# Patent

## Title
Titania-bound zeolite EU-2 composition and method of making and using such composition

## Abstract

Catalyst composition useful in the catalytic dewaxing of a waxy hydrocarbon feedstock which catalyst composition includes a mixture of zeolite EU-2 and titania and may further include a noble metal. The zeolite EU-2 has a molar bulk ratio of silica-to-alumina (SAR) of greater than 100:1. The zeolite or mixture may have been dealuminated such as by acid leaching using a fluorosilicate salt or by steam treating.

## Background
This application claims the benefit of U.S. Provisional Application No. 61/604,818, filed Feb. 29, 2012, which is incorporated herein by reference.


This invention relates to a titania-bound zeolite catalyst composition that is useful as a component of or as a catalyst for the dewaxing of a hydrocarbon oil feed, the preparation of the composition, and use of the composition in the processing of hydrocarbon oil feedstocks.
A crystalline zeolite designated as ZSM-48 is described in U.S. Pat. No. 4,397,827. The '827 patent indicates that the ZSM-48 zeolite can be used as a catalyst in intimate combination with an additional hydrogenating component such as certain Group VI and Group VIII metals including the noble metals of platinum and palladium. Other catalysts may be formed by compositing the ZSM-48 crystals with inorganic materials such as clays, silica and other metal oxides and porous matrix materials. Another zeolite that appears to be the same or closely related to ZSM-48 is described in U.S. Pat. No. 4,876,412 and is referred therein as zeolite EU-2. Zeolite EU-2 can be associated with an inorganic matrix or catalyst support material and a hydrogenation or dehydrogenation component to provide a catalyst. The zeolite EU-2 may have uses in such catalytic processes as hydrocracking, reforming and hydroprocessing.
In U.S. Pat. No. 7,077,948 is disclosed a catalytic dewaxing process for lowering the pour point or cloud point of an oil feed by selectively converting its components having a high pour point to ones having a lower pour point. The catalyst used in this dewaxing process comprises a hydrogenation component, a surface dealuminated aluminosilicate zeolite crystallite and a low acidity refractory oxide binder material that is essentially free of alumina. The list of possible suitable aluminosilicate zeolite crystallites includes ZSM-48. The preferred aluminosilicate zeolites are those having an MFI topology such as ZSM-5 zeolite. It is preferred for the crystallites to be smaller than 10 microns. The low acidity referactory oxide binder material is essentially free of alumina and may include silica, zirconia, titanium dioxide, germanium dioxide, boria and mixtures of two or more thereof. The most preferred binder is silica. The dealumination may be performed using an aqueous solution of a fluorosilicate salt. The hydrogenation component may be nickel, cobalt, platinum or palladium.
U.S. application No. US 2009/0186754 discloses a dewaxing catalyst that has a relatively high activity as compared to other dewaxing catalysts when used in the treatment of feeds having high levels of either sulfur or nitrogen. The dewaxing catalyst comprises a zeolite with a low silica-to-alumina ratio and having a high ratio of zeolite surface area to external surface area, a low surface area binder, and a metal hydrogenation component. The zeolite is selected from those that provide for dewaxing by isomerization of hydrocarbon feedstocks, but the zeolite more preferably selected from those having a unidimensional pore structure. Suitable zeolites are those having 10-member ring structures including EU-2, ZSM-23 and ZSM-48 zeolites. The preferred silica-to-alumina ratio of the zeolite is 100:1 or less. The low surface area binder has a surface area of 100 m2/g or less. The metal hydrogenation component of the dewaxing catalyst may be selected from Groups 6-12 of the Periodic Table (based on IUPAC system) and the binder material may be metal oxides such as alumina, silica, titania, zirconia, and silica-alumina. Certain exemplified catalysts include extrudates of ZSM-48 and titania or silica loaded with platinum. There is no indication that these catalysts are dealuminated. There are ongoing efforts to provide improved catalysts for use in the catalytic dewaxing of hydrocarbon feedstocks. Such improvements may include dewaxing catalysts having enhanced activity or which provide for improved lube stock yields when processing certain hydrocarbon feedstocks.
Accordingly, provided is an inventive catalyst composition that comprises a mixture that comprises titania and a zeolite EU-2 having a molar bulk ratio of silica-to-alumina (SAR) of greater than 100:1. Also provided is a process for the catalytic dewaxing of a hydrocarbon oil feeds. This process comprises contacting, under catalytic dewaxing conditions, the hydrocarbon oil feed with a catalyst composition comprising a mixture comprising zeolite EU-2 having a SAR of greater than 100:1, titania and a noble metal selected from the group consisting of platinum and palladium. Further provided is a method of preparing a dewaxing catalyst composition. This method comprises mixing zeolite EU-2 having a SAR of greater than 100:1 with titania and then forming the mixture into a particle that may further be treated and impregnated with a noble metal to thereby provide a dewaxing catalyst.
The composition of the invention is useful in the catalytic dewaxing of waxy hydrocarbon feedstocks, and it exhibits exceptional catalytic activity for the isomerization of normal paraffins to isoparaffins while still providing for a high base oil yield. In general, the inventive composition comprises a mixture of a titanium dioxide (TiO2) binder and a zeolite EU-2 having a SAR of greater than 100:1. The mixture of the composition may further include a noble metal component, such as platinum or palladium, that is incorporated into the mixture. The zeolite component of the mixture or the mixture itself, or both, may also be dealuminated.
The molar bulk ratio of silica-to-alumina of the zeolite is also referred to as the overall ratio. Such ratio is different from the silica-to-alumina ratio of the crystalline framework of the zeolite.
The bulk ratio or overall ratio, i.e., SAR, of the zeolite may be determined by one or more of the chemical analysis techniques or analytical methods known to those skilled in the art. Such techniques or analytical methods may include atomic adsorption, X-ray fluorescence, atomic emission spectroscopy, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and mass spectrometry.
The ZSM-48 zeolite is disclosed and described in the patent literature. One early patent, U.S. Pat. No. 4,397,827, provides a detailed description of the ZSM-48 zeolite composition and its physical properties and method of preparing the ZSM-48 zeolite. Also, a related, if not identical, zeolite, EU-2, is disclosed in another early patent, U.S. Pat. No. 4,876,412, which provides a detailed description of the EU-2 zeolite composition and its physical properties and method of preparing the zeolite EU-2.
The EU-2 and ZSM-48 zeolites are closely related to each other, and, most likely, they are zeolites having identical zeolite structures and topology. Thus, they are believed to be substantially the same zeolite compound. It, therefore, should be understood that the term EU-2 is used in this description and in the claims as a reference to both EU-2 and ZSM-48 whether or not they are zeolites having separate and distinguishable compositions, structures or topologies or exhibit distinguishable properties such as X-ray powder diffraction patterns or other properties. Thus, when the term EU-2 is used in reference to a specific zeolite of the invention or in describing the inventions herein, the term is intended to encompass either the EU-2 zeolite alone, or the ZSM-48 zeolite alone, or both zeolites EU-2 and ZSM-48.
There are further disclosures within the patent literature of possible other types of zeolites EU-2 or ZSM-48 or variations in the method of preparing or synthesizing zeolites EU-2 or ZSM-48. Some of these zeolites and methods are described in such patents as U.S. Pat. Nos. 4,741,891; 4,836,996; 5,961,951; 7,482,300; and 8,003,074, all of which are encompassed by the term EU-2 in the current description and claims.
It will be appreciated from the above that the EU-2 zeolite component of the current composition has a known structure that is well defined, and it may be prepared by known methods for making such EU-2 zeolites.
One important feature of the inventive composition is for the EU-2 zeolite component to have a SAR that is sufficiently high to provide for a final dewaxing catalyst of the invention that exhibits desired catalytic properties of high dewaxing activity while providing for a high dewaxed product yield. To provide for this, the EU-2 zeolite component should have a SAR that is greater than 100:1. Preferably, the SAR of the EU-2 zeolite component is greater than 110:1, or greater than 120:1, or greater than 130:1 or even greater than 140:1. An upper limit to the SAR of the EU-2 zeolite component can be less 1000:1, but, more typically, the upper limit of the SAR of the EU-2 zeolite component is less than 500:1 or even less than 300:1 or less than 250:1.
If the starting EU-2 zeolite used to prepare the inventive composition already has a sufficiently high SAR such that it provides for the desired catalytic properties of the final catalyst composition of the invention, then it is generally not necessary to subject the zeolite to a separate dealumination treatment in order to increase its SAR to a desired value. However, if the SAR of the starting EU-2 zeolite is too low, it may be subjected to dealumination so as to thereby dealuminate the zeolite in order to provide a dealuminated EU-2 zeolite having the desired high SAR that can be used as a component of the inventive composition. Furthermore, it can be beneficial to subject high SAR EU-2 zeolite to dealumination in order to even further decrease the alumina content at the surface.
The expression dealumination is used herein to indicate that the aluminum and/or aluminum containing compounds, such as alumina, are removed from the bulk of the zeolite. The aluminum and aluminum containing compounds can, but need not, be part of the zeolite framework.
The EU-2 may be dealuminated before it is mixed with the titania binder component of the inventive composition or, alternatively, the EU-2 zeolite may be dealuminated after it has been mixed with the titania binder component of the inventive composition so as to provide a treated mixture of EU-2 zeolite and titania. The dealuminated zeolite, either as powder or as part of the mixture, preferably has an average aluminium concentration which is at least 1.1 times the aluminium concentration at the surface, preferably at least 1.2, more specifically at least 1.3, more specifically at least 1.4, more specifically at least 1.5, more specifically at least 1.6, more specifically at least 1.7, more specifically at least 1.8, most preferably at least 2 times the aluminium concentration at the surface.
The average aluminium concentration can be determined by any one of a number of chemical analysis techniques. Such techniques include X-ray fluorescence, atomic adsorption and inductive coupled plasma-atomic emission spectroscopy (ICP-AES). For the present invention, the average aluminium concentration is to be determined by X-ray fluorescence.
The aluminium concentration at the surface can be determined by any method known to those skilled in the art such as by secondary ion mass spectrometry (SIMS) or by X-ray photoelectron spectroscopy (XPS). For the present invention, XPS is to be used.
In preparing the inventive composition, the EU-2 zeolite preferably is dealuminated either by acid leaching or by steam treating. It is a preferred embodiment of the invention to either acid treat or steam treat the EU-2 zeolite component after it has been mixed and combined with the titania binder material and formed into an agglomerate or particle that has been calcined to provide a calcined particle. The steam treatment is effected by contacting the zeolite, and, preferably the calcined particle of the mixture of zeolite and titania, with steam at an elevated temperature in the range of from 250° C. to 650° C. The preferred temperature at which the steam treatment is conducted is in the range of from 400° C. to 550° C. The steam treatment can be accomplished in an atmosphere of 100% steam or in an atmosphere consisting of steam or some other gas which is essentially inert to the zeolite. A similar treatment can be accomplished at lower temperatures and elevated pressure, e.g., from 180° C. to 370° C. at from 10 to 200 atmospheres.
It is particularly preferred to use an acid treatment method to dealuminate the EU-2 zeolite component, either separately or when it is combined as a mixture with the titania binder material, of the inventive composition.
Among the available methods of acid treatment the most preferred is a dealumination process which comprises contacting the zeolite, either separately or when it is combined as a mixture with the titania binder material, with a solution of a fluorosilicate salt wherein the fluorosilicate salt is represented by the formula:

(A)2/bSiF6 

wherein ‘A’ is a metallic or non-metallic cation other than H+ having the valence ‘b’. Examples of cations with the valence ‘b’ are alkylammonium, NH4+, Mg++, Li+, Na+, K+, Ba++, Cd++, Cu+, Ca++, Cs+, Fe++, Co++, Pb++, Mn++, Rb+, Ag+, Sr++, Tl+, and Zn++. Preferably ‘A’ is the ammonium cation.

The solution comprising the fluorosilicate salt preferably is an aqueous solution. The concentration of the salt preferably is at least 0.004 mole of fluorosilicate salt/liter, more preferably, the salt concentration is at least 0.006 mole of fluorosilicate salt/liter, and, most preferably, it is at least 0.008 mole of fluorosilicate salt/liter. The concentration preferably is at most 0.5 mole of fluorosilicate salt/l, more preferably at most 0.3 mole of fluorosilicate salt/liter, and, most preferably, at most 0.1 mole of fluorosilicate salt/liter.
The weight ratio of fluorosilicate salt solution to the zeolite used in the treatment of the zeolite is in the range of from 50:1 to 1:4 of fluorosilicate solution to zeolite. If the zeolite is present together with binder, the binder is not taken into account for these weight ratios.
The pH of the aqueous fluorosilicate containing solution preferably is in the range of from 2 and 8, and, more preferably, in the range of from 3 and 7.
The EU-2 zeolite or EU-2 zeolite-containing material or calcined particle comprising EU-2 zeolite and titania is contacted with the fluorosilicate salt solution for a time period sufficient to provide a desired dealuminated EU-2 zeolite having an SAR within the desired range. Typically, the contacting time period is in the time range of from 0.5 hours to 20 hours. A more specific contacting time period is in the range of from 1 to 10 hours.
The temperature at which the fluorosilicate salt solution is contacted with the EU-2 zeolite or EU-2 zeolite-containing material or calcined particle comprising EU-2 zeolite and titania is in the range of from 10° C. to 120° C., and, more specifically, of from 20° C. to 100° C.
Titanium dioxide (TiO2), also referred to herein as titania, is an important and significant component of the inventive composition. Without wanting to be bound to any particular theory, it is believed, however, that it is the unique combination of a high SAR EU-2 zeolite component with a titania component, as opposed to other refractory metal oxide compounds, such as, silica, alumina, magnesia, zirconia, thoria, beryllia, and combinations thereof, which provides a composition having the exceptionally good dewaxing catalytic properties as are described herein. Thus, it is an embodiment of the invention for the titania component of the composition to have either a low concentration or material absence or substantial absence of any of the aforementioned refractory metal oxide compounds other than titania. These embodiments are more fully described below.
It is also recognized that other additional features of the mixture of high SAR EU-2 zeolite and titania can provide further embodiments of the inventive composition or contribute to the referenced exceptional properties. Such other features include, for example, the use of a titania component of a particular polymorphic form or combination of forms or a titania component having a high surface area. These embodiments are more fully described below.
The titania component of the invention may be in any one or a combination or mixture of its several forms or polymorphs of rutile, anatase or brookite. The titania may be present in the pure form of any one of the polymorphs, but, if the titania present in the inventive composition is in other than a pure form, i.e., 100 percent of a specific titania polymorph, it typically is in the anatase form in an amount exceeding 50 wt % with the balance being either the rutile form or brookite form or a combination of both such forms.
In the more desirable compositions of the invention, the balance of the titania that is not in the anatase form is predominantly in the rutile form. It is preferred for the titania component to comprise, consist essentially of, or consist of more than 60 wt % anatase titania and less than 40 wt % rutile titania. In a more preferred composition, the titania component should contain at least 70 wt % up to 100 wt % anatase titania, but, most preferably, the titania component of the inventive composition contains titania having at least 75 wt % or at least 80 wt % up to 100 wt % of the anatase form of titania. Good results have been achieved using titania having in excess of 70 wt % anatase titania and titania that is essentially 100 wt % of the anatase form of titania. Especially good results have been achieved using titania having of from 70 to 95% wt of the anatase form of titania.
The B.E.T surface area of the titania used in the preparation of the inventive composition should be such as to provide for the good catalytic dewaxing properties that are noted herein, but the surface area of the titania may vary substantially depending upon the particular form or mixture of forms of titania used. Thus, the surface area of the titania may be in the range of from 10 m2/g to 700 m2/g or even in the range of from 20 m2/g to 400 m2/g. One embodiment of the invention, however, uses in the preparation of the inventive composition a titania material having a high surface area that is, generally, depending upon the form of titania that is used, greater than 100 m2/g. In an embodiment of the invention, the titania of the catalyst composition has a high surface area of greater than 125 m2/g or greater than 150 m2/g or even greater than 175 m2/g. An upper limit for the surface area for the high surface area titania is less than 700 m2/g or less than 500 m2/g or even less than 400 m2/g.
Very suitable titania starting materials are available from Millenium Chemicals, Degussa and Haishunde. For example, Millenium's DT-51D and G5 grades; Degussa's P25 grade; and Haishunde's grade FCT010925.
The EU-2 zeolite content of the final composition of the invention should be at least 10 wt % and at most 70 wt % of the total dry weight of the composition. The titania content of the final composition of the invention can be in the range of from at least 30 wt % and no more than 90 wt % of the total dry weight of the composition. It is preferred for the EU-2 zeolite content of the composition to be at most 60 wt %, and, more preferred, at most 55 wt %. It is further preferred for the EU-2 zeolite content of the composition to be at least 20 wt %, but, more preferred, at least 25 wt %, and, most preferred, at least 30 wt %. The titania content of the composition, on the other hand, can be at least 40 wt %, or, even, at least 45 wt %. It is preferred for the titania content of the composition to be no more than 80 wt %, but, more preferred, no more than 75 wt %, and, most preferred, no more than 70 wt %.
It is a desirable feature of the invention for the titania component of the inventive composition to contain a low concentration of silica (SiO2), especially, a low concentration of amorphous silica, but, also, a low concentration of crystalline silica other than the zeolite itself, if present in the titania component. Thus, the titania component has a material absence of silica or a substantial absence of silica, generally, an amount of less than 5 wt % silica. Thus, the titania component can contain less than 3 wt % silica, but, it is more preferred that it contains less than 1 wt % silica. In the most preferred compositions of the invention, the titania component can have less than 0.1 wt % silica or even less than 0.05 wt % silica.
It can also be desirable for the titania component of the inventive composition to have a low concentration of alumina (Al2O3). Generally, the titania component contains less than 5 wt % alumina. It is preferred for the titania component to have a material absence of alumina or a substantial absence of alumina. Thus, the titania component can contain less than 3 wt % alumina, but, it is more preferred that it contains less than 1 wt % alumina. In the most preferred compositions of the invention, the titania component can have less than 0.1 wt % alumina or even less than 0.05 wt % alumina.
When referring herein to the material absence of a compound, what is meant is that the referred to compound is absent in an amount such that the component does not affect the basic properties of the composition as they are defined herein, such as, for example, the catalytic and physical properties of the inventive catalyst composition which contains the component.
In another embodiment of the inventive composition, the mixture, which may be in the form of a particle, comprising, consisting essentially of, or consisting of, EU-2 zeolite, preferably, a high SAR EU-2 zeolite and titania, may further be treated by any of the methods referenced herein in order to dealuminate the zeolite and to provide a treated mixture that comprises the dealuminated mixture and further comprises dealuminated EU-2 zeolite.
It is, therefore, desirable for the mixture to have a low concentration of silica, and, in particular, the mixture should have a material absence of silica (other than silica contained in the EU-2 zeolite framework) or, preferably, a substantial absence of silica (other than silica contained in the EU-2 zeolite framework). Thus, generally, the mixture contains an amount of silica that is less than 5 wt % of the total dry weight of the mixture, and the mixture can contain less than 3 wt % silica. It is more preferred for the mixture to contain less than 1 wt % silica, and, it is most preferred for the mixture to contain less than 0.1 wt % silica or even less than 0.05 wt % silica.
It is understood that the reference herein to the wt % silica of the mixture or the reference to the amount, concentration, or absence of silica that is contained in the mixture both exclude or is a reference to the silica other than the silica that is contained in the EU-2 zeolite framework itself.
It is further desirable for the treated or untreated mixture of EU-2 and titania of the inventive composition to have a low concentration of alumina (other than the alumina contained in the EU-2 zeolite framework) that is generally less than 5 wt % of the total dry weight of the mixture. It is preferred, however, for the mixture to have a substantial absence of alumina (other than the alumina contained in the EU-2 zeolite framework). Therefore, the mixture typically should contain less than 3 wt % alumina, but, more preferably, it contains less than 1 wt % alumina.
It is understood that the reference herein to the wt % alumina of the mixture or the reference to the amount, concentration, or absence of alumina that is contained in the mixture both exclude or is other than the alumina that is contained in the EU-2 zeolite framework itself.
The inventive composition may further comprise a noble metal component which is selected from the group consisting of palladium and platinum. The preferred noble metal, however, is platinum. The noble metal component is incorporated into the mixture or particle after its treatment or dealumination, if the mixture or particle is subjected to a treatment or a dealumination step, or, otherwise, the noble metal component is incorporated into the untreated mixture or particle.
Any known suitable means or method may be used to incorporate the noble metal component into the mixture or particle, but, one suitable method is by incipient wetness impregnation using a salt solution of the of the noble metal. If platinum is incorporated into the mixture or particle, possible suitable impregnation solutions may include platinum compounds such as chloroplatinic acid (H2PtCl6(H2O)6); platinous chloride (PtCl2); and the various compounds containing the platinum amine complex, e.g. tetrammineplatinum nitrate, Pt(NH3)4(NO3)2, or tetrammineplatinum chloride hydrate, Pt(NH3)4Cl2.xH2O. The solution used for incorporating the noble metal most preferably is a basic aqueous solution, preferably having a pH greater than 8, more preferably greater than 9, most preferably greater than 10. The mixture or particle is impregnated with the noble metal solution, dried at standard drying conditions, such as, for example, a drying temperature in the range of from 90° C. to 200° C., and, thereafter, calcined at standard calcination conditions, such as, for example, a calcination temperature in the range of from 250° C. to 600° C., more specifically of from 350 to 600° C., more specifically of from 400 to 500° C., most specifically of from 420 to 480° C.
It is desirable for the composition of the invention that comprises the mixture and a noble metal to have a noble metal content in the range of upwardly to about 3 wt % based on the noble metal as an element, regardless of its actual form, and the total dry weight of the composition. It is preferred for the noble metal component to be present in the composition at a concentration in the range of from 0.1 wt % to 3 wt %. More preferably, the noble metal component is present in the composition in an amount in the range of from 0.2 wt % to 2 wt %, and, most preferably, it is in the range of from 0.3 wt % to 1 wt %.
It is further desirable for the composition that contains a noble metal component to also have a material absence of a Group VIII metal other than the noble metal component. The composition that comprises the mixture and a noble metal, therefore, should also have a material absence of a Group VIII metal other than platinum or palladium. Thus, the composition generally should have a cobalt or nickel concentration that is less than 1 wt % of the composition, but it is particularly desirable for the composition to have a substantial absence of such Group VIII metals as cobalt and nickel, which is generally less than 0.1 wt % of the composition or lower.
In the method of preparing or manufacturing the composition of the invention, a mixture comprising the EU-2 zeolite component and the titania component is prepared by any suitable means or method known to those skilled in the art for mixing or combining the separate components to thereby provide the mixture. The mixture may suitably be prepared by co-mulling a EU-2 zeolite powder and a titania powder to form the mixture. Other materials, such as, for example, water, a peptizing agent, or a plastizing agent, may be mixed with the EU-2 zeolite and titania components to assist in the formation of an extrudable mass that can be extruded to form the mixture into a particle or extrudates. While other methods of forming the mixture into a particle may be used, extrusion is one of the preferred methods.
The particle that comprises, consists essentially of, or consists of EU-2 zeolite and titania undergoes a drying step in order to provide a dried particle. Any suitable conventional means or method known to those skilled in the art for drying particulate compositions can be used in drying the particle. The typical drying conditions can include a drying temperature in the range of from 90° C. to 200° C. The dried particle is then calcined to thereby provide a calcined particle by using any suitable conventional means or method known to those skilled in the art for calcining particulate compositions. Typical calcination conditions include a calcination temperature in the range of from 250° C. to 1000° C., but, preferably, in the range of from 300° C. to 800° C., more preferably in the mage of from 400 to 700° C., most speficially in the range of from 450 to 650° C. such as 500 or 625° C.
The calcined particle may then have incorporated therein a noble metal component, but, in an embodiment of the invention, the calcined particle undergoes a dealumination step preferably comprising either steam treating or acid treating by such methods as described in detail above. It is a preferred embodiment of the invention for the calcined particle to be subjected to an acid treating step whereby it is treated with a solution of fluorosilicate salt in the manner described above to thereby provide an acid treated particle that preferably further comprises dealuminated EU-2 zeolite.
The acid treated particle is then dried and calcined as described above to provide a catalyst carrier to be loaded with the noble metals as described elsewhere herein. The noble metal is incorporated into the catalyst carrier by the methods as described in detail above to provide a catalyst composition that comprises, consists essentially of, or consists of EU-2 zeolite, having a high SAR, and titania and a noble metal.
The compositions of the invention may have possible application or use as a catalyst in a wide variety of hydrocarbon conversion processes such as in hydrocracking, isomerization, hydrogenation, dehydrogenation, polymerization, reforming, catalytic hydrocracking, toluene disproportionation, and ethylbenzene conversion. Certain of the compositions have been found to be especially suitable for use in catalytic dewaxing applications.
Catalytic dewaxing is used to improve the cold flow properties of distillate hydrocarbon and lubricating base oil feedstocks by selective hydroisomerization or hydrocracking, or both, of the normal and slightly branched paraffins contained in such feedstocks. These reactions result in converting the components of an oil feedstock that have a high melting temperature which imparts a high pour point to the oil feedstock to other components that have a lower melting temperature which imparts a lower pour point to the oil feedstock. The high melting temperature compounds are referred to as waxes. Wax compounds can include, for example, high melting temperature normal paraffins, isoparaffins and mono-ringed compounds. The dewaxing process reduces the pour point of the oil feedstock preferably by at least 10° C., and, more preferably, by at least 20° C.
Suitable hydrocarbon oil feeds to be employed in the process according to the present invention are mixtures of high-boiling hydrocarbons, such as, for instance, heavy oil fractions. It has been found particularly suitable to use vacuum distillate fractions derived from an atmospheric residue, i.e. distillate fractions obtained by vacuum distillation of a residual fraction that is obtained by atmospheric distillation of a crude oil, as the feed. The boiling range of such a vacuum distillate fraction is usually between 300° C. and 620° C., suitably between 350° C. and 580° C. However, deasphalted residual oil fractions, including both deasphalted atmospheric residues and deasphalted vacuum residues, may also be applied. If the vacuum distillate fractions contain substantial amounts of sulphur- and nitrogen-containing contaminants, for example, having sulfur levels of up to 3% by weight and nitrogen levels up to 1% by weight, it may be advantageous to treat this feedstock by a hydro-desulfurization and hydrodenitrogenation step prior to the catalytic dewaxing process according to the present invention.
Dewaxing generally comprises contacting feedstock with a catalyst composition according to the present invention at a temperature of up to 450° C., more specifically at a temperature in the range of from 250° C. to 400° C., but, preferably, in the range of from 275° C. to 350° C., and at a total pressure in the range of from 5 to 200×105 Pa, more specifically in the range of from 15 to 170×105 Pa, and, preferably, in the range of from 25 to 150×105 Pa. The liquid hourly space velocity preferably is in the range of from 0.1 to 10 h−1.
The feedstock to be subjected to dewaxing is, preferably, either a gas oil or a lube oil basestock, but, more preferably, it is a lube oil base stock. Among these feedstocks, it is preferred for them to be wax-containing feeds that boil in the lubricating oil range typically having a 10% distillation point at 200° C. or higher as measured by ASTM D-2887-93. Examples of feeds having relatively high amounts of waxy compounds are synthetic waxy raffinates (Fischer-Tropsch waxy raffinates), hydrocracker bottom fractions (hydrowax), i.e. those fractions having a final boiling point of at least 320° C., preferably at least 360° C. and slack waxes obtained from the dewaxing of hydroprocessed or solvent refined waxy distillates. These feeds have a wax content of at least 50% by weight, preferably at least 80% by weight and more preferably at least 90% by weight. The wax content is provided by the compounds contained in the feed which are plastic at ambient temperature and melt above 45° C. to give a low viscosity liquid. The amount of wax can be determined by the ASTM method D3235. The process of the present invention can be used to prepare lubricating base oils having viscosity indices (VI) above 120 and particularly above 135.
Furthermore, the feedstocks may have been hydrotreated and/or hydrocracked before being subjected to dewaxing. Hydrotreating generally involves contacting feedstock with a hydrotreating catalyst at a temperature of up to 500° C., more specifically of from 250 to 500° C., and a hydrogen partial pressure of from 10 to 200×105 Pa, more specifically of from 30 to 130×105 Pa.
Hydrocracking generally involves contacting feedstock with a hydrocracking catalyst at a hydrogen partial pressure (at the reactor inlet) in the range from 3×106 to 2.9×107 Pa, more preferably from 8×106 to 1.75×107 Pa and a ratio of hydrogen gas to feedstock (total gas rate) in the range from 100 to 5000 Nl/kg, but preferably in the range from 200 to 3000 Nl/kg.
The following examples are presented only to illustrate certain aspects of the invention, but they are not intended to in any way be limiting.


Example I
This Example I describes the preparation of the comparative Composition I (zeolite EU-2 /silica) and the inventive Compositions II and III (zeolite EU-2/titania). The zeolite EU-2 used in the preparation of the compositions had a SAR of 158 and was made by the method described in U.S. Pat. No. 4,741,891.
Composition I (Comparison)
An extrudable mass was prepared by combining 50 wt % zeolite EU-2, 25 wt % of amorphous precipitated silica powder (Sipernat-50 as obtained from Evonik) and 25 wt % of an ammonium stabilized commercially available silica sol (sold under the trade name Bindzil 30NH3/220 by Eka Chemicals). The weight amounts are basis dry components. The mass was extruded to give extrudates having a cylinder shape and an average diameter of 1.6 mm. These extrudates were dried at 120° C. and calcined at 625° C. for 1 hour resulting in white calcined extrudates.
These extrudates were treated at a temperature of 90° C. for 5 hours with 0.01 M aqueous ammonium hexafluorosilicate (AHS) solution. The weight ratio of solution to extrudates was 5:1. Subsequently, the extrudates were separated from the solution, washed with deionized water, and dried at 120° C. for 2 hours followed by calcination at 500° C. for 1 hour.
Thereafter, 0.7% wt/wt platinum was incorporated into the composition by pore volume impregnation during about 10 minutes with an aqueous solution containing tetramine platinum nitrate (Pt(NH3)4(NO3)2) (3.37% w/w Pt).
The impregnated composition was not washed, but it was equilibrated during 1.5 hours on a rolling bed, dried for 10 minutes at 180° C. (temperature incrementally increased at a rate of 15° C./minute). The temperature was raised again at an incremental rate of 30° C./minute to 290° C. (internal 270° C.) and held stable during 12 minutes. Then, the catalyst was cooled down to room temperature.
Composition II (zeolite EU-2 and titania)
An extrudable mass was prepared by combining 50 wt % zeolite EU-2 and 50 wt % 100% anatase titania powder sold by Millenium Specialty Chemicals Inc. identified as Millenium's G5 grade titania having a nitrogen B.E.T. surface are of 293 m2/g and a bulk density of 0.56 g/ml. The weight amounts are basis dry components. The mass was extruded to give extrudates having a cylinder shape and an average diameter of 1.6 mm. These extrudates were dried at 120° C. and calcined at 625° C. for 1 hour to provide calcined extrudates.
These extrudates were treated at a temperature of 90° C. for 5 hours with 0.01 M aqueous ammonium hexafluorosilicate (AHS) solution. The weight ratio of solution to extrudates was 5:1. Subsequently, the extrudates were separated from the solution, washed with deionized water, and dried at 120° C. for 2 hours followed by calcination at 500° C. for 1 hour.
Thereafter, 0.7% wt/wt platinum was incorporated into the composition by pore volume impregnation during about 10 minutes with an aqueous solution containing tetramine platinum nitrate (Pt(NH3)4(NO3)2) (3.37% w/w Pt).
The impregnated composition was not washed, but it was equilibrated during 1.5 hours on a rolling bed, dried for 10 minutes at 180° C. (temperature incrementally increased at a rate of 15° C./minute). The temperature was raised again at an incremental rate of 30° C./minute to 290° C. (internal 270° C.) and held stable during 12 minutes. Then, the catalyst was cooled down to room temperature.
Composition III (zeolite EU-2 and titania)
This composition was prepared in the same manner as described above for Composition II with the exception that the titania powder is Degussa (Evonik) P25 80 wt % anatase and 20 wt % rutile titania.
Example II
This Example II describes the performance testing of the compositions of Example I in the catalytic dewaxing of a waxy raffinate feed and presents the results thereof.
The catalyst under scrutiny was dried at 250° C. for 3 hours. Subsequently, the catalyst was mixed with sufficient inert material to assure proper plug flow conditions and loaded into a single tube test reactor of down flow mode. Subsequently, a hydrogen partial of 40 bar was applied and the temperature was increased from room temperature to 125° C. at a rate of 20° C./h, and held for two hours. The temperature was then increased further to 300° C. at a rate of 50° C./h, and held for 8 hours to ensure proper reduction of the metallic phase.
The reactor was cooled to 200 ° C. and then the feed having the properties presented in Table 1 was introduced at a weight hourly space velocity of 1.0 kg feed per liter catalyst per hour, together with hydrogen at a rate of 500 Nl per kg of feed. After feed break through, the temperature was increased to 250° C. in 4 hours, and held overnight. The temperature was then adjusted to obtain a liquid product cloud point of −30° C. The cloud points were measured according to ASTM D 2500.
The performance of catalysts I, II and III is shown in Table 2. The expression % w of stands for the weight percent on feed, 400° C.+ stands for product having a boiling point above 400° C. measured according to ASTM D-2887. The yield of 400° C.+ product can be considered equivalent to the base oil yield. Treq is the temperature required to reach the target total liquid product pour point (TLP PP) of −30° C.







TABLE 1





Waxy Raffinate Feed Properties



















Feed





Density at 70/4° C.
g/ml
0.7844



Carbon content
% w
85.28



Hydrogen content
% w
14.72



Sulphur content,
ppmw
<10



Nitrogen content,
ppmw
<1



UV Mono-aromatics Aromatics
mmol/100 g
0.30



Pour Point
° C.
+48



Cloud Point
° C.
+56



TBP-GLC



0.5% w recovery (IBP)
° C.
289



10% w recovery
° C.
405



50% w recovery
° C.
461



90% w recovery
° C.
520



98% w recovery
° C.
548



99.5% w recovery
° C.
567

















TABLE 2







Catalyst Performance Results










Waxy Raffinate @ TLP PP = −30° C.














Yield 400° C.+



Catalyst
Treq (° C.)
(% wof)







I
358
74.4



II
330
73.2



III
329
75.5










As may be seen from the data presented in Table 2, the Catalysts II and III with the titania binder exhibits significantly better catalytic dewaxing activity than the comparative Catalyst I that uses a silica binder with the activity gain being approximately 28 to 29° C. It is theorized that an interaction between the silica and zeolite of Catalyst I in some way impacts the catalytic activity of the composition.

## Claims

1. A catalyst composition comprising a mixture comprising titania and zeolite EU-2 having a molar bulk ratio of silica-to-alumina (SAR) of greater than 115:1; wherein said zeolite EU-2 is present in said composition in an amount of at least 10 wt. % and at most 60% wt and said titania is present in said composition in an amount of no more than 90% wt, with such % wt being based on the dry weight of said composition; and wherein said titania has a high surface area greater than 105 m2/gm.

2. A catalyst composition as recited in claim 1, further comprising a noble metal selected from the group consisting of platinum and palladium.

3. A catalyst composition as recited in claim 1, wherein said mixture contains zeolite EU-2 particles of which the average aluminum concentration is at least 1.1 times the aluminum concentration at the surface of the EU-2 particles.

4. A catalyst composition as recited in claim 1, wherein said catalyst composition is substantially free of silica other than the silica contained in said zeolite EU-2 framework.

5. A catalyst composition as recited in claim 1, wherein said catalyst composition is substantially free of alumina other than the alumina contained in said zeolite EU-2 framework.

6. A catalyst composition as recited in claim 1, wherein said zeolite EU-2 has a molar bulk ratio of silica-to-alumina greater than 120:1 and said titania has a B.E.T. surface area greater than 125 m2/gm.

7. A catalyst composition as recited in claim 1, wherein more than 60 wt % of said titania is in the form of anatase titania.

8. A catalyst composition as recited in claim 1, wherein said zeolite EU-2 content of said composition is at least 25 wt % and at most 55 wt % and the titania content of said composition is at least 30 wt % and no more than 75 wt %.

9. A catalyst composition as recited in claim 1, wherein said zeolite EU-2 has a molar bulk ratio of silica-to-alumina greater than 130:1 and said titania has a B.E.T. surface area greater than 150 m2/gm.

10. A catalyst composition as recited in claim 1, wherein said zeolite EU-2 content of said composition is at least 30 wt % and at most 60 wt % and the titania content of said composition is at least 40 wt % and at most 90 wt %.

11. A catalyst composition as recited in claim 1, further comprises a noble metal selected from the group consisting of platinum and palladium; and wherein said zeolite EU-2 has a molar bulk ratio of silica-to-alumina greater than 130:1 and less than 500:1; said titania has a B.E.T. surface area greater than 175 m2/gm and less than 700 m2/gm; said zeolite EU-2 content of said composition is at least 10 wt % and at most 55 wt %; and said titania content of said composition is at least 45 wt % and no more than 70wt % of said composition.

12. A catalyst composition as recited in claim 11, wherein said titania includes more than 60 wt % titania in the anatase form and less than 40 wt % in the rutile form.

13. A method for preparing said catalyst composition of claim 1, wherein said method comprises: preparing a mixture comprising at least 40 wt. % and no more than 80 wt. % titania, having a high surface area greater than 105 m2/gm, ant at most 60wt. % zeolite EU-2 having a molar bulk ratio of silica-to-alumina (SAR) of greater than 115:1 and forming said mixture into a particle.

14. A method as recited in claim 13, further comprising: drying and calcining said particle to thereby provide a calcined particle.

15. A method as recited in claim 14, further comprising: subjecting said calcined particle to dealumination to thereby provide a dealuminated particle comprising dealuminated zeolite.

16. A method as recited in claim 15, further comprising:
incorporating a noble metal into said dealuminated particle to thereby provide a catalyst composition comprising zeolite EU-2, titania and said noble metal.

17. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 1.

18. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 2.

19. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 3.

20. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 4.

21. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 5.

22. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 6.

23. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 7.

24. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 8.

25. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 9.

26. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 10.

27. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 11.

28. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the catalyst composition of claim 12.