C1-C4 size (m) 5.0 619 14.2 13.8 72.0 1.0 602 10.1 15.9 74.0 0.1 593 9.7 15.8 74.5 Feed: Inter neutral; conditions same as Table 5.

pp (K) 265 271 266 271 279 279 H2/Oil (v/v):

DWO pp (K) 263 264 261

Table 7. Influence of acid strength on dewaxing activity of MFI Zeolite TPD of NH3; Reaction Temp. pp of DWO C5+ ( wt%) peak max. (K) (K) (K) ZSM-5 (Al) 698 623 263 70.6 ZSM-5 (Fe) 628 641 264 77.5 Feed: Atm. GO; catalyst: Pt-H-ZSM-5; press: 50 MPa; WHSV (h-1): 2; H2/Oil (v/v): 300

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Design of catalysts for pour .... by S. Sivasanker Bulletin of the Catalysis Society of India 2 (2003) 100-106

Table 8. Influence of metal component on hydrodewaxing Catalyst / metal Dewaxing Temp. Catalyst / metal (K) H-ZSM-5 295 H-ZSM-5 / Pd H-ZSM-5 / Ni 298 H-ZSM-5 / Pd-Zn Feed: Heavy neutral; press: 3 MPa; WHSV (h-1): 0.65; H2/Oil: (v/v): Table 9. Influence of feed paraffin content on DWO yield. Feed n-paraffin DWO pp pp content (wt %) (K) (K) Spindle (SP) 16 263 27 Light neutral (LN) 12 263 46 Inter neutral (IN) 8 267 54 Heavy neutral (HN) 4 273 58 Bright stock (BS) 273 60 The addition of a metallic component to a cracking catalyst often enhances its activity, reduces deactivation and improves its regenerability. The influence of three different metallic components on the performance of ZSM-5 in the dewaxing of a heavy neutral feed are presented in Table 8. It is noticed that for the highly S-rich (1.1 wt %) feed used, Pd based catalysts are less active than the Ni-catalyst. Even though the Ni-catalyst possesses nearly the same activity as metal free ZSM-5, the presence of Ni enhances catalyst life and improves the regenerability of the catalyst in H2 and O2. Five different feeds were dewaxed with a Ni-ZSM-5 catalyst. The results of the studies are presented in Table 9. The temperature and space velocity were varied to obtain the desired pp for the different LOBS. It is noticed that the pour point reduction (pp) and product yield depend on the n-paraffin content of the parent feed. 3.2. Pour point reduction by isomerization The desired characteristics of the molecular sieve to be used in the isomerization catalysts are: 1) high isomerization activity with low cracking activity, 2) large amount of acid sites with uniform distribution of acidity and 3) poremouth activity. Among the various zeolites and molecular sieves available, SAPO-11

Dewaxing Temp. (K) 310 315 400; DWO pp: 273 K

DWO yield (wt %) 72.5 75.0 79.0 83.3 86.9

has been found to possess the above characteristics to a good measure. Acid centres are created in silicoaluminophosphate (SAPO) molecular sieves when a Si4+ ion replaces a P5+ ion in the framework of the parent aluminophosphate (AlPO4) generating a negative charge, and the negative charge is balanced by a H+ ion. It is also possible that a number of Si4+ ions replace many Al3+ and P5+ ions in a group forming a SiO2 island. Such SiO2 islands are expected to result in less number of acid centres (per Si4+) than the isolated Si4+ ions [9]. Besides SiO2 islands, SiO2-Al2O3 patches with very strong acidity may also result. Thus, when Si incorporation is not uniform, a material with lower number of acid sites and containing a broad distribution of both weak and strong acid sites might result. Our studies on different SAPOs confirmed these ideas and novel synthetic methods were developed that could produce a better distribution of Si4+ in SAPO frameworks resulting in more uniform acidity distribution and greater activity and selectivity in isomerization reactions [7,8]. Two SAPO-11 samples (a) and (na) were prepared using, respectively, the conventional published procedure [6] and by an improved method [7]. The XRD patterns of the two samples were similar. The 27Al MAS NMR spectra of the samples were also similar consisting of a single line 104

Design of catalysts for pour .... by S. Sivasanker Bulletin of the Catalysis Society of India 2 (2003) 100-106

around = 38 ppm due to Al3+ ions in Td sites in the framework. There were, however, marked differences in the 29Si MAS NMR spectra of the two samples. The NMR chemical shift of the isolated Si ions [Si(4Al)] is around = -90 to 95 ppm, while it is around 105 to 110 ppm for the Si ions in SiO2 islands. In general, due to the large number of Si species possible in the SAPOs, in most cases, two broad features corresponding to the isolated and island type Si species are noticed. The 29Si MAS NMR spectra of the two SAPO-11 samples are presented in Figure 1. It is noticed that the signal due to isolated Si species is more prominent than the one due to Si islands in the case of SAPO-11 (na) and is vice versa for SAPO-11 (a).

The compositions of the two samples [(Al0.59P0.32Si0.07)O2 for SAPO-11(na) and (Al0.57P0.38Si0.5)O2 for SAPO-11(a)] reveal that there is a greater substitution of P5+ by Si4+ in SAPO-11 (na) than in SAPO-11(a). This provides additional evidence for the presence of more isolated Si species in SAPO-11(na). The TPD of pyridine adsorbed over these samples revealed that SAPO-11(na) possesses a larger number of acid centres than SAPO-11(a) [7]. Not only does it possess more weak acid sites (pyridine desorbing < 300oC), it also possesses more moderate acid sites (pyridine desorbing > 300oC). This confirms that the Si ions are better dispersed in the framework in SAPO-11(na).

Table 10. Studies on pour point reduction of a hydrocracker bottoms feed for LOBS productiona: Characteristics of feed and product fractionsb. Feed Product fractions 643 673 K 673 713 K Density @ 288 K (g/cc) 0.8321 0.8298 0.8312 Viscosity @ 373 K (cst) 3.53 2.45 3.31 Viscosity Index 107 112 Pour point (K) 300 249 261 S (ppm) <50 N (ppm) <20 Sim. Dist. (D-2887) IBP ((K) 483 515 587 50% (K) 685 650 680 95% (K) 760 695 722 -1 Catalyst: Pt-SAPO-11; Press: 100Mpa; Temp (K): 613; WHSV (h ): 1.0; H2/Oil (v/v): 400; a: experiments done by CPCL R & D; b: Feed provided by CPCL, analysis done by CPCL. A comparison of the performance of the catalyst prepared by the improved (optimized) method is presented in Fig. 2. It is noticed that the improved SAPO-11 has a higher conversion besides a larger I/C ratio even at high conversions. Studies over model hydrocarbons such as n-hexane and n-hexadecane were carried out to optimize the Pt loading of the catalyst. The results revealed that a Pt loading of about 0.5% is most suited for maximum isomerization selectivity. The pour point reduction of a LOBS feedstock (hydrocracker bottoms) through isomerization of the waxy component was investigated over Pt(0.5%)-SAPO-11, with good distribution of Si4+ ions, prepared by the improved method. The pp of the feed was 300 K. The characteristics of the feed and two product fractions are presented in Table 10. It is seen that a significant decrease in product pp is achieved over the SAPO-11 catalyst. The yield of the dewaxed oil was >90% and the VI of the fractions was ~110.

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Design of catalysts for pour .... by S. Sivasanker Bulletin of the Catalysis Society of India 2 (2003) 100-106

Si(4Al)

Si(4Si

Fig.1. 29Si MAS NMR spectra of SAPO-11 samples synthesized by different methods; SAPO-11 (a), conventional method; SAPO-11 (na), improved method. 4. Conclusions

Fig.2. Influence of preparation method on the performance of SAPO-11 in the transformation of n-hexane (-------, Conventional preparation procedure; ______, improved preparation procedure)

Pour point reduction of lube oil base stocks can be typically carried out by two catalytic processes, one based on shape-selective cracking and another based on wax isomerization. The design of the catalysts for the two processes are different based on the nature of the reaction considerations. References 1. Sequeira, A. Jr., Lubricating Base Oil and Wax Processing, Marcel Dekker Inc., New York (1994). 2. Smith, K.W., Starr, W.C., Chen, N.Y., Oil and Gas Journal, May 26, p.75 (1980).

3. Miller, S.J., Microporous Materials, 2, 439 (1994). 4. Le Page, J-F, Applied Heterogeneous Catalysis, Editions Technip, Paris (1987). 5. Kulkarni, S.B., Shiralkar, V.P., Kotasthane, A.N., Borade, R.B., Ratnasamy, P., Zeolites, 2, 313 (1982). 6. Lok, B.M., Messina, C.A., Patton, R.L., Gajek, R.T., Cannon, T.R., Flanigen, E.M., U.S. Patent 4,40,871 (1984). 7. Sinha, A.K., Sivasanker, S., Ratnasamy, P., Ind. Eng. Chem. Res., 37, 2208 (1998). 8. Sinha, A.K., Sainkar, S.S., Sivasanker, S., Micropor. Mesopor. Mater. 31, 321 (1999). 9. Barthomeuf, D, Zeolites, 14, 394 (1994).

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