NL1027901C2 - Hydroisomerization processes using sulfurized catalysts. - Google Patents

Description

Hydroisomerization processes using sulfurized catalysts

Field of the invention 5

The present invention relates generally to the production of Fischer-Tropsch-derived basic lubricating oils. More particularly, the present invention relates to the use of sulphurized, form-selective, noble metal-containing molecular sieve catalysts with an average pore size 10 for producing in a high yield base lubricating oils with high viscosity indices and low pour points.

Background of the Invention Refining operations that produce large quantities of high quality base lubricants are desired. The demand for refineries for producing high-quality basic lubricants for operating modern machines and cars is increasing. Many refining processes produce large quantities of lighter quality products at the expense of producing basic lubricating oil products.

It is known from the prior art to produce base lubricating oils using hydroisomerization processes. For example, U.S. Pat. Nos. 5135638 and 5082986 describe highly shape-selective catalysts for hydroisomerizing waxy feeds. U.S. Pat. No. 5135638 discloses that hydroisomerization dewaxing at low pressure and a low liquid space velocity per hour provides improved isomerization selectivity, resulting in more isomerization and less cracking of the feed, thus yielding a higher yield. obtained. Accordingly, it is described in U.S. Pat. No. 5,113,538 that the yield of the base lubricating oil products obtained can be improved by lowering the pressure at which a hydroisomerization process is carried out.

It is also known from the prior art to use base metal catalysts and noble metal catalysts in hydroisomerization processes. These catalysts can be applied to molecular sieve supports. By way of example, U.S. Pat. No. 5,885,438 describes a process for producing a high viscosity index lubricant from a wax-like hydrocarbon feed, which catalytically dewaxes wax-like paraffin oils present in the feed by isomerization in the presence hydrogen and in the presence of a zeolite isomerization catalyst with a low acidity and large pores. The catalysts of U.S. Patent No. 5,885,438 include a noble metal hydroisomerization catalyst such as Pt. It is further described in US patent 5885438 that platinum or palladium catalysts have a good hydrogenation activity, but only in the absence of sulfur.

There remains a need for effective and efficient processes for producing high yields of a high quality base lubricating oil from a wax-like hydrocarbon feed.

Summary of the invention

Embodiments of the present invention relate to processes for producing high yields of a base lubricating oil from a waxy hydrocarbon feed. In one embodiment, the method comprises, in operation, sulfurizing a shape-selective, noble metal-containing molecular sieve catalyst with an average pore size to provide a sulfurized catalyst. The wax-like hydrocarbon feed is hydroisomerized by contacting the wax-like hydrocarbon feed with the sulfurized catalyst under hydroisomerization conditions to produce a base lubricating oil. Optionally, the sulfurized catalyst can be sulfurized again.

In another embodiment, the method comprises presulfurizing a shape-selective, noble metal-containing molecular sieve catalyst with an average pore size to provide a sulfurized catalyst. The wax-like hydrocarbon feed is contacted with the sulfurized catalyst under hydroisomerization conditions. The sulfurized catalyst is again sulfurized. A basic lubricating oil is isolated.

Brief description of the drawings 027901-3

Figures 1-2 illustrate the effect on yield and viscosity index of using a sulfurized SAPO-11 catalyst to hydroisomerize a waxy Fischer-Tropsch feed at 1000 psig.

Figures 3-4 illustrate the effect on yield and viscosity index of using a sulfurized SAPO-11 catalyst to hydroisomerize a waxy Fischer-Tropsch feed at different pressures.

Figures 5-6 illustrate the effect on yield and viscosity index of using a sulfurized zeolite catalyst to hydroisomerize a waxy Fischer-Tropsch feed at 1000 psig.

Figure 7 illustrates the effect on the iso-to-normal C4 ratio of using a SAPO catalyst sulfurized in operation.

Figure 8 illustrates the effect on the amounts of light hydrocarbons produced using a pre-sulphurized SAPO catalyst.

Figures 9A-C illustrate the effect on yield, viscosity index and temperature of using a pre-sulphurized SAPO catalyst to hydroisomerize a waxy Fischer-Tropsch feed at different pressures.

Detailed description of the invention

According to the method according to the present invention, it has surprisingly been discovered that by sulfurizing a form-selective noble metal-containing molecular sieve catalyst with an average pore size, the selectivity for hydroisomerization with respect to hydrocracking is improved and thus the yield of produced base lubricating oil is increased . Accordingly, contacting a wax-like hydrocarbon with a sulfur-pore, form-selective, noble metal-containing molecular sieve catalyst with an average pore size gives a high yield of a high quality base lubricating oil.

30

Sulfurizing the catalyst 1027901-4

It has been discovered that the hydroisomerization selectivity (the preference for isomerization reactions over cracking reactions) of form-selective noble metal-containing molecular sieve catalysts with an average pore size is improved as the catalyst is sulfurized. According to the present invention, the catalyst can be sulfurized before or during the hydroismerization reaction. A precious metal is any metal that is resistant to corrosion or oxidation. A noble metal-containing catalyst is any catalyst that contains a noble metal. Precious metal catalysts include platinum, palladium, and mixtures thereof.

According to the present invention, the shape-selective noble metal-containing molecular sieve catalyst with an average pore size is carried out for carrying out the hydroisomerization process. The catalyst can be sulfurized at various stages of the hydroisomerization process. The catalyst can be sulfurized to carry out the hydroisomerization reaction. According to the present invention, the sulfur sulphurization process is called "pre-sulphurization" of the catalyst when it is conducted before the waxy feed is fed to the reactor for carrying out the hydroisomerization process. The sulfurization process is called "sulfurization during operation" if it is performed after the hydroisomerization reaction is initiated. The sulfurization process during operation can be performed simultaneously with the hydroisomerization process by applying a feed for the hydroisomerization process which includes the required sulfur for sulfurization. Alternatively, the sulfur process can be carried out during use by pausing the hydroisomerization reaction process, sulfurizing the catalyst and then resuming the hydroisomerization reaction process. When the hydroisomerization process is paused, the sulfurization of the catalyst can be carried out according to the same techniques that are used to presulfurize the catalyst. The sulfurization process is referred to as "resulfurization" when the catalyst that was initially sulfurized or sulfurized in a previous sulfur step when in use is again subjected to a sulfurization process. The resulfurization can be carried out simultaneously with the hydroisomerization process or by pausing the hydroisomerization process as described above for sulfurization during operation. According to the present invention, the catalyst is preferably presulfurized.

1027901-5

According to the present invention, the sulphurization of the form-selective noble metal-containing molecular sieve catalyst with an average pore size can be carried out according to techniques for sulphurizing catalysts known to the skilled person. For example, the catalyst can be sulfurized by contacting the catalyst with a sulfur-containing species, usually in the presence of hydrogen. Mixtures of hydrogen and hydrogen sulfide, carbon disulfide or a mercaptan such as butyl mercaptan are commonly used for sulfurizing. Sulfurization can be carried out by contacting the catalyst with hydrogen and a sulfur-containing hydrocarbon oil (referred to as a non-diluted feed), such as acidic kerosene or gas oil, or sulfurization can be accomplished by adding active sulfur to the wax-like hydrocarbon feed (referred to as a sulfur-mixed feed).

In particular, pre-sulphurization can be achieved by techniques known to those skilled in the art. Methods have been developed by those skilled in the art for pre-sulphurizing in situ fresh catalyst batches for fixed bed reactor systems at the beginning of each series. These methods usually include a step of heating gas and a step of drying the catalyst in the reactor vessel, followed by wetting / soaking the catalyst with start-up oil and then sulfurizing in a step involving either a non-diluted feed (a feed) - which contains naturally occurring sulfur compounds) or a diluting feed (a feed to which active sulfur compounds are added) is used. In addition, in the sulfurization step, H 2 / H 2 S can be used to sulfurize the catalyst in the vapor phase. Examples of sulfurization techniques known in the art have been discussed and published by Harman Hallie at a catalyst symposium in Amsterdam, May 1982, and published in the December 20, 1982 issue of Oil and Gas Journal. Another description is given in a report titled "Properties and Application of Commercial Presulfiding Agents" by William J. Tuzynski, presented at the NPRA conference in 1989.

According to embodiments of the present invention, sulfurizing the catalyst comprises adding at least one mole of sulfur per mole of noble metal present in the catalyst, preferably platinum and / or palladium. The noble metal is dispersed in the shape-selective noble metal-containing molecular sieve catalyst with an average pore size. It will be apparent to those skilled in the art that the number of moles of metal in the catalyst is calculated by calculating the number of grams of catalyst times the weight percentage of the metal divided by the molecular weight of the metal. In a preferred embodiment, the molar ratio of sulfur to noble metal is at least 3: 1. In an example of this embodiment, sufficient sulfur is added to a pre-sulfur treatment step such that this results in a molar ratio of sulfur to noble metal of at least 2: 1. Additional sulfur is added to the catalyst in the course of the hydroisomerization process so that this results in a molar ratio of sulfur to noble metal of at least 3: 1. In another embodiment, the ratio is 5: 1.

In general, pre-sulfur techniques employing non-diluted feeds include the decomposition of sulfur compounds in H 2 S, wherein the sulfur compounds are naturally present in a selected start-up hydrocarbon feedstock. The reactor temperatures in these techniques generally range from about 300 to 350 ° C (572 to 662 ° F). In contrast, sulfur-sulfur techniques using diluted feeds can be performed by injecting active, sulfur-containing organic compounds into a selected start-up hydrocarbon feed such that the injected compounds decompose into H 2 S at temperatures lower than those required for decomposition of naturally occurring sulfur compounds (if present). Preferred extenders are dimethyl sulfide and dimethyl disulfide, since these compounds allow sulfurization processes to be carried out at temperatures ranging from about 250 to 275 ° C.

The sulfurization and start-up processes are tailor-made to maintain the quality of the initial conditions of the waxy hydrocarbon feed and hydrocarbon temperature so that the sulfurization and hydrogenation reactions do not create adverse temperature conditions in the interior of the catalyst pellets. . Such adverse temperature conditions can result in the deposition of carbon or the sintering of metal, both of which reduce the activity of the catalyst and are therefore undesirable. The severity of the hydrogenation reactions that take place during the initial conditioning and sulfurization period of the catalyst is limited by the quality of the initial waxy hydrocarbon feed (e.g., the sulfur content) and the reactor temperatures, which prevail until the sulfurization reactions decrease or essentially stop. Current prior art techniques allow an in-situ pre-sulfurization to be initiated at temperatures lower than about 200 ° C (392 ° F) and completed before the temperatures are higher than about 300 ° C (572 ° F).

Techniques are known for pre-treating catalysts by impregnating with a sulfur compound (e.g., a polysulfide, such as described in U.S. Patent No. 5786293) before the catalysts are fed into the reactor. This is called ex-situ pre-sulfur. If ex-situ pre-sulphurts are used, the catalyst may still have to dry, wet, and undergo conversion to a metal sulfide state in the reactor during the start-up processes. An inexpensive method for the ex-situ sulphurization of fresh catalyst batches to be added to an operating reactor operated at elevated temperatures and hydrogen pressures is described in U.S. Patent Application 2002/0043483, the contents of which are in wholly incorporated herein.

15

Wax-like hydrocarbon feeds

Feeds useful in the hydroisomerization processes of the present invention are waxy hydrocarbons including gas oil, lubricating oil raw material, synthetic oil, wax obtained via Fischer-Tropsch, oligomerized olefins obtained via Fischer-Tropsch, foot oils, slag wax, oily wax, normal alpha olefin wax, microcrystalline wax and mixtures thereof. The preferred feeds are Fischer-Tropsch-obtained waxes, slag wax, oily waxes, normal-alpha-olefin waxes and oligomerized Fischer-Tropsch-derived olefins. Waxes obtained via Fischer-Tropsch are particularly preferred foods.

In some embodiments of the present invention, it is desirable to use waxy hydrocarbon feeds that contain less than 10 ppm of sulfur. Therefore, waxy feeds containing high sulfur contents (higher than 10 ppm) for the hydroisomerization reaction are preferably subjected to a hydrotreatment in order to remove sulfur. Therefore, waxy hydrocarbon feeds with low sulfur contents, preferably lower than 10 ppm sulfur, are preferred. These feeds with a low sulfur content include Fischer-Tropsch wax, oligomerized Fischer-Tropsch olefins, 1027901 8-alpha-olefin olefin wax, and slag wax obtained from hydroprocessed feeds.

The wax-like hydrocarbon feed contains at least 10 weight percent wax and often contains more than 50 weight percent wax and often more than 80 weight percent wax.

5

Fischer-Tropsch synthesis

Preferably, the wax-like hydrocarbon feed according to the present invention is obtained from a wax-like feed obtained via Fischer-Tropsch.

In Fischer-Tropsch chemistry, syngas is converted into liquid hydrocarbons under reaction conditions through contact with a Fischer-Tropsch catalyst. Typically, methane and optionally heavier hydrocarbons (ethane and heavier) can be passed through a conventional syngas generator to provide synthesis gas. In general, synthesis gas contains hydrogen and carbon monoxide and may contain smaller amounts of carbon dioxide and / or water. The presence of sulfur, nitrogen, halogen, selenium, phosphorus and arsenic impurities in the syngas is undesirable. Therefore, and depending on the quality of the syngas, it is preferable to remove sulfur and other contaminants from the feed before the Fischer-Tropsch chemistry is performed. Means for removing these contaminants are well known to those skilled in the art. For example, ZnO protection beds are preferred for the removal of sulfur contaminants. Means for removing other contaminants are well known to those skilled in the art. It may also be desirable to purify the syngas for the Fischer-Tropsch reactor to remove carbon dioxide produced during the syngas reaction and any additional sulfur compounds that have not yet been removed. This can be done, for example, by contacting the syngas with a moderately alkaline solution (e.g., aqueous potassium carbonate) in a packed column.

During the Fischer-Tropsch process, contacting a synthesis gas comprising a mixture of H 2 and CO under suitable reaction conditions of temperature and pressure produces liquid and gaseous hydrocarbons with a Fischer-Tropsch catalyst. The Fischer-Tropsch reaction is usually conducted at temperatures of about 149-371 ° C (300-700 ° F), preferably about 204 ° C-228 ° C (400 ° F-550 ° F); pressures of about 0.7-41 bar (10-600 psia), preferably 1027901 _____ 9 2-21 bar (30-300 psia); and catalyst space rates of about 100-10,000 .000% cm / g / hour, preferably about 300-3000 cm / g / hour. Examples of conditions for carrying out Fischer-Tropsch type reactions are well known to those skilled in the art.

The products of the Fischer-Tropsch synthesis process can vary from C 1 to C 200 +, not the major part in the range from C 5 to C kxh -. The reaction can be conducted in a variety of reactor types, such as, for example, fixed bed reactors containing one or more catalyst beds, slurry reactors, fluidized bed reactors, or a combination of different types of reactors. Such reaction processes and reactors are well known and documented in the literature.

In the Fischer-Tropsch suspension process, which is preferred in the practice of the invention, superior heat (and mass) transfer characteristics are used for the highly exothermic synthesis reaction and paraffinic hydrocarbons with a relatively high molecular weight can be obtained. produced as a cobalt catalyst is used. In the slurry process, a syngas comprising a mixture of hydrogen and carbon monoxide is bubbled upwards as a third phase through a slurry comprising a particulate hydrocarbon synthesis catalyst of the Fischer-Tropsch type that is dispersed and suspended in a slurry. deert liquid comprising hydrocarbon products of the synthesis reaction which are liquid under the reaction conditions. The molar ratio of hydrogen to carbon monoxide can vary roughly from about 0.5 to about 4, but more usually is in the range of about 0.7 to about 2.75 and preferably from about 0.7 to about 2.5. A particularly preferred Fischer-Tropsch process is described in EP 0609079, which should also be considered as fully incorporated herein for all purposes.

In general, Fischer-Tropsch catalysts contain a Group VIII transition metal on a metal oxide support. The catalysts may also contain (a) noble metal promoter (s) and / or crystalline molecular sieves. Suitable Fischer-Trop-30 sch catalysts include one or more of the metals Fe, Ni, Co, Ru and Re, with cobalt being preferred. A preferred Fischer-Tropsch catalyst comprises effective amounts of cobalt and one or more of the metals Re, Ru, Pt, Fe, Ni, Th, Zr, Hf, U, Mg and La on a suitable inorganic carrier material, preferably a 1027901 support material comprising one or more refractory metal oxides. In general, the amount of cobalt present in the catalyst is between about 1 and about 50 weight percent of the total catalyst composition. The catalysts can also contain basic oxide promoters such as TI10, La2C> 3, MgO and T102, promoters such as Ζ1Ό2, noble metals (Pt, Pd, Ru, Rh, Os, Ir), coin metals (Cu, Ag, Au) and other transition metals such as Fe, Mn, Ni and Re. Suitable support materials include aluminum oxide, silicon dioxide, magnesium oxide and titanium oxide or mixtures thereof. Preferred supports for cobalt-containing catalysts include titanium oxide. Useful catalysts and their preparation are known and are illustrated in U.S. Pat. No. 4,566,863, which is intended to be illustrative but not limiting with regard to the choice of the catalyst.

Certain catalysts are known to provide chain growth probabilities that are relatively low to medium and the reaction products include a relatively high content of low molecular weight olefins (C2-8) and a relatively low content of high molecular weight waxes (C30 +). Certain other catalysts are known to provide relatively high chain growth probabilities and the reaction products include a relatively low content of low molecular weight olefins (C2-8) and a relatively high content of high molecular weight waxes (C30 +). Such catalysts are generally known to those skilled in the art and can easily be obtained and / or prepared.

The product of a Fischer-Tropsch process contains mainly paraffins. The products of Fischer-Tropsch reactions generally include a light reaction product and a wax-like reaction product. The light reaction product (i.e., the condensate fraction) comprises hydrocarbons boiling at a temperature below about 700 ° F (e.g., tail gases up to medium distillate fuels), largely in the range of C5 -C20, with decreasing amounts up to about C30. The wax-like reaction product comprises hydrocarbons boiling at a temperature above about 600 ° F (e.g., vacuum gas oil up to and including heavy paraffins), largely in the range of C20 +, with decreasing amounts to C10.

Both the light reaction product and the wax-like product are essentially paraffinic. The wax-like product generally comprises more than 70 weight percent of normal paraffins and often more than 80 weight percent of normal paraffins. The light reaction product comprises paraffinic products with a significant content of alcohols and olefins. In some cases, the light reaction product may comprise as much as 50 percent by weight, and even more, of alcohols and olefins. It is the wax-like reaction product (i.e., the wax fraction) that can be used as feed for the methods of the present invention.

According to the present invention, base lubricating oils can be prepared by hydroisomerizing waxy Fischer-Tropsch reaction products. Other methods that can be used in preparing base lubricating oils from waxy Fischer-Tropsch reaction products include hydrotreating, oligomerization, solvent dewaxing, atmospheric and vacuum distillation, hydrocracking, hydrofinishing and other forms of hydroprocessing.

Hydroisomerization

According to the present invention, the wax-like hydrocarbon feeds are subjected to a hydroisomerization process using molding-selective, noble metal-containing molecular sieve catalysts with an average pore size. Hydroisomerization is intended to improve the cold flow properties of a basic lubricating oil by selectively adding branching to the molecular structure. With hydroisomerization, a high conversion of wax-like hydrocarbon feed into non-wax-like isoparaffins is ideally achieved while reducing cracking conversion.

According to the present invention, the hydroisomerization is carried out using a shape-selective, noble metal-containing molecular sieve catalyst with an average pore size. The term "average pore size," as used herein, means an effective pore opening in the range of about 4.0 to about 7.1 A if the porous inorganic oxide has a calcined form. The shape-selective molecular sieves with an average pore size used in the practice of the present invention are generally molecular sieves with a 1-D 10, 11 or 12 ring. The preferred molecular sieves according to the invention are of the 1-D 10-ring variety, with molecular sieves having a 10- (or 11- or 12-) ring 10 (or 11 or 12) tetraedrically coordinated have atoms (T atoms) that are bound to oxygen atoms. In the 1-D molecular sieve, the 10-ring (or larger) pores are parallel to each other and do not form an interconnection. The classification of intrazeolite channels as 1-D, 2-D and 3-D is represented by R.M. Barrer in Zeolites, Science and Technology, published by F.R. Rodrigues, L.D. Rollman and C. Naccache, NATO ASI Series, 1984, which classification as a whole must be considered as inserted herein (see in particular page 75).

The shape-selective noble metal-containing molecular sieve catalysts with an average pore size according to the present invention can be zeolietic molecular sieves, non-zeolietic molecular sieves or mixtures thereof. Preferably, shape-selective noble metal-containing molecular sieve catalysts with an average pore size are non-zeolietic.

As used herein, non-zeolietic molecular sieve refers to a molecular sieve comprising a crystalline, three-dimensional microporous backbone structure of tetrahedral A102 and PO2 oxide units, and optionally one or more metals in tetrahedral coordination with oxygen atoms. Preferably, non-zeolietic molecular sieves are characterized by a three-dimensional microporous skeletal structure of tetrahedral AIO 2 and PO 2 oxide units with an anhydrous unitary formula based on: (MxAyPz) 02 where: "M" is at least one element other than aluminum and phosphorus, represents that an oxide in tetrahedral coordination with Al 2 O 2 and PO 2 can form oxide structural units in the crystalline molecular sieve; and "x", "y" and "z" represent the molar fractions of element "M", aluminum and phosphorus, respectively, where "x" has a value equal to or greater than zero (0) and "y" and " z "each have a value of at least 0.01.

In a preferred embodiment, the metallic element "M" is selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, silicon, titanium, vanadium, nickel and zinc and more preferably selected from the group consisting of silicon, magnesium, manganese, zinc and cobalt; and even more preferably silicon. As used herein, element "M" is considered a component of the non-zeolietic molecular sieve.

1027901-13

According to the present invention, preferred shape-selective molecular sieves with a medium pore size and used for hydroisomerization are non-zeolietic molecular sieves. Preferred shape-selective non-zeolite molecular sieves with a medium pore size are based on aluminum phosphates (i.e., SAPO catalysts) such as SAPO-11, SAPO-31 and SAPO-41. SAPO-11 and SAPO-31 are more preferred, with SAPO-11 being the most preferred. SM-3 is a preferred medium-pore size selective SAPO and has a crystal structure that is within that of the SAPO-11 molecular sieves. The preparation of SM-3 and its unique properties are described in U.S. Patent Nos. 4,943,424 and 5158665.

In another embodiment of the present invention, a zeolite molecular sieve can be used. These include ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite and ferrierite, with SSZ-32 and ZSM-23 being preferred.

A preferred average pore size molecular sieve is characterized by selected crystallographic free diameters of the channels, selected crystal size (corresponding to a selected channel length) and selected acidity. Desired crystallographic free diameters of the channels of the molecular sieves are in the range of about 4.0 to about 7.1 Å, with a maximum crystallographic free diameter of no more than 7.1 and a minimum crystallographic free diameter of not less than 3.9 A. Preferably, the maximum crystallographic free diameter is not greater than 7.1 and the minimum crystallographic free diameter is not less than 4.0 A. Most preferably, the maximum crystallographic free diameter is not greater than 6 , And the minimum crystallographic free diameter not less than 4.0 A. The crystallographic free diameters of the channels of the molecular sieves are published in the "Atlas of Zeolite Framework Types", fifth revised edition, 2001, of Ch. Baerlocher, W.M. Meier and D.H. Olson, Elsevier, biz. 10-15, which is incorporated herein by reference.

A particularly preferred average pore size molecular sieve useful in the present process is described, for example, in U.S. Patent Nos. 5,113,538 and 5,282,958, the contents of which are incorporated by reference in their entirety. In U.S. Pat. No. 5,228,958, such an average pore size molecular sieve has a crystal size of no more than about 0.5 microns and pores with a minimum diameter of at least about 4.8 Å and with a maximum diameter of about 7 A. The catalyst has a sufficient acidity, so that 0.5 grams thereof if it has been placed in a tube reactor at 370 ° C, a pressure of 1200 psig, a hydrogen flow rate of 5 160 ml / min and a feed rate of 1 ml / min at least 50% hexadecane. The catalyst also exhibits an isomerization selectivity of 40 percent or higher (the isomerization selectivity is determined as follows: 100 x (weight percentage of branched C | 6 in product) / (weight percentage of branched C16 in product + weight percentage of C13. In product) when used under conditions leading to a conversion of 96% normal hexadecane (n-Q 6) into other species).

Such a particularly preferred molecular sieve can be further characterized by pores or channels with a crystallographic free diameter in the range of about 4.0 to 7.1 A and preferably in the range of 4.0 to 6.5 A. The crystal tallographic free diameters of the channels of molecular sieves are published in the "Atlas of Zeolite Framework Types", fifth revised edition, 2001, of Ch. Baerlo-cher, W.M. Meier and D.H. Olson, Elsevier, biz. 10-15, which is incorporated herein by reference.

If the crystallographic free diameters of the channels of a molecular sieve are unknown, the effective pore size of the molecular sieve can be measured using standard adsorption techniques and hydrocarbonaceous compounds with known minimum kinetic diameters. See Breek, Zeolite Molecular Sieves, 1974 (in particular Chapter 8); Anderson et al., J. Catalysis 58, 114 (1979); and U.S. Patent No. 4,440,871, the relevant parts of which are incorporated herein by reference. Standard techniques are applied when conducting adsorption measurements to determine the pore size. It is appropriate to consider a particular molecule as excluded if it does not reach at least 95% of its equilibrium adsorption value on the molecular sieve in less than about 10 minutes (p / p0 = 0.5; 25 ° C). Molecular sieves with a medium pore size usually allow molecules with kinetic diameters of 5.3 to 6.5 Angstrom with little hindrance.

Hydroisomerization catalysts useful in the present invention include a catalytically active noble metal. The presence of a catalytically active noble metal leads to product improvement, in particular viscosity index and stability.

102 7901 "15

Typically, catalytically active noble metals include platinum and palladium and mixtures thereof, with platinum being preferred. When platinum and / or palladium is used, the total amount of the active noble metal is usually in the range of 0.1 to 5 weight percent of the total catalyst, usually 0.1 to 2 weight percent, 5 and no more than 10 weight percent.

The carrier of a refractory oxide can be selected from those oxide supports that are commonly used for catalysts, including silica, aluminum oxide, silica-alumina, magnesium oxide, titanium oxide, and combinations thereof.

The conditions for the hydroisomerization are adjusted to achieve a basic lubricating oil with specific branching properties, as described above, and are therefore dependent on the properties of the feed used. In general, the conditions for hydroisomerization in the present invention are mild, so that the conversion of wax to materials boiling at a temperature between about 650 and 1400 ° F is kept between about 40 and 95% by weight in producing the base lubricating oil.

Mild hydroisomerization conditions are achieved by operating at a lower temperature, generally between about 390 and 650 ° F, and at a liquid space velocity per hour (LHSV) that is generally between about 0.5 and 20 hours. 20. The pressure is usually about 15 to 2500 psig, preferably about 50 psig to 2000 psig, more preferably about 100 to 1500 psig, even more preferably about 150 psig to 1000 psig and even more preferably about 250 to 600 psig. Using the sulfurized, form-selective noble metal-containing molecular sieve catalysts with an average pore size, low pressure can provide improved isomerization selectivity, resulting in more isomerization and less cracking of the feed, thus obtaining a higher yield. . Examples of methods are described in U.S. Patent Nos. 5135638, 5246566 and 6337010, the contents of which are incorporated herein by reference in their entirety.

In addition, using the sulfurized, form-selective, noble metal-containing molecular sieve catalysts with an average pore size according to the present invention, the hydroisomerization process can be carried out at higher pressures while maintaining an acceptable yield and quality of the basic lubricating oil product 1027901 16. . In fact, the present invention provides a hydroisomerization process that can be carried out at relatively higher pressures and with which an acceptable yield of a high quality basic lubricating oil product is achieved. By carrying out a hydroisomerization process using a sulfurized, shape-selective, noble metal-containing molecular sieve catalyst with an average pore size, an acceptable yield of a high-quality basic lubricating oil is provided even at relatively high pressures. Although sulfurizing the catalyst improves the yield of the produced basic lubricating oil when the hydroisomerization reaction is carried out at both relatively high and relatively low pressures, the effect on the yield of the produced basic lubricating oil product is more evident when the hydroisomerization is carried out at high pressure. Because problems may arise if the hydroisomerization process is operated at relatively lower pressures, by using the sulfurized catalysts of the present invention, a process is surprisingly provided wherein the hydroisomerization can be operated at a relatively higher pressure while an acceptable yield of a basic lubricating oil high quality is achieved. Therefore, in one embodiment, it is preferable to perform the hydroisomerization at a relatively higher pressure (i.e., between about 500 and 1000 psig).

Hydrogen is present in the reaction zone during the hydroisomerization process, usually in a hydrogen to feed ratio of about 0.5 to 30 MSCF / bbl (one thousand standard cubic feet per vessel), preferably about 1 to about 10 MSCF / bbl. Hydrogen can be separated from the product and returned to the reaction zone.

25

Solvent dewaxing

According to the present invention, at least a portion of the base lubricating oil produced by the hydroisomerization process is subjected to solvent dewaxing. Solvent dewaxing techniques are known in the art. Solvent dewaxing can be used to remove the remaining wax-like molecules by dissolving the wax-like components in a solvent such as methyl ethyl ketone, methyl isobutyl ketone or toluene; Precising the wax-like components; and then removing the wax-like components by filtration. Solvent dewaxing is discussed in "Chemical Technology of Petroleum", third edition, William Gruse and Donald Stevens (McGraw Hill, New York, 1960), pages 566-570. See also U.S. Patent Nos. 4,477,333, 3773650 and 3775288.

According to the present invention, solvent dewaxing can be used advantageously to dewax at least a portion of the product from the hydroisomerization process to remove residual unreacted waxy components after the isomerization step (s). The wax extracted from a solvent dewaxing process (referred to as "slag wax") can be recycled to the hydroisomerization process of the present invention to obtain even higher yields of base lubricating oil.

DVD treatment and DVD finishing 15

Hydrotreating and hydrofinishing are optional processing steps that may also be included in the methods of the present invention. Hydrotreating can be carried out for the hydroisomerization process at the waxy hydrocarbon feed. Hydrotreating involves a catalytic process, usually carried out in the presence of free hydrogen, the primary purpose of which is the removal of various metal contaminants, such as arsenic; heteroatoms such as sulfur and nitrogen; and aromatic compounds from the diet. In general, during the hydrotreating step, it is desirable to minimize the amount of cracking of hydrocarbon molecules (i.e., breaking down larger molecules into smaller molecules). During hydrotreating, unsaturated hydrocarbons are either fully or partially hydrogenated. The waxy hydrocarbon feed for the present process can be hydrotreated before the hydroisomerization.

Catalysts used in carrying out hydrotreating operations are known in the art. See, for example, U.S. Pat. Nos. 4,347,121 and 4,810,357, the contents of which are incorporated by reference in their entirety, for general descriptions of hydrotreating and of conventional catalysts used in this process. Suitable catalysts include Group VIIIA noble metals (according to the International Union of Pure and Applied Chemistry rules from 1975), such as platinum or palladium on an aluminum oxide or silicon-containing matrix, and Group VIII and Group VIB metals, such as nickel-molybdenum or nickel-tin on an aluminum-oxide or silicon-containing matrix. U.S. Pat. No. 3,852,207 describes a suitable noble metal catalyst and mild conditions for carrying out the reaction. Other suitable catalysts are described, for example, in U.S. Pat. The non-noble metal hydrogenation metals, such as nickel molybdenum, are usually present as oxides in the final catalyst composition, but can be used in their reduced or sulfurized forms.

Preferred non-noble metal catalyst compositions contain more than about 5 weight percent, preferably about 5 to 40 weight percent molybdenum and / or tungsten, and at least about 0.5 weight percent and generally about 1 to 15 weight percent nickel and / or cobalt, determined as the corresponding oxides. Catalysts containing noble metals, such as platinum, contain more than 0.01 percent metal, in some embodiments between 0.1 and 1.0 weight percent metal. Combinations of noble metals can also be used, such as mixtures of platinum and palladium.

Conventional hydrotreating conditions vary over a wide range.

In general, the total LHSV is about 0.25 to 2.0 hours, preferably about 0.5 to 1.0 hours. The hydrogen partial pressure in hydrotreating may be higher than 200 psia and preferably ranges from about 500 to 2000 psia. Hydrogen recycling rates are usually higher than 50 SCF / Bbl and are preferably between 1000 and 5000 SCF / Bbl. Temperatures in a hydrotreating reactor range from about 150 to 400 ° C (300 to 750 ° F) and preferably range from 230 to 315 ° C (450 to 600 ° F).

Hydrofmishing is a hydrotreating process that can be carried out as the final step in the production process from base lubricating oil to the base lubricating oil product. This last step is intended to improve the UV stability and appearance of the product by removing trace amounts of aromatics, olefins, color bodies and solvents. As used herein, the term UV stability refers to the stability of the base lubricating oil or the finished lubricant upon exposure to UV light and oxygen. Instability is indicated if a visible precipitate is formed, which is usually observed as flakes or cloudiness, or a darker color develops upon exposure to ultraviolet light and air. A general description of hydrofinishes can be found in U.S. Pat. Nos. 3,852,207 and 46,73487. Treating with clay to remove these contaminants is an alternative final process step.

Oligomerization 10

The waxy hydrocarbon feed used in the processes of the present invention may include oligomerized Fischer-Tropsch olefins. Depending on the conditions under which the Fischer-Tropsch synthesis is carried out, the Fischer-Tropsch condensate contains different amounts of olefins. In addition, most Fischer-Tropsch condensates contain some alcohols that can be easily converted to olefins by dehydration. As already stated, the condensate can also be enriched with olefin via a cracking operation, for example by thermal cracking. In an embodiment of the present invention, these olefins may be oligomerized to produce Fischer-Tropsch olefins. During oligomerization, the lighter olefins are not only converted to heavier molecules, but the carbon skeleton of the oligomer exhibits branching at the points of the molecular addition. As a result of the introduction of branching into the molecule, the pour point of the products is lowered.

Oligomerization of olefins is reported in the literature and a variety of commercial processes are available. See, for example, U.S. Pat. Nos. 4417088, 4434308, 4827064, 4827073 and 4990709. Although different types of reactor configurations can be used, the fixed catalyst bed reactor is used commercially. More recently, a method for carrying out the oligomerization in an ionic liquid medium has been proposed. Because oligomerization catalysts are very active and the contact between the catalyst and the reagents is efficient, the separation of the catalyst from the oligomerization products is simplified.

1027901-20

Oligomerization reactions proceed under a large number of circumstances. Typical temperatures for carrying out the reaction range from about 0 to 425 ° C (32 to 800 ° F). Other conditions include a space velocity of 0.1 to 3 hours and a pressure ranging from about 0 to 2000 psig. Catalysts for the oligomerization reaction can be almost any acidic material, such as, for example, zeolites, clays, resins, BF3 complexes, HF, H 2 SO 4, AlCl 3, ionic liquids (preferably ionic liquids comprising a Bronsted or Lewis acid component or a combination of Bronsted and Lewis acid components), transition metal-based catalysts (such as Cr / SiC> 2), superacids and the like. In addition, non-acid oligomerization catalysts, including certain organometallic or transition metal oligomerization catalysts, can be used, such as, for example, zirconocenes.

Basic lubricating oil products and properties 15

Base lubricating oils prepared according to the methods of the present invention have a high quality, as characterized by the viscosity index and the pour point of the base lubricating oil. Accordingly, the basic lubricating oils have high viscosities, low pour points and exceptionally high VIs.

Basic lubricating oils with high viscosity indices are desired. The viscosity index (VI) is an empirical, unitless number that reflects the effect of the temperature change on the kinematic viscosity of the oil. The viscosity of liquids changes with temperature and liquids become less viscous when heated; the higher the VI of an oil, the lower its tendency to change viscosity with temperature. Lubricants with a high VI are needed where a relatively constant viscosity is required at widely varying temperatures. For example, in a car, engine oil must flow freely enough to allow cold starting, but after heating it must be viscous enough to provide complete lubrication. The VI can be determined as described in ASTM D 30 2270-93. The base lubricating oils of the present invention have a high viscosity index ranging from about 140 to 190.

The pour point is the temperature at which a sample of the basic lubricating oil begins to flow under carefully controlled conditions. Where pour point 1027901-21 is given herein, unless otherwise stated, this has been determined according to the standard analytical method ASTM D 5950-02. The basic lubricating oils of the present invention have excellent pour points. The pouring points of the basic lubricating oils are between approximately -5 and -60 ° C. Preferably the pouring points of the base lubricating oils are lower than -9 ° C, more preferably <-15 ° C and even more preferably lower than -15 ° C.

The cloud point is a measure that is complementary to the pour point and is represented as the temperature at which a sample of the base lubricating oil begins to develop a haze under carefully specified conditions. The cloud point can for example be determined according to ASTM D 5773-95. The basic lubricating oils with an optimized branching according to the present invention have cloud points lower than 0 ° C.

In addition, the base lubricating oils of the present invention usually have high oxidation stability, high UV stability, low volatility, and excellent low temperature properties. The base lubricating oils of the present invention have a kinematic viscosity between about 2 and 40 cSt at 100 ° C. Preferably the base lubricating oils of the present invention have a kinematic viscosity higher than 2.6 cSt at 100 ° C, more preferably higher than 3 cSt at 100 ° C.

The American Petroleum Institute (API) has classified base oils according to their chemical composition. As defined by the API, the oils from group III are oils with a very high viscosity index (> 120) with a total sulfur content of less than 300 ppm and a content of saturated compounds greater than or equal to 90%. API Group III oils are also traditionally prepared by vigorous hydrocracking and / or isomerization of the wax. Base lubricating oils according to the present invention are generally classified as base oils from API group III. When prepared from wax-like feeds with a low total sulfur content, such as Fischer-Tropsch feeds, the base lubricating oils also have a total sulfur content of less than 300 ppm.

Base lubricating oils of the present invention prepared from waxy Fischer-Tropsch feeds generally have a total sulfur content of less than about 5 ppm. Total sulfur is determined using ultraviolet fluorescence according to ASTM D 5453-00.

1027901-22

Mixtures

The base lubricating oils of the present invention can be used alone or can be mixed with additional base oils selected from the S group consisting of conventional base oils from group I, conventional base oils from group II, conventional base oils from group III, isomerized petroleum wax, polypropylene alpha-olefins (PAO), poly-internal-olefins (PIO), di-esters, polyol esters, phosphate esters, alkylated aromatics and mixtures thereof.

Because the base lubricating oils of the present invention have excellent cold flow properties, high VIs and high oxidation stability, they are ideal blending raw materials for working up conventional base lubricating oils.

It is preferred that when the base lubricating oils of the present invention are mixed with one or more additional base lubricating oils, the additional base oils are present in an amount less than 95% by weight of the total base oil composition obtained.

Ready lubricants

Base lubricating oils are the most important component of finished lubricants and these generally comprise more than 70% of the finished lubricants. Ready lubricants include a basic lubricating oil and at least one additive. Finished lubricants can be used in cars, diesel engines, axles, transmissions and industrial applications. Ready lubricants must meet the specifications for their intended application, as defined by the relevant regulatory organization.

The basic lubricating oils of the present invention are useful in commercial ready lubricants. Due to the excellent VIs and low temperature properties thereof, the base lubricating oils of the present invention are suitable for formulating finished lubricants intended for many of these applications. In addition, the excellent oxidation stability of the base lubricating oils of the present invention makes them useful in ready lubricants for many high temperature applications.

1027901 * 23

The basic lubricating oils of the present invention are suitable for blending into a wide variety of ready lubricants, including but not limited to automotive engine oils, natural gas engine oils, automatic transmission fluid, industrial gear oils, turbine oils, textile oils, oils for heat transfer, hydraulic oils, paper machine oils, pivot oils, rock drilling oils, pump oils, compressor oils, road oils, and metalworking fluids. The basic lubricating oils of the present invention can also be used as recovery fluids, packer fluids, core drilling fluids, completion fluids, and in other oilfield and well operating applications.

Additives that can be mixed with the base lubricating oil of the present invention to provide a finished lubricant composition include those intended to improve selected properties of the finished lubricant. Common additives include, for example, anti-wear additives, EP agents, detergents, dispersants, antioxidants, agents that lower the pour point, agents for improving the VI, agents for modifying the viscosity, agents for modifying the friction , emulsifiers, anti-foaming agents, corrosion inhibitors, rust inhibitors, swelling sealing agents, emulsifiers, wetting agents, lubricating enhancing agents, metal deactivators, gelling agents, tackifying agents, bactericides, additives containing the liquid prevent loss, dyes and the like.

Other hydrocarbons, such as those described in U.S. Patent Nos. 5,596,883 and 5,190,912, may be mixed with the base lubricating oil, provided that the finished lubricant has the necessary pour point, kinematic viscosity, flash point and toxicity properties. These other hydrocarbons include base oils that are particularly useful in drilling fluids. For example, U.S. Pat. No. 5,596,883 relates to a substantially non-toxic base oil consisting essentially of branched paraffins or branched parafins substituted with an ester functionality, or mixtures thereof, the base oil preferably being between contains about 18 and about 40 carbon atoms per molecule and more preferably between about 18 and about 32 carbon atoms per molecule. U.S. Patent No. 5189012 relates to synthetic hydrocarbons selected from the group consisting of branched 1027901 "24 oligomers synthesized from one or more olefins containing a C 2 to C 14 chain and the oligomers having an average molecular weight of 120 to 1000.

Typically, the total amount of additives in the finished lubricant is from about 1 to about 30 percent by weight of the finished lubricant. However, since the base lubricating oils of the present invention have excellent properties including a low pour point, high VIs and excellent oxidation stability, a smaller amount of additives may be required to meet the specifications for the finished lubricant than is usually required with base oils. prepared by other methods. The use of additives in formulating ready lubricants is well documented in the literature and well known to those skilled in the art.

Examples 15

The invention is further illustrated by the following illustrative, non-limiting examples.

Each of these examples was conducted in a continuous flow high pressure test installation designed for hydroprocessing waxy carbon-hydrogen feeds. The isomerization catalyst was platinum prepared on SAPO-11 in a laboratory and contained 15 weight percent Catapal alumina binder. The catalyst was milled to 24-42 mesh before being charged to the reactor. The process conditions include a 1.0 hour LHSV over the isomerization catalyst and an H 2 flow rate at one-time throughput of 5,300 SCF / bbl. The complete ef-25 fluence of the isomerization reactor was fed directly to a second reactor containing a ground Pt-Pd / SiCVAbOs hydrofinish catalyst operated at 450 ° F and a 2 hour LHSV. The feed used for these examples was a hydrotreated wax obtained via Fischer-Tropsch and the properties of the feed (the hydrotreated Fischer-Tropsch wax) are as follows:

Specific weight, API 40.3 Nitrogen, ppm 1.6 1027901 "25

Sulfur, ppm 2

Sim. Dist., Wt.% Temperature (° F)

St / 5 512/59 / 10/30 637/708 50 76 70/90 827/911 95 / EP 941/1047

In the following examples, the effectiveness of sulfurizing the hydroisomerization catalyst is evaluated by measuring the 650 ° F + yield (weight percent) and the viscosity index of the isomerized Fischer-Tropsch wax.

It is known from the prior art that 650 ° F + yield (weight percent) is the weight percentage of the total product boiling at a temperature higher than 650 ° F and is defined or calculated at a specific pour point.

Example 1: 10

Hydroisomerization using a sulfurized SAPO catalyst at 1000 psig.

This example illustrates the effect of sulfurizing a SAPO-11 catalyst. In Figure 1, the 650 ° F + yield (weight percent) obtained when a wax obtained via Fischer-Tropsch is hydroisomerized is plotted as a function of the pour point (° C) for three situations: 1) if the SAPO-11 catalyst is not is sulphurized for the hydroisomerization reaction, 2) if the catalyst was pre-sulphurized and 3) if the catalyst was sulphurized again after it had been in operation for 2040 hours. Each of the three experiments was carried out at a hydrogen partial pressure of 1000 psig.

For comparison purposes, data points can be considered at a pour point of approximately -15 ° C. The 650 ° F + yield for the unsulfurized catalyst was about 32 weight percent, which increased to a yield of about 50 weight percent when the catalyst was presulfurized, representing an increase of about 18 weight percent. After re-sulfurizing the catalyst, the yield increased by a further 15% by weight to about 65% by weight.

The viscosity index was correspondingly improved by the sulfurization, as shown in Figure 2. At a pour point of -15 ° C, the viscosity index of the hydroisomerized wax increased from about 155 to 162 by pre-sulphurizing the catalyst and by resulphurization after 2040 hours of operation, the viscosity index increased even further to approximately 172. This represents an absolute increase of approximately 7 by presulphurization and approximately 10 by resulphurization.

Example 2:

Hydroisomerization using a sulfurized SAPO catalyst at different pressures. The effects of sulfurization at two different pressures (and the effects of pressure without sulfurization) are shown in Figures 3 and 4. The curves at 1000 psig in Figures 3 and 4 are the same as those in Figures 1 and 2; in other words, the data at 1000 psig has just been re-released. A decrease in the hydrogen partial pressure of 1000 to 300 psig during the hydroisomerization results in an increase in the 650 ° F + yield of approximately 35 to 68 weight percent and an increase in the viscosity index of approximately 155 to 168. This example thus shows that the yield of the hydroisomerization and viscosity index both increase as the hydroisomerization pressure is lowered.

In addition, comparing Figures 1 and 2 with Figures 3 and 4 illustrates that the sulfurization of a SAPO-11 had a greater beneficial effect at higher pressures (e.g., 1000 psig) than at lower pressures (e.g., 300 psig). Sulfurizing the SAPO-11 catalyst had a moderate effect on the 650 ° F + yield at 300 psig and a moderate effect on the viscosity index (an increase of about 5) in the range of the poured out points. Again, the pressures in this context relate to the hydrogen partial pressure in the hydroisomerization reactor, although the hydrogen partial pressure is substantially the same (or substantially the same) as the total pressure.

Example 3 1027901 "27

Hydroisomerization using a sulfurized zeolite catalyst

This example was carried out as described for Example 1, but using SSZ-32 as the catalyst. Figure 5 shows the 650 ° F + yield (weight percentage) from Fischer-Tropsch wax that is hydroisomerized at 1000 psig for both sulfurized and non-sulfurized SSZ-32 catalysts. The yield was approximately 55 (at a pour point of -15 ° C). Similarly, the viscosity index was approximately 175.

10

Example 4:

Hydroisomerization using a sulphurized SAPO catalyst 15 in operation

The effect of in-operation sulfurization on the ratio of iso-to-normal C4 is shown in Figure 7. In this example, a SAPO-11 catalyst was sulphurized after 150 hours of a hydroisomerization process when in use and the ratio of iso-to-normal C4 was plotted as a function of time. Figure 7 illustrates that the sulfur in operation of the catalyst resulted in an increase in the ratio of iso-to-normal C4 from about 0.2 to higher than 0.8, which is a more than 4-fold increase represents. A higher ratio of iso-to-normal C4 indicates improved selectivity for isomerization reactions relative to catalyst cracking reactions.

25

Example 5:

Hydroisomerization using a presulfurized S APO catalyst. The effect of pre-sulphurizing a SAPO-11 catalyst on the amounts of light hydrocarbons produced by hydroisomerization is shown in Figure 8. The total pressure in the reactor was 1000 psig and the temperature 1027901-28 was 650 ° F. There is a significant decrease in the amounts of normal and normal C5 and a much smaller decrease in the amounts of iso-C4 and 150 SO-C5.

Example 6: 5

Hydroisomerization using a pre-sulphurized SAPO catalyst at different temperatures

Figures 9A-C illustrate some observed relationships between the hydroisomerization temperatures and pressures. The graph in Figure 9 is a hydroisomerization temperature graph as a function of the pour point for each of the four tests (at total pressures of 150, 300, 500 and 1000 psig) shown in Figures 9A and 9B, with the the first figure shows the results of the 650 ° F + yield (weight percent) and the last figure shows the results of the viscosity index. An advantage of producing base lubricating oils at low pressure, in addition to improved production yields and viscosity indices with a sulfurized SAPO catalyst according to the present embodiments, is that the hydroisomerization process can be carried out at significantly lower operating temperatures than is otherwise the case.

By lowering the temperature of the hydroisomerization reaction, a larger temperature range is provided at which the reaction can be operated. In Figure 9C, at a pour point of, for example, -15 ° C, the temperature required by the suitable hydroisomerization catalyst is lowered by about 22 ° C when the operating pressure is lowered from 1000 to 500 psig. Under analogous conditions, the required temperature is lowered by approximately 37 ° C when the operating pressure is lowered from 1000 to 300 psig. Finally, the required temperature is lowered by approximately 47 ° C if the operating pressure is lowered from 1000 to 150 psig.

All publications, patents and patent applications mentioned in this application are hereby to be considered in their entirety to the same extent as inserted as if the description of each individual publication, patent application or patent in particular and separately in its entirety is as herein inserted.

Various modifications and changes to this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention. Other objects and advantages will be apparent to those skilled in the art after considering the foregoing description. Accordingly, the invention encompasses all structures and methods that fall within the scope of the appended claims.

1027901 "

Claims (26)

A method for producing a base lubricating oil from a wax-like hydrocarbon feed, the method comprising: a) sulfurizing a shape-selective noble metal-containing molecular sieve catalyst with an average pore size to provide a sulfurized catalyst, wherein the molar ratio of sulfur to noble metal in the sulfurized catalyst is greater than one; and b) hydroisomerizing the wax-like hydrocarbon feed by contacting the wax-like hydrocarbon feed with the sulfurized catalyst under hydroisomerization conditions to produce a base lubricating oil. The method of claim 1, wherein the sulfurizing step is a pre-sulfuric step. The method of claim 1, wherein the sulfurizing step is a sulfur step when in operation. 20 The process according to claim 2, wherein the molar ratio of sulfur to noble metal in the sulfurized catalyst before the hydroisomerization step is at least 2: 1 and wherein the molar ratio of sulfur to noble metal in the sulfurized catalyst during the hydroisomerization step is at least 3: 1. 25 The method according to claims 2 or 4, wherein the molar ratio of sulfur to noble metal in the sulfurized catalyst is at least 3: 1. The process according to claim 2, 4 or 5, wherein the molar ratio of sulfur to noble metal in the sulfurized catalyst is at least 5: 1. A method according to any one of the preceding claims 1-6, wherein the wax-like hydrocarbon feed is selected from the group consisting of gas oil, lubricating oil raw material, synthetic oil, wax obtained via Fischer-Tropsch, oligomerized, via Fischer-Tropsch olefins obtained, foot oils, slag wax, defoiled wax, normal alpha-olefin wax, microcrystalline wax and mixtures thereof. The method of claim 7, wherein the wax-like hydrocarbon feedstock is a wax obtained via Fischer-Tropsch. The method of any one of the preceding claims 1-8, wherein the molecular sieve has channel diameters in the range of 4.0 to 7.1 A. 10 The method of claim 9, wherein the molecular sieve is non-zeolietic. 11. The method of claim 10, wherein the catalyst is a SAPO catalyst. The method of claim 11, wherein the SAPO catalyst is selected from the group consisting of SAPO-11, S APO-31 and S APO-41. The method of any one of claims 1 to 12, wherein the noble metal is selected from the group consisting of platinum, palladium, and mixtures thereof. 14. A method according to any one of claims 1-13, wherein the pre-sulfur step comprises contacting the catalyst with a sulfur-containing species in the presence of hydrogen, the sulfur-containing species being selected from the group consisting of hydrogen sulfide, carbon disulfide and a mercaptan. The method of claim 14, wherein the wax-like hydrocarbon feed contains less than 10 ppm of sulfur. 30 The method of any one of the preceding claims 1-15, wherein the wax-like hydrocarbon feedstock is a sulfur-mixed feedstock. 1027901 * » A method according to any one of the preceding claims 1-16, wherein the hydroisomerization conditions comprise a total pressure between 150 and 1000 psig. 18. The method of claim 17, wherein the hydroisomerization conditions comprise a total pressure between 150 and 500 psig. The method of claim 18, wherein the hydroisomerization conditions comprise a total pressure between 150 and 300 psig. The method of claim 17, wherein the hydroisomerization conditions comprise a total pressure between 500 and 1000 psig. A method according to any one of the preceding claims 1-20, wherein between 40 and 95% by weight of the basic lubricating oil has a boiling point between 650 and 1400 ° F. 15 The method of any one of the preceding claims 1-21, wherein the base lubricating oil has a viscosity index between 140 and 190. 23. A method according to any one of the preceding claims 1-22, wherein the basic lubricating oil has a pour point between -5 and -60 ° C. The method of any one of claims 1-23, wherein the base lubricating oil has a viscosity at 100 ° C of more than 3 cSt. The method of any one of the preceding claims 1-24, further comprising solvent dewaxing at least a portion of the base lubricating oil, wherein a slag wax is removed. 26. The method of claim 25, further comprising hydroisomerizing the slag wax with the wax-like hydrocarbon feed. 1027901 "