DE69533139T2 - WACHSHYDROISOMERISIERVERFAHREN - Google Patents

Description

cross-reference on related Registrations

This registration concerns the same time pending Registration, serial number 08 / 017,949 (continuation of S.N. 07 / 548,702), with the title "Production of High Viscosity Index Lubricants "which is a two step process for Manufacture of lubricants with a high viscosity index by hydrocracking and hydroisomerizing raw paraffin feeds using a zeolite hydroisomerization catalyst Low acidity beta describes. The serial number 08 / 017.955, also with the title "Production of High Viscosity Index Lubricants ", describes a process for hydroisomerizing wax under Use of zeolite catalysts with a regulated low acidity at high pressure. The present application is a partial continuation of Serial number 08 / 017.955. The present application is also a partial continuation of the Serial number 08 / 017,949. The serial number 08 / 017.955 is in the present application mentioned as a reference. The corresponding European patent No. 464,547A1 (which the use of zeolite beta with a low acidity for isomerizing wax) is also mentioned as a reference. The This application also concerns the pending application S.N. 08 / 303,091, in which two catalysts for dewaxing are synergistic act, creating a lubricant with a high viscosity index is produced.

Territory of invention

The invention relates to the manufacture of high viscosity index lubricants by isomerization of raw paraffins using large pore zeolites and a small crystal size. The Can wax hydrocracked size before isomerization. The waxes can before hydrocracked after isomerization. The isomerization product can also with either a solvent or by catalytic measures be dewaxed to reach the pour point to be achieved.

general State of the art

Lubricants based on mineral oil become conventional produced by a separation sequence in the petroleum refinery carried out which is the fractionation of a paraffinic crude oil at atmospheric pressure, followed by fractionation under vacuum, thereby producing distillate fractions (Neutral oils) and a residue fraction generated after deasphalting and rigorous solvent treatment can also be used as a lubricant base material. This refined residue fraction will usually referred to as Brightstock. Neutral oils after solvent extraction, thereby removing components with a low viscosity index (VI) conventional dewaxing, either with a solvent or catalytic Dewaxing process, subjected to the desired To achieve pourpoint. The dewaxed base oil can do that Hydrofinishing to improve stability and color body to remove. The viscosity index (VI) reflects the amount of decrease in viscosity, which a lubricant experiences with increasing temperature. The Products from solvent dewaxing are dewaxed base oil and paraffin gossip. Paraffin gums typically contain 60 to 90% Wax, the rest of which is entrained oil. In some cases it is desirable to clean the paraffin gums from the entrained oil by the paraffin gums a deoiling step is subjected to paraffin wax with dewaxing solvents dilute and is filtered at a temperature higher than that in the filtering step is used, which serves to create paraffin gossip. The cleaned Wax is de-oiled Wax denotes and contains more than 95% wax. The by-product of the second filtration typically contains 50% wax and is used as a floor oil designated.

Catalytic dewaxing of base oils is typically done by cracking the wax molecules into low-boiling Products are transferred or by adding the wax molecules areomerized, thereby producing species that are dewaxed oil remain. Catalysts for the dewaxing obtain the high yield primarily by that she Have pore structures that are cyclic and strong cracking inhibit branched species, generally with dewaxed Lubricating oil connected are while almost linear molecules, of which the wax is generally made, easier access to the catalytically active places possible is. Catalysts that allow access of species based on the Molecular size clearly decrease, are called shape selective. A higher shape selectivity of a Catalyst for dewaxing increases frequently the yield of dewaxed oil.

The shape selectivity of a dewaxing catalyst is practically limited by its ability to convert wax molecules that have a slightly branched structure. These types of species are more commonly associated with higher boiling base oils such as Brightstock. Highly shape-selective dewaxing catalysts may not be able to handle high-boiling branched wax species convert, which leads to a cloudy appearance of the lubricating oil at ambient temperature and a high cloud point in relation to pour point.

Conventional refining processes of lubricating oils are based on the appropriate selection and use of the crude oils, usually with paraffinic in character, in reasonable quantities of lubricating oil fractions with the ones you want qualities produce. The range of allowed crude sources however, can be expanded through the process of hydrocracking lubricating oil raw materials of poor or poor quality, usually with a higher one Aromatic content as the best paraffinic crude oils. The procedure for hydrocracking lubricating oil, that is in the petroleum refining industry well established generally a first hydrocracking step, which at high pressure, high temperature and in the presence of a bifunctional catalyst carried out which is a partial saturation and ring opening of the aromatic components present in the feed are. The hydrocracked product is then dewaxed subjected to achieve the pour point to be achieved since the hydrocracked product usually Species with a relatively high pour point. The liquid product on the dewaxing step becomes common a low temperature hydrogen treatment step and subjected to high pressure to increase the aromatic content of the lubricating oil desired Decrease value.

Current trends in design of automotive engines are at higher operating temperatures connected as the performance of the motors increases. These higher operating temperatures require ever better quality lubricants. A the demands are higher viscosity indexes (VI) to the effects of higher Operating temperatures to the viscosity of engine lubricants reduce. High VI values have become conventional through use of means to improve the VI, e.g. B. polyacrylates and polystyrenes, reached. VI improvers tend to degrade high temperatures and high shear rates that occur in the engine. The tougher Conditions associated with high performance engines lead to an even faster breakdown of oils, the significant amounts use funds to improve VI. So there is always a need for lubricants for Motor vehicles based on fluids with a high viscosity index based and the opposite are resistant to high temperature and high shear rate conditions, that occur in modern engines.

Synthetic lubricants made by Polymerization of olefins in the presence of certain catalysts have shown excellent VI values, their production however, is relatively expensive. Hence there is a need for manufacture of high VI lubricants made from mineral oil materials by process can be generated comparable to those currently used in oil refineries.

U.S. Patent No. 4,975,177 discloses a two-stage dewaxing process for producing high VI base oils from waxy feeds. In the first stage of this process, the waxy feed is catalytically dewaxed by isomerization over zeolite beta, which contains a noble metal. The examples use a pressure below 6996 kPa _a (1000 psig) and a medium acidity catalyst with an α value of about 55. The product of the isomerization step still contains waxy species and must be further dewaxed to achieve the pour point to be achieved. Dewaxing in the second stage either uses solvent dewaxing, in which case the retained wax can be recirculated to the isomerization stage to maximize yield, or catalytic dewaxing. Catalysts that can be used in this second stage are ZSM-5, ZSM-22, ZSM-23 and ZSM-35. To maintain yield and VI, the second stage dewaxing catalyst should have a selectivity similar to solvent dewaxing. U.S. Patent 4,919,788 also describes a two-stage dewaxing process in which the waxy feed is partially dewaxed by isomerization over a silicon-containing catalyst Y or beta containing a noble metal. Examples indicate a pressure of less than 10030 kPa _a and a zeolite beta catalyst with moderate acidity and an α value of 55. This product is then dewaxed to the desired pour point using either solvent dewaxing or catalytic dewaxing. Catalysts for dewaxing with high shape selectivity, such as ZSM-22 and ZSM-23, are preferred catalysts.

Serial number 08 / 017,949 is disclosed a two-stage hydrocracking and Hydroisomerization. The first stage uses a bifunctional one Catalyst containing a metal hydrogenation component an amorphous acid carrier includes. The second stage, the hydroisomerization step, is over zeolite Beta done. The subsequent one Dewaxing is optional, but recommended. Then you can either dewax the solvent or catalytic dewaxing can be applied to the VI and pour point to be achieved.

In SN 08 / 017,955, a raw paraffin feed is subjected to the hydroisomerization over a zeolite catalyst with low acidity containing noble metal. The paraffins present in the feed are selectively converted to isoparaffins with a high VI, but with a lower pour point, so that with a minimal amount of subsequent dewaxing, a final lubricating oil product with good viscosimetric properties is produced. The process, which operates at high pressure, is for the quality improvement of waxy feeds, such as paraffin gums, with an aromatic content greater than about 15% by weight in high viscosity index lubricating oils with high yields in a single pass and with limited dewaxing required of the product well suited.

U.S. Patent No. 5,302,279 (and the analog European patent application EP 464 547 A1 ) describes the use of a form of low acidity zeolite beta for the isomerization and dewaxing of furfural raffinates. The examples showed the improved selectivity of a catalyst with low acidity over one with high acidity.

U.S. Patent No. 5,282,958 has the better isomerization for n-hexadecane shown using zeolites with the same pores and small crystal size, although the listed Crystal sizes all extremely small and do not match the measurements made by others in the field of catalyst production. Moreover allow the zeolites with restricted medium pores, such as ZSM-22 and ZSM-23 used in this patent access into the lattice of the catalyst not as easily as other molecular sieves with medium and large Pores. The reactions of molecules lubricant type are likely to occur near the pore opening of the Medium pore catalysts. The crystal size of ZSM-22 or ZSM-23 affected probably the isomerization selectivity is not as clear as in Catalysts with a less restrictive pore structure.

Short description the invention

The concept of the present invention involves a process for isomerization and dewaxing of paraffinic or waxy feed materials under Use of molecular sieves with large pores and a small one Crystal size for generation of high quality lubricant base materials with a VI of at least 130. Molecular sieves useful in this invention with big Pores are defined so that they have a constraint index of less than 1, and include the Zeolites beta, mordenite and Y. Large pore molecular sieves assign accessible Pore structures to make from waxy feed materials, especially those materials that are high molecular weight species contain to produce highly branched paraffins. This branched Paraffins have a high VI and a low pour point. Since the isomerization takes place within the pores of the catalyst, allows a small crystal size that branched Diffuse paraffins easily from the zeolite pores without cracking, which leads to high lubricating oil yields leads.

The present invention includes treating a waxy hydrocarbon feedstock over one Isomerization catalyst that branches into waxy species Paraffins transferred. The Formation of these branched paraffins, which have high viscosity indices and have low pour points results in a lubricant base material with excellent quality.

The feed materials used in this invention contain at least 20% wax, and preferably contain more than 50% wax. The feed material can be pretreated prior to isomerization to remove nitrogen and sulfur containing species and to reduce their aromatic content. The crude or pretreated feedstock is contacted with a large pore, low acidity noble metal molecular sieve over which a substantial portion of the wax in the feed is isomerizes to produce species typically associated with lubricating oil base materials. The isomerization typically takes place at a pressure of 4238 kPa _a (600 psig) to 20786 kPa _a (3000 psig). The isomerization effluent can be subjected to hydrogen treatment to remove residual aromatics. The zeolite beta catalyst illustrated in the examples of this invention has a crystal diameter of less than 0.1 µm in order to maximize the relative rate of isomerization versus that of cracking. Small diameter crystals allow isomerized species to diffuse easily from the lattice of the catalyst, reducing the possibility of them being cracked. The prior art explained above in the general prior art shows a better selectivity of the catalyst with low acidity over one with higher acidity. A low acidity of the zeolite combined with a high activity of metals is necessary for a high isomerization selectivity, but does not guarantee such selectivity. The crystal size of certain molecular sieves has been found to be an important factor affecting isomerization selectivity. Large crystals extend the diffusion path for the isomerized species to exit the lattice, increasing the possibility of the isomerized molecule being cracked inside the lattice. The invention explains here in detail the selectivity advantage for the isomerization of waxy feeds, such as paraffin wax, with a zeolite beta catalyst with small crystals and low acidity.

The present invention uses zeolite beta loaded with a noble metal such as Pt to selectively isomerize waxy species to high VI lubricants. This catalyst has one high isomerization selectivity, tolerance for moderate amounts of sulfur and nitrogen and an accessible pore structure, so that the conversion of voluminous wax molecules is possible. The selectivity of zeolite beta loaded with Pt is optimized if it has a low acidity of the zeolite, a good dispersion of the metals and a small crystal size.

description the drawing

The figure compares the selectivity at the Isomerization of wax for two silica-bound zeolite beta catalysts with low acidity, which is loaded with Pt. One has a small crystal size and the others have a big one Crystal size.

Full Description of the invention

In the process of the invention, feeds are used with a relatively high wax content in a hydroisomerization process converted to high VI lubricant, where a low zeolite hydroisomerization catalyst acidity is used, which has a small crystal size. The subsequent dewaxing may be required to remove residual wax from the isomerization step to remove. The products have good viscometric properties marked, belongs to it a high viscosity index, typically at least 140 ° C at a pour point of -17.78 ° C (0 ° F) and usually in Range from 143 to 147.

feed

The processes according to the invention can be carried out with a wide range of feeds derived from mineral oil, creating a range of lubricant products with good performance is produced. These features include a low pour point, a low cloud point and a high viscosity index. The quality of the product and the yield with which it is obtained depend on of quality the feed and its suitability for treatment with the catalysts of the invention from. Products with the highest VI are through the use of preferred wax loads, such as Paraffin gums, soil oil, deoiled Wax, vacuum distillates derived from waxy crude oils, wax from a Fischer-Tropsch process, petrolatum, vacuum gas oil or one Raffinate from solvent extraction of vacuum distillate. Products with lower VI values can can also be obtained from other feeds that have a lower Initial amount of waxy components included.

The feeds that used can be should have an initial boiling point that is not lower than the starting boiling point of the desired Is lubricant. A typical initial boiling point of the feed exceeds 343 ° C (650 ° F). feedstocks of this type that can be used include vacuum gas oils as well also other high-boiling fractions, such as distillates from vacuum distillation of atmospheric Residues, raffinates from solvent extraction of these distillate fractions, hydrocracked vacuum distillates and Dewax wax from solvent of raffinates and hydrocracked products.

Feeding may be required prepare to be satisfactory in the hydroisomerization step can be treated. The preparatory steps, the general are required are those that have a low component VI, such as aromatics and polycyclic naphthenes, as well as nitrogen and remove sulfur-containing species.

Suitable pretreatment steps for preparing feeds for hydroisomerization are those that remove aromatics and other low VI components from the original feed. The hydrogen treatment is particularly at high hydrogen pressure, which is effective for saturating the aromatics, for. B. 5600 kPa _a (800 psig) or above is an effective pretreatment step. The mild hydrocracking can also be used as a pretreatment and is preferred in the present invention when pretreatment is required. Example 3 below illustrates the hydrocracking conditions used in the present invention to prepare a feed for the dewaxing process. A pressure greater than 6996 kPa _a (1000 psig) is preferred for the hydrocracking treatment. Hydrocracking removes nitrogen and sulfur-containing species and reduces the aromatic content, as shown in Table 6 below. Hydrocracking has also slightly changed the feed boiling range in this example, causing it to boil in a lower range. Commercial catalysts, such as nickel tungsten fluoride on aluminum oxide (NiWF- / Al ₂ O ₃ ), can be used for the hydrocracking pretreatment.

The preferred gas oil and vacuum distillate feeds are those with a high wax content determined according to ASTM D-3235, preferably more than about 30% by weight, and more preferably more than 50% by weight. This type of feed includes certain oils from Southeast Asia and mainland China. Minas Gas Oil from Tunisia is one such feed. These feeds usually have a high paraffin content, which is determined by conventional analysis for paraffins, naphthenes and aromatics. The properties of typical loads of this type are described in SN 07 / 017,955. A preferred feed has a wax content of at least 40% by weight and an aromatic content of less than 25% by weight.

As already stated, the Wax content of preferred feeds high before pretreatment, generally at least 30% by weight (determined according to ASTM Test D-3235). The wax content is before pretreatment even more common at least 60 to 80% by weight, with the rest trapped oil which includes isoparaffins, aromatics and naphthenes. This wax-like, highly paraffinic wax materials due to their relatively low levels of aromatics and naphthenes usually one low viscosity, although the high content of waxy paraffins gives them melting points and gives pourpoints with which they can be used as lubricants without further treatment become unacceptable. Wax loads are in S.N. 07 / 017,955 explained further.

The most preferred type of Wax loading is paraffin gossip (see table below 2). These are waxy products that come directly from a solvent dewaxing process, z. B. a dewaxing process with MEK (methyl ethyl ketone) / toluene or MEK / MIBK (methyl isobutyl ketone) or propane. The paraffin gum, which is a solid to semi-solid product, that is primarily strong waxy paraffins (mainly n- and monomethyl paraffins) together with trapped oil be used directly or an initial deoiling step from the conventional Undergo character to remove the trapped oil. The removal of the oil leads to a harder one stronger paraffin wax, which can then be used as a feed can. The by-product of the deoiling step is called soil oil referred to and can also be used as a feed for this process become. floor oil contains the biggest part the one in the original Paraffingatsch existing aromatics and with these aromatics biggest part of heteroatoms. Paraffin gossip and soil oil typically require pretreatment before catalytic dewaxing. The oil content de-oiling Wax can be quite low, and for this purpose, can be used for reproducibility a measurement of the oil content the procedure of ASTM D721 may be required because of the above called test D-3235 at an oil content less than about 15% by weight to lower reliability inclines.

In Table 1 below are the compositions of some typical waxes are listed.

Table 1 Wax composition - crude oil "Arab Light"

A typical paraffin wax feed has the composition shown in Table 2 below. This paraffin wax is obtained from the solvent dewaxing (MEK) of a neutral oil obtained from the crude oil "Arab Light" at 65 mm ² / s (cSt) at 40 ° C (300 SUS). Table 2 Properties of paraffin gossip Degree API 39 Hydrogen,% by weight 15.14 Sulfur, wt% 0.18 Nitrogen, ppmw 11 Melting point, ° C (° F) 57 (135) KV at 100 ° C, cSt 5,168 PNA % By weight paraffins 70.3 naphthenes 13.6 aromatics 16, 3

Simulated distillation:

Another paraffin gossip that is for use in the method according to the invention is suitable has the properties below as part of Example 3 listed in Table 6 are. This wax is dewaxed by solvent of a high-boiling neutral furfural raffinate. How already explained Hydrocracking can be applied to pre-paraffin gossip to prepare for hydroisomerization.

Hydrocracking process (optional)

When hydrocracking is used as a pretreatment step, an amorphous bifunctional catalyst is preferably used to promote the saturation and ring opening of the poor quality aromatic component in the feed, producing hydrocracked products that are relatively more paraffinic. The hydrocracking is carried out at high pressure to favor the saturation of the aromatics, but the boiling range conversion is kept at a relatively low level to minimize the cracking of the saturated components of the feed and the products caused by the saturation and ring opening of the aromatic materials were obtained. In accordance with these objectives of the process, the hydrogen pressure in the hydrocracking stage is at least about 5500 kPa _a (800 psig), and is usually in the range of 6900 kPa _a (1000 psig) to 20700 kPa _a (3000 psig). Normally, a partial pressure of hydrogen of at least 10500 kPa _a (1500 psig) is best to achieve a high level when aromatics are saturated. Circulation rates of hydrogen of at least about 178 nl / l (1000 scf / bbl), preferably in the range from 900 nl / l (2000 scf / bbl) to 1800 nl / l (8000 scf / bbl) are suitable.

In the hydrocracking process, the conversion of the feed to products boiling below the boiling range of lubricating oil, typically 345 ° C (650 ° F) products, is limited to no more than 50% by weight of the feed and is usually no more than 30% by weight of the feed to maintain the desired high yields characteristic of this process in one pass. The actual conversion depends on the quality of the feed, with paraffin wax feeds requiring less conversion than petrolatum, where it is necessary to remove more poor quality polycyclic components. For paraffin wax feeds derived from the dewaxing of neutral feedstocks, conversion to 345 ° C (650 ° F) products for all practical purposes is no higher than 10 to 20% by weight, with most paraffin wax 5 to 15 % By weight are typical. Petrolatum feeds can involve higher conversions because they typically contain more poor quality components. For petrolatum feeds, the hydrocrack conversion is typically in the range of 15 to 25% by weight to produce high VI products. The conversion can be maintained at the desired level by controlling the temperature in the hydrocracking stage, which is typically in the range of 315 to 430 ° C (600 to 800 ° F) and more usually in the range of approximately 345 to 400 ° C (650 to 750 ° F). Changes in space velocity can also be used to control severity, although this is less common in practice given the mechanical stress on the system. The space velocity is generally in the range of 0.25 to 2 LHSV, h ^-1 and usually in the range of 0.5 to 1.5 LHSV.

A characteristic of the hydrocracking process is the use of a bifunctional catalyst comprising an acidic carrier. Generally speaking, these catalysts include a metal component to promote the desired aromatic saturation reactions, and a combination of base metals with an iron group (Group VIII) metal is commonly used in combination with a Group VIB metal. The base metal, such as nickel or cobalt, is therefore used in combination with molybdenum or tungsten. The preferred combination is nickel / tungsten as it has proven to be very effective in promoting the desired hydrocracking reaction of aromatics. Noble metals such as platinum or palladium can be used because they have good hydrogenation activity when no sulfur is present, but they are usually not preferred. The amounts of metals present on the catalyst are conventional for this type of lubricating oil hydrocracking catalyst and are generally in the range of 1 to 10% by weight of Group VIII metal and 10 to 30% by weight of the metal Group VI, based on the total weight of the catalyst. If a noble metal component, such as platinum or palladium, is used instead of a non-noble metal, such as nickel or cobalt, relatively smaller amounts are required in view of the higher hydrogenation activities of these noble metals, typically about 0.5 to 5% by weight being sufficient. The metals can be introduced by any suitable method, including impregnation on the porous support after it has been formed into particles of the desired size, or addition to a gel of the support materials prior to calcination. The addition to the gel is a preferred method when relatively large amounts of the metal components are to be added, e.g. B. more than 10% by weight of Group VIII metal and more than 20% by weight of Group VI metal. These processes are conventional in character and are used for the manufacture of catalysts for hydrocracking lubricating oil.

The metal component of the catalyst is generally made from a porous, amorphous support Metal oxide worn, and for alumina is preferred for this purpose, although also silica-alumina can be used. In the carrier can other metal oxide components are also present, although their presence less desirable is. In accordance with the requirements for a catalyst for hydrocracking lubricating oil the carrier a pore size and distribution have that are appropriate to the relatively voluminous components of the high-boiling charges in the inner pore structure of the Catalyst can penetrate, in which the desired Hydrocracking reactions take place. For this purpose the catalyst has normally a minimum pore size of about 50 Å, that is, not less than about 5% of the pores have a pore size of less than 5 nm (50 Å), being the largest part the pores a pore size in the range from 5 to 40 nm (50 to 400 Å) has (with no more than 5% having a pore size of more than 40 nm (400 Å)), preferably no more than about 30% pore sizes in the range from 20 to 40 nm (200 to 400 Å) to have. Preferred hydrocracking catalysts are at least 60% of the pores in the range of 5 to 20 nm (50 to 200 Å). The Pore size distribution and other properties of some typical hydrocracking catalysts of lubricating oil (LHDC) which for which are suitable for use in hydrocracking are as follows Table 3 shown:

Table 3 Properties of catalysts for the LHDC

To achieve the desired conversion, the catalyst can be promoted with fluorine, if necessary, either by introducing fluorine into the catalyst during manufacture or by hydrocracking in the presence of a fluorine compound that is added to the feed. Fluorine-containing compounds can be introduced during the preparation of the catalyst by impregnation with a suitable fluorine compound, such as ammonium fluoride (NH ₄ F) or ammonium bifluoride (NH ₄ F · HF), the latter of which is preferred. The amount of fluorine used in catalysts containing this element is preferably about 1 to 10% by weight based on the total weight of the catalyst, usually about 2 to 6% by weight. Fluorine can be introduced by adding the fluorine compound to a gel of the metal oxide support during the preparation of the catalyst or by impregnating after the catalyst particles have been formed by drying or calcining the gel. If the catalyst contains a relatively large amount of fluorine as well as large amounts of metals as listed above, it is preferred to introduce the metals and the fluorine compound into the metal oxide gel before the gel is dried and calcined to produce the finished catalyst particles ,

The activity of the catalyst can also at the desired one Value is maintained by fluorinating in situ, using a fluorine compound added to the stream over the catalyst at this stage of the process flows. The fluorine compound can be fed continuously or discontinuously can be added, or in another embodiment, a first Activation step carried out be in which the fluorine compound without the feed, e.g. B. in a stream of hydrogen, about the catalyst flows with it the fluorine content of the catalyst is increased before the actual one Hydrocracking is initiated. Fluorination of the catalyst in situ in this way is preferably made to before the Procedure to produce a fluorine content of about 1 to 10%, afterwards the fluorine can be reduced to sufficient entertainment values, the desired one activity preserved. Suitable compounds for fluorination in situ are Orthofluorotoluene and difluoroethane.

The ones present on the catalyst Metals are preferably used in and for their sulfide form For this purpose, the previous sulfidation of the catalyst should be carried out before hydrocracking is initiated. The sulfiding poses is a recognized technique and is typically performed by the catalyst, usually in the presence of hydrogen, with a gas containing sulfur Is brought into contact. A mixture of hydrogen and hydrogen sulfide, Carbon disulfide or a mercaptan such as butol mercaptan For this Purpose conventional. The previous sulfiding can also be carried out by the catalyst with hydrogen and a sulfur-containing hydrocarbon oil, such as acidic kerosene or gas oil, is brought into contact.

hydroisomerization

The ones in the original wax load paraffinic components have high viscosity indices, however, have relatively high pour points. The object of the method according to the invention consequently, is a selective conversion of the waxy Species to make while the conversion of stronger branched species is minimized, which are characteristic of lubricating oil components. The wax is preferably converted by isomerization, making stronger branched species are generated, the lower pourpoints and Cloud points exhibit. The isomerization is accompanied by some cracking, the extent of Cracking changes with the degree of conversion of the wax.

catalyst for the hydroisomerization

The hydroisomerization in this invention The catalyst used is one that has high selectivity for isomerization from waxy, linear or almost linear paraffins to less waxy, owns isoparaffinic products. Have catalysts of this type a bifunctional character, being a metal component on a porous carrier with a big one Pore size and a relative low acidity include. The acidity is kept low at this stage of the process, to lessen the conversion to products that are outside the boiling range of lubricating oil boil. Generally speaking the catalyst should have an α value of before adding the metals have no more than 30, with preferred values no more than 20 (see example 1).

The α value is an approximate description of the catalytic cracking activity of the catalyst in comparison with a standard catalyst. The α test indicates the relative rate constant (rate of conversion of n-hexane per volume of catalyst per unit time) of the test catalyst in relation to the standard catalyst, which is assumed to be α = 1 (rate constant = 0.016 s ⁻¹ ). The α test is described in U.S. Patent 3,354,078 and J. Catalysis, 1, 527 (1965); 6, 278 (1966) and 61, 395 (1980), which are referred to for the description of the test. The experimental conditions of the test which served to determine the α values mentioned in this description include a constant temperature of 538 ° C and a variable flow rate as described in detail in J. Catalysis, 61, 395 (1980) ,

The hydroisomerization catalyst comprises a large pore molecular sieve, generally a zeolite or silica: aluminophosphate. The sieve with large pores is carried by a porous binder. Large pore zeolites usually have at least one pore channel consisting of 12-membered oxygen rings. Zeolites Beta, Y and Mordenite are large pore zeolites. The catalysts of the invention have a crystal diameter of less than 0.1 μm so that the relative rate of isomerization compared to that of cracking is maximized. Small diameter crystals allow isomerized species to diffuse easily from the crystal lattice, creating a ge there is less chance that they will be cracked.

The preferred hydroisomerization catalyst uses zeolite beta, since this zeolite has been shown to have excellent activity for the isomerization of paraffins in the presence of aromatics, as described in US Pat US 4,419,220 is disclosed. The forms of low acidity zeolite beta can be obtained by synthesis of a silicon-rich form of zeolite, e.g. B. with a silica / alumina ratio of more than about 500: 1, or more easily by steaming the zeolites with a lower silica / alumina ratio up to the required acidity value. They can also be obtained by extraction with acids such as dicarboxylic acids as disclosed in U.S. Patent No. 5,200,168. U.S. Patent No. 5,238,677 discloses the synthesis of dealuminized mordenite by extraction with oxalic acid. U.S. Patent No. 5,164,169 discloses the preparation of high-silica zeolite beta using a chelating agent such as tertiary alkenolamines in the synthesis mixture. US Patent No. 3,308,069 describes the synthesis of zeolite beta with a crystal size in the range from 0.01 to 0.05 μm. Catalysts with crystal sizes in this range are used in the present invention. The crystal size does not exceed 0.1 µm in the present invention, although a crystal size of 0.01 to 0.05 µm is preferred.

The most preferred zeolites undergo rigorous steaming and have a silica / alumina ratio of Grid of at least 200: 1 and more preferably of more than 400: 1.

The steam treatment conditions should can be adjusted to the desired α value in the finished catalyst achieve, and typically 100% vapor atmospheres at temperatures from about 427 to 595 ° C (800 to about 1100 ° F) used. Steam treatment is usually about 12 to 120 Hours, typically about 96 hours, at temperatures above than 538 ° C (1000 ° F) carried out, to the one you want Decrease in acidity to reach.

Another manufacturing process of a low-acidity zeolite beta catalyst to replace part of the aluminum in the lattice of the zeolite another trivalent element, like boron, resulting in a lower one leads to intrinsic value of acidic activity in the zeolite. The preferred zeolites of this type are those which contain boron in the lattice. Boron is common to the zeolite lattice added before adding other metals. For zeolites of this type the grid is basically there made of silicon, which coordinates tetrahedrally and with each other oxygen bridges connected is. The minor Amount of an element (alumina in the case of an aluminosilicate zeolite Beta) is also coordinated and forms part of the grid. The zeolite contains in the pores of the structure also material, although this is not part of the lattice that form the characteristic structure of the zeolite represents. The term boron "in Grid "serves here the distinction between a material in the lattice of the zeolite, which is shown by the fact that it to ion exchange capacity of the zeolite, and a material that is present in the pores and does not affect the total ion exchange capacity of the zeolite. Zeolite Beta has at temperatures of 316 up to 399 ° C a compulsory index of 0.60 to 2.0, although compulsory indices of less are preferred as 1.

Process for the production of zeolites high silica content containing boron in the lattice known and z. For example, described in U.S. Patent No. 4,269,813. A procedure for the production of zeolite beta, which contains boron in the lattice in U.S. Patent No. 4,672,049. As stated there, can the amount of boron contained in the zeolite can be changed by different Amounts of borate introduced into the solution forming the zeolite be, e.g. B. by using different amounts of boric acid in relation to to the forces of silica and alumina. For the description of the procedures, According to which these zeolites can be produced is based on these descriptions Referred.

The low acidity zeolite beta catalyst should contain at least 0.1% by weight boron, preferably at least 0.5% by weight boron, in the lattice. Boron can be added to the grid before adding other metals. The maximum amount of boron is usually about 5% by weight of the zeolite and in most cases no more than 2% by weight of the zeolite. The grid usually also includes some alumina. In the state in which the zeolite is synthesized, the ratio of silicon dioxide: aluminum oxide is usually at least 30: 1. A preferred zeolite beta-substituted catalyst is prepared by steaming an originally boron-containing zeolite which is at least 1 wt .-% boron (as B ₂ O ₃ ) contains, which leads to a final α value of not more than about 20 and preferably not more than 10.

characteristics

The acidity can be reduced if nitrogen compounds, e.g. B. NH ₃ or organic nitrogen compounds are introduced with the feed for the hydroisomerization catalyst. However, the total nitrogen content of the feed should not exceed 100 ppm and should preferably be less than 20 ppm. The catalyst can also contain metals that reduce the number of highly acidic sites on the catalyst and improve the selectivity for isomerization reactions over cracking reactions. Preferred metals for this purpose are those belonging to the class of group IIA metals, like calcium and magnesium.

The zeolite is bonded to a matrix material to produce the final catalyst, and conventional very low acidity matrix materials such as alumina, silica-alumina and silica are suitable for this purpose, although alumina such as alpha-boehmite (alpha-alumina monohydrate) is also suitable can be used provided that they do not impart substantial acidic activity to the catalyst associated with the matrix. The zeolite is usually bonded to the matrix in amounts by weight of 8:20 to 20:80, typically 80:20 to 50:50 zeolite: matrix. The connection can be carried out by conventional measures, including joint grinding of the materials, followed by extrusion to the desired finished catalyst particles. A preferred method for extruding the zeolite with silica as a binder is in US Pat US 4,582,815 disclosed. If the catalyst is to be steamed to achieve the desired low acidity, it is carried out, as is conventional, after the catalyst has been formulated with the binder. The preferred binder for the steamed catalyst is alumina.

The hydroisomerization catalyst includes also a metal component to achieve the desired hydroisomerization reactions to promote, which require mediation by a hydrogenation / dehydrogenation component because them over unsaturated transition species run. To maximize the isomerization activity of the catalyst, metals with a strong hydrogenation function are preferred, and from for this reason platinum and other precious metals such as rhenium, Gold and palladium are preferred. The amount of the hydrogenation component a noble metal is typically in the range of 0.1 to 5% by weight of the total catalyst, usually from 0.1 to 2% by weight; a preferred catalyst comprises 0.3 to 2 wt% Pt a carrier, the zeolite beta comprises. The platinum can be made according to conventional Processes are introduced into the catalyst, including ion exchange with cations of a platinum complex, such as platinum tetraamine, or that Impregnate with solutions of soluble Platinum compounds, e.g. B. with platinum tetraamine salts such as platinum tetraamine chloride. The catalyst can undergo final calcination in conventional Conditions are subjected to the precious metal in its reduced To convert form and to give the catalyst the required mechanical strength. Before use, the catalyst may undergo prior sulfidation be subjected as described above for the pretreatment of the catalyst before hydrocracking has been described.

hydroisomerization

The conditions for hydroisomerization (also referred to as isomerization) are set so that the task the isomerization of the waxy, linear and almost linear paraffinic components in the waxy feed to less waxy isoparaffinic materials with a relatively lower Pourpoint however solved high VI becomes. The process is preferably carried out in the presence of hydrogen carried out, whereby 40 to 90% by weight of the wax contained in the feed. This Goal is achieved, converting to products outside the boiling range of lubricating oil, Materials minimized at 345 ° C- (650 ° F-) becomes. Since the for the hydroisomerization catalyst used has a low acidity the conversion to low-boiling products usually at a relatively low Value, and by appropriate selection of the severtiy can carry out the Procedure for versus the isomerization cracking can be optimized. At conventional space velocities of about 1 and the use of a Pt / zeolite beta catalyst with an α value of less than 20, the temperatures for the hydroisomerization are typically in the range of about 288 to 427 ° C (550 to 800 ° F), preferably 300 to 415 ° C (about 570 to about 780 ° F), the conversion to 345 ° C- (650 ° F-typically about 5 to 30% by weight, more usually 10 to 25% by weight of the waxy feed.

Hydroisomerization occurs at a hydrogen partial pressure (reactor inlet) of at least 5516 kPa _a (800 psig), usually 5516 to 20785 kPa _a (800 to 3000 psig) and in most cases 5516 to 17340 kPa _a (800 2500 psig). The circulation rates of hydrogen are usually in the range of about 90 to 900 nl / l (500 to 5000 scf / bbl). Since some saturation of the aromatic components present in the original feed takes place on the catalyst in the presence of the hydrogenation component in the form of a noble metal, hydrogen is consumed in the hydroisomerization, although the desired isomerization reactions are in a hydrogen equilibrium; for this reason, it may be necessary to adjust the hydrogen circulation rates according to the aromatics content of the feed and also the temperature used in the hydroisomerization, since higher temperatures are associated with more cracking and consequently with higher olefin production, some of which are in the boiling range of lubricating oil are so that the stability of the product must be ensured by saturation. Circulation rates of hydrogen of at least 180 nl / l (1000 scf / bbl) normally provide enough hydrogen to compensate for the expected consumption of hydrogen as well to ensure a low aging rate of the catalyst.

A deterrent between beds is desired so that the temperature is maintained in this process. As a deterrent cold hydrogen is generally used, but it can also a liquid Deterrence, usually the recirculated product.

dewaxing

Depending on the wax content of the Feeding can also be a final dewaxing step be required to get the one you want To reach the pour point of the product. It is a remarkable one Feature of the method according to the invention, that this required extent of Dewaxing is relatively low. Typically the loss is at the final Dewaxing step no more than 15 to 20% by weight of the feed to the dewaxer and can be lower. At this Site can be either catalytic dewaxing or solvent dewaxing are used, and if a device for solvent dewaxing the removed wax can be used for a second pass recirculates the isomerization step for hydroisomerization become. The requirements for the dewaxing plant for this Product are relatively small, and the method according to the invention provides a significant improvement over the Process using only amorphous catalysts, in which one significant dewaxing is required. The high isomerization selectivity of the zeolite catalysts with big Enables pores it that high Wax conversions can be achieved in a single pass, typically about 80% compared to 50% for the process with an amorphous catalyst so that the throughput the plant is significantly improved.

In another embodiment can instead of attempting solvent dewaxing a shape selective catalyst for dewaxing can be used. This catalyst is removed the n-paraffins along with the waxy, slightly branched paraffins, while the stronger branched isoparaffins remain in the process stream. shape-selective Catalytic dewaxing processes use catalysts the for the removal of n-paraffins and slightly branched paraffins much more selective than the large pore isomerization catalyst, like zeolite beta. The selective catalytic dewaxing takes place as described in U.S. Patent No. 4,919,788, followed by the description this phase is referred to. The catalytic dewaxing step in the method according to the invention is preferably with a limited shape-selective dewaxing catalyst carried out, the one on a restricted crystalline material with medium pores, such as an aluminosilicate, based. A restricted medium crystalline material has at least one channel of 10-membered Oxygen rings with a channel that intersects them with 8 elements Wrestle on. ZSM-23 provides the for Zeolite is preferred for this purpose, although especially with low boiling ones Starting materials also other strongly shape-selective zeolites, such as ZSM-22 or the synthetic ferrierite ZSM-35 can be used can. Silicoaluminophosphates, such as SAPO-11 and SAPO-41, can be used as selective dewaxing catalysts are used.

The preferred catalysts for use as dewaxing catalysts are relatively restricted, medium pore size zeolites. Such preferred zeolites have a Constraint Index in the range of 1 to 12 which is determined by the method described in U.S. Patent No. 4,016,218. These preferred zeolites are also characterized by certain sorption properties which are related to their properties with respect to a relatively restricted diffusion. These sorption properties are those described in U.S. Patent No. 4,810,357 for zeolites such as zeolite ZSM-22, ZSM-23, ZSM-35 and ferrierite. These zeolites have pore openings which result in a particular combination of sorption properties, namely (1) a ratio of the sorption of n-hexane to o-xylene, based on volume percent, of more than about 3, the sorption at P / P ₀ = 0.1 and a temperature of 50 ° C for n-hexane and 80 ° C for o-xylene, and (2) the ability at 1000 ° F and a pressure of 1 atmosphere from a mixture of n-Hexane / 3-methylpentane / 2,3-dimethylbutane with a weight ratio of 1/1/1 3-methylpentane (3MP) preferentially cracking over the double-branched 2,3-dimethylbutane (DMB), the ratio of the rate constants k _3MD / k _{DMB determined} at a temperature of 538 ° C (1000 ° F) is greater than about 2.

The term "P / P ₀ " agrees with its usual meaning as used in the literature, e.g. B. in "The Dynamic Character of Adsorption" by JH deBoer, 2nd ed., Oxford University Press (1968), and represents the relative pressure, which defines the ratio of the partial pressure of the sorbate to the vapor pressure of the sorbate at the sorption temperature becomes. The ratio of the rate constants k _3MD / k _DMB is determined in the usual way from the first order kinetics using the following equation: k = (1 / T c ) 1n (1/1 - ε) where k is the rate constant for each component, T _{c is} the contact time and ε is the proportional conversion of each component.

Zeolites that meet these requirements in terms of sorption, conclude that of course occurring zeolite ferrierite as well as the synthetic zeolites ZSM-22, ZSM-23 and ZSM-35. These zeolites lie at least partially in the acidic form or the hydrogen form before when in the process according to the invention be used.

The manufacture and the properties of the ZSM-22 zeolite are described in U.S. Patent No. 4,810,357 (Chester), what for this description is referred to.

The synthetic zeolite is ZSM-23 in U.S. Patent Nos. 4,076,842 and 4,104,151, followed by the description of this zeolite, its manufacture and properties becomes.

The synthetic crystalline material with medium pore size, the is referred to as ZSM-35 ("Zeolite ZSM-35 "or simply" ZSM-35 ") is in US patent No. 4,016,245, whereupon for the description of this zeolite and reference is made to its manufacture.

The synthesis of SAPO-11 is in US patents Nos. 4,943,424 and 4,440,871. The synthesis of SAPO-41 is described in U.S. Patent No. 4,440,871.

Ferrierite is a naturally occurring one Material described in the literature, see e.g. B. D. W. Breck, ZEOLITE MOLECULAR SIEVES, John Wiley and Sons (1974), pp. 125-127, 146, 219 and 625, whereupon the description of this zeolite is referred to.

The shape-selective catalytic Dewaxing catalysts used in dewaxing preferably include a metal hydrogenation / dehydrogenation component. Although it may not be essential, the selective ones To promote crack reactions, has been shown to be present this component is desirable is to promote certain isomerization reactions that lead to synergism contribute to this dewaxing system with two catalysts. The presence of the metal component leads to an improvement in the Product, especially the VI and the stability and also helps the aging to delay the catalyst. Shape-selective catalytic dewaxing is usually done in the presence of hydrogen under pressure. The metal is preferred Platinum or palladium. The amount of the metal component is typically 0.1 to 10% by weight. If necessary, matrix materials and Binders can be used.

The form-selective dewaxing using highly restricted, very shape-selective catalysts can be in the same general manner as other catalytic Dewaxing processes, such as those for the first isomerization phase described, carried out become. For a more detailed explanation of the shape-selective catalytic dewaxing step refer to U.S. Patent 4,919,788.

The extent of conversion to lower boiling Species in the dewaxing stage change depending on the extent of the dewaxing required at this point, d. H. after the difference between the pour point to be achieved and the pour point of the drain from the isomerization stage. It also depends on the selectivity of the one used shape-selective catalyst. At lower pour points of the product and with relatively few selective dewaxing catalysts it higher Conversions and a correspondingly higher hydrogen consumption.

After the pour point of the oil through selective dewaxing has been reduced to the desired value is the dewaxed oil Undergo treatments such as hydrogen treatment around color bodies to remove and a lubricating oil product with the ones you want To produce properties. Fractionation can be used to remove the lead and the regulations regarding the volatility to fulfill. Suitable hydrogen treatment processes are in claims 15, 16, 27 and 28 listed.

Products

The products of this process are materials with a high VI and a low pour point, which are obtained with an excellent yield. In addition to excellent viscometric properties, they are also very stable, both oxidative and thermal as well as against UV light. With the preferred Wax loads for this process are typically VI values reached in the range of 130 to 150, and it can be used in yields the product of at least 50% by weight, usually at least 60% by weight, based on the original Wax loading, easily achieve values of at least 140.

Examples

example 1

A low acidity zeolite beta catalyst was prepared by first extruding a mixture of 65 parts by weight of zeolite beta and 35 parts by weight of silicon dioxide (SiO ₂ ). The at the The zeolite beta used in its production has a SiO ₂ : Al ₂ O ₃ ratio of 600, an average crystal size of 1 to 3 μm, measured by scanning electron microscopy (SEM). Details of the synthesis are given in U.S. Patents 5,232,579, 5,164,169 and 5,164,170. The mixture of zeolite beta and silica was mixed with an aqueous alkali solution to form a paste and extruded by standard methods known to those skilled in the catalyst preparation art. The extrudate was dried at 121 ° C (250 ° F) for 8 hours at 5 V./V. a 1N NH ₄ NO ₃ solution to reduce the amount of sodium. The reduced sodium extrudate was then heated in N ₂ to 482 ° C (900 ° F) and held at that temperature for 3 hours before being exposed to air at 538 ° C (1000 ° F) for 6 hours to allow the organic compounds to dissolve decompose that had been used in the manufacture of the zeolite beta. This catalyst was then exposed to 100% steam at 101 kPa _a (0 psig) for a sufficient time (24 hours) for its α activity to decrease to less than 15.

This steam deactivated zeolite Material containing beta was then exchanged with an aqueous solution of Platinum tetrammine chloride dihydrate maintained at pH 7 to 8 subjected. The catalyst replaced with platinum was replaced with water rinsed, to remove chlorides and then heated in air to 349 ° C (660 ° F) and kept at this temperature for 3 hours. The finished catalyst contained 0.6% by weight of platinum and has the properties listed in Table 4.

Table 4 Properties of the Pt / Beta catalyst associated with silica

Example 2

A catalyst containing zeolite beta was prepared by first extruding a mixture of 65 parts by weight of zeolite beta and 35 parts by weight of silicon dioxide (SiO ₂ ). The zeolite beta used in this preparation had a SiO ₂ : Al ₂ O ₃ ratio of 50, an average crystal size of less than 0.05 μm, which had been measured using the SEM, and was in accordance with the following standard methods for zeolite beta MIDW quality has been synthesized. The zeolite beta and silica mixture was mixed with an aqueous alkali solution to form a paste and extruded by standard methods known to those skilled in the art of catalysts. The extrudate was dried at 121 ° C (250 ° F) for 8 hours. The sodium-containing extrudates were then heated in N ₂ to 482 ° C (900 ° F) and held at that temperature for 3 hours before being exposed to air at 538 ° C (1000 ° F) for 6 hours to decompose the organic compounds that had been used in the manufacture of the zeolite beta. This catalyst was then exposed to a 2M aqueous oxalic acid solution at 71 ° C (160 ° F) for a total of 6 hours. The zeolite beta catalyst treated with oxalic acid was then heated to 538 ° C (1000 ° F) for 2 hours. The material had an α value of less than 10 and a sodium content of 525 ppmw.

This catalyst treated with oxalic acid Zeolite Beta was then exchanged with an aqueous solution of Platinum tetramine chloride dihydrate, which was kept at pH 5 to 6, subjected. The catalyst replaced with platinum was replaced with water rinsed, to remove chlorides and then heated in air to 349 ° C (660 ° F) and kept at this temperature for 3 hours. The finished catalyst contained 0.5% by weight of platinum and has that in the table above 4 listed Characteristics.

Example 3

Paraffin gum, which originated from the solvent dewaxing of a high-boiling neutral furfural raffinate at 97 mm ² / s (cSt) (450 SUS), was hydrocracked at a mild severity to reduce its sulfur and nitrogen content. The conditions for the mild hydrocracking step were: 2 LHSV, 404 ° C (760 ° F), partial pressure 13891 kPa _a (2000 psig H ₂ ). The properties of paraffin gossip and stripped, Hydrocracked product are listed in Table 5.

Wachsausbeute = (Ausbeute der Destillationsrückstände gegenüber der wachsartigen Beschickung) × (Ausbeute des ölfreien Wachses vom Lösungsmittelentparaffinieren auf der Basis der Beschickung zur Vorrichtung für das Lösungsmittelentparaffinieren) Schmierölausbeute = 100 – Wachsbeschickung – 650°F+-Umwandlung, durch simulierte Destillation gemessen The mild hydrocracking step converted 16% of the paraffin wax feed to products boiling below 650 ° F (343 ° C) and also converted 17% of the wax in the feed. The wax conversion and the lubricating oil yield are calculated using the following equations. Because of the agreement, the yield of the dewaxed oil was corrected to a pour point of 0 ° F.

Wax yield = (yield of the distillation residues compared to the waxy feed) × (yield of the oil-free wax from solvent dewaxing based on the feed to the device for solvent dewaxing) Lube oil yield = 100 - wax loading - 650 ° F + -Conversion, measured by simulated distillation

Table 5 Properties of the feed material

Table 5 continued

Example 4

The mildly hydrocracked paraffin grease from Example 3 was implemented in separate experiments over the Pt / Beta catalysts from Examples 1 and 2. The reaction conditions were 13891 kPa _a (2000 psig) and LHSV = 1 for the catalyst of Example 1 and LHSV = 1.25 for the catalyst of Example 2. The catalyst temperature was changed to make changes in the severity of the reaction. Before the liquid feed was introduced, both catalysts were presulfided to a maximum temperature of 371 ° C (700 ° F) with a mixture of 2% by volume H ₂ S / 98% by volume H ₂ .

The reactor effluent from these experiments was analyzed by simulated distillation to convert into products at 343 ° C (650 ° F-) and then distilled to the nominal cut point of 343 ° C (650 ° F). The wax and lubricating oil yields and the wax conversions were calculated based on the equations of Example 3 calculated and are listed in Table 6. The Figure shows the relative dependency the lubricating oil yield of wax conversion for these two catalysts.

The selectivity for the wax isomerization of the Small crystal catalyst (Example 2) was significantly higher than that of the catalyst with large Crystals (example 1). The lubricating oil yield had for the Pt / Beta catalyst the maximum value with small crystals at 64%, whereas the catalyst with large crystals only reached 52%. In accordance the sequential network of isomerization reactions, followed by shape-selective cracking resulted in both catalysts low wax conversions (less than 40%) similar yields. If the Severity of the reaction increased, the crack rate at the catalyst with big Crystals in proportion to the isomerization rate, however, so that at a Wax conversion of 50% by the rate of generation of lubricating oil Isomerization coincided with the rate of loss of lubricating oil due to cracking. An increase the wax conversion over led this point to a reduction in the lubricating oil yield. In contrast to the relationship remained between isomerization and cracking in the catalyst with small Crystals up to high wax conversions. The speeds these two reactions were not equivalent until a wax conversion of 80% was reached.

Practical application of the invention exists about the obvious higher ones Yields for the catalyst with small crystals, in the ability of the catalyst to act selectively with a high wax conversion. This reduces the amount of wax in circulation and the required size of the reactors, to produce a given amount of a high VI base material.

The acidity of the zeolite can also play an important role in determining the isomerization selectivity. While the Pt / beta catalyst with large crystals had a higher α value compared to the version with small crystals (13 versus 8), it is likely that the difference in selectivity observed between these catalysts is not primarily a function of acidity was. The Un The difference in the α values is not significantly high.

Table 6 Selectivity in the Isomerization of Wax of the Pt / Beta Catalysts Bound With Silica Catalyst of Example 1 (1 to 3 μm, 13 ∝)

Example 2 catalyst (0.05 μm, 8 8)

Claims (26)

Process for producing a lubricating oil with a viscosity Index (VI) of at least 130 from a waxy hydrocarbon feed with a wax content of at least 20% by weight, which is the catalytic Dewaxing the wax-like substances present in the feed Paraffins, primary by isomerization, in the presence of hydrogen and in the presence a molecular sieve with large Pores and low acidity comprises that selected from the group which consists of zeolite beta, Y and mordenite, with at least a pore channel with a main dimension of more than 0.7 nm and with a crystal size of less than 0.1 μm, an α value of not more than 30 and the one hydrogenation component from one Contains precious metal. The method of claim 1, wherein the molecular sieve with big Pores at least one pore channel made of 12-membered oxygen rings has. The method of claim 1, wherein the zeolite beta an α value of no more than 20. The method of claim 1, wherein the molecular sieve with big Pores a crystal size of less than 0.05 μm having. The method of claim 1, wherein the molecular sieve with big Pores is a zeolite beta with low acidity, which is the steam treatment has undergone a relationship of silicon dioxide: aluminum oxide of the lattice of at least 200 : 1 has. The method of claim 1, wherein the molecular sieve with big Pores an isomerization catalyst from a boron-containing zeolite Beta includes in which the boron is present as a lattice component of the zeolite beta. The method of claim 1, wherein the molecular sieve with big Pores 0.3 to 2 wt .-% Pt on a support comprising zeolite beta. The method of claim 1, wherein the feed a waxy hydrocarbon feed with a wax content of at least 40% by weight and an aromatic content of less than 25 wt .-% comprises. The method of claim 1, wherein the feed material selected from the group is that from raw paraffin, de-oiled Wax, wax from a Fischer-Tropsch process, floor oils, petrolatum, Vacuum gas oil or raffinate from solvent extraction a vacuum distillate. The method of claim 1, wherein the method in Presence of hydrogen is carried out, reducing 40 to 90 % By weight of the wax contained in the feed is converted. The method of claim 1, wherein the conditions include a partial pressure of hydrogen in the range of 4238 to 20786 kPa _a (600 to 3000 psig) and a temperature of 288 to 427 ° C (550 to 800 ° F). The method of claim 1, wherein the catalytic dewaxed feed another selective dewaxing is subjected to achieve the pour point to be achieved. The method of claim 12, wherein the further dewaxing either by solvent or catalytic measures is achieved. The method of claim 1, wherein the catalytically dewaxed feed the hydrogen treatment is subjected by at a pressure in the range of about 3549 to about 20786 kPa _a (500 to about 3000 psig), a reaction temperature in the range of about 260 to about 427 ° C (500 to about 800 ° F), a space velocity that is in the range of about 0.1 to about 10 LHSV, and a circulation rate of hydrogen in one pass that is from about 178 to about 1780 nl / L (1000 to about 10,000 scf / b) is brought into contact with a catalyst comprising a hydrogenation component made of a metal on a porous carrier material in order to improve the heat and oxidation resistance of the lubricating oil. The method of claim 12, wherein the feed is subjected to the selective dewaxing hydrotreating by at a pressure in the range of about 3549 to about 20786 kPa _a (500 to about 3000 psig), a reaction temperature in the range of about 260 to about 427 ° C (500 to about 800 ° F), a space velocity that is in the range of about 0.1 to about 10 LHSV, and a hydrogen circulation rate in one pass that is from about 178 to about 1780 nl / l (1000 to about 10,000 scf / b) is contacted with a catalyst comprising a metal hydrogenation component on a porous support material to improve the heat and oxidation resistance of the lubricating oil. Process for producing a lubricating oil with a viscosity Index (VI) of at least 130 from a waxy hydrocarbon feed with a wax content of 20 of at least 20 wt .-%, wherein the Procedure includes the following steps: a) hydrocracking the Feed to reduce both their nitrogen content and also remove naphthenic and aromatic components, thereby the VI is improved, the hydrocracking process making contact the feed comprising a catalyst consisting of a hydrogenation component consists of a metal on air acidic carrier. b) Catalytic Dewaxing the wax-like substances present in the feed Paraffins, primary by isomerization, in the presence of hydrogen and in the presence a molecular sieve with large Pores and low acidity, that selected from the group which consists of zeolite beta, Y and mordenite, with at least a pore channel with a main dimension of more than 0.7 nm and a crystal size of less than 0.1 μm, an α value of not more than 30 and the one hydrogenation component from one Contains precious metal. The method of claim 16, wherein the molecular sieve with big Pores at least one pore channel made of 12-membered oxygen rings has. The method of claim 16, wherein the zeolite is beta an α value of no longer than 20. The method of claim 16, wherein the molecular sieve with big Pores is a zeolite beta with low acidity, that of steam treatment has undergone a relationship of silicon dioxide: aluminum oxide of the lattice of at least 200 : 1 has. The method of claim 16, wherein the molecular sieve with big Pores 0.3 to 2 wt .-% Pt on a support comprising zeolite beta. The method of claim J7, wherein the feed material selected from the group is that from raw paraffin, de-oiled Wax, wax from a Fischer-Tropsch process, floor oils, petrolatum, Vacuum gas oil or raffinate from solvent extraction a vacuum distillate. The method of claim 16, wherein the conditions of step (b) include a partial pressure of hydrogen in the range of 4238 to 20786 kPa _a (600 to 300 psig) and a temperature of 288 to 427 ° C (550 to 800 ° F). The method of claim 16, wherein the step effluent (b) subjected to further selective dewaxing, to reach the pour point to be achieved. The method of claim 23, wherein the further dewaxing either by a solvent or through catalytic measures is achieved. The method of claim 16, wherein at least a part of the effluent is subjected to the step (b) the hydrogen treatment by keeping it at a pressure in the range of about 3549 to about 20786 kPa _a (500 to about 3000 psig), a reaction temperature in the range of about 260 to about 427 ° C (500 to about 800 ° F), a space velocity that is in the range of about 0.1 to about 10 LHSV and a circulation rate of hydrogen in one pass that is from about 178 to about 1780 nl / l (1000 to about 10000 scf / b) is contacted with a catalyst comprising a hydrogenation component made of a metal on a porous support material to improve the heat and oxidation resistance of the lubricating oil. The method of claim 23, wherein the effluent from step (b) of claim 16, after further selectively dewaxing, is subjected to the hydrogen treatment by being at a pressure in the range of about 3549 to about 20786 kPa _a (500 to about 3000 psig) Reaction temperature in the range of about 260 to about 427 ° C (500 to about 800 ° F), a space velocity that is in the range of about 0.1 to about 10 LHSV, and a circulation rate of hydrogen in one pass that is about 178 up to about 1780 nl / l (1000 to about 10000 scf / b) is contacted with a catalyst comprising a metal hydrogenation component on a porous support material to improve the heat and oxidation resistance of the lubricating oil.