KR101385333B1 - Isomerization Process Using Metal-Modified Small Crystallite MTT Molecular Sieve - Google Patents

Abstract

The present invention relates to a process for dewaxing a hydrocarbon feed by isomerizing the feed into small crystal sieves having a MTT framework, the catalyst comprising Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd. At least one metal selected from the group consisting of and at least one group VIII metal. There is also provided a dewaxing process for producing products boiling above 343 ° C. (650 ° F.) with a slope of zero or less on the Pour Point vs. Viscosity Graph and having a low pour point and high viscosity index. The dewaxing method includes isomerizing dewaxing a feed having a viscosity of 100 ° C. of at least 2.5 mm ² / s on a metal modified molecular sieve to produce a product having a low pour point and a high viscosity index, the graph of the pour point and viscosity index The fitted line at has a slope of zero or less and the yield of the product is high.

Isomerization, Desoldering, Molecular Sieve, Metal Modification, MTT Framework, Structural Phase

Description

Isomerization Process Using Metal-Modified Small Crystallite MTT Molecular Sieve

The present invention relates to a method for isomerizing straight and weakly branched paraffin feeds having 10 or more carbon atoms using a catalyst comprising a metal loaded small crystal MTT molecular sieve. The invention also relates to a dewaxing process for producing a product having an improved viscosity index at low boiling points.

The production of Group II and III base oils using hydroprocessing has recently become very popular. Catalysts demonstrating improved isomerization selectivity and conversion are continually searched. As mentioned in US Pat. No. 5,282,958, column 1-2, ZSM-22, ZSM-23, ZSM-35, SSZ-32, SAPO-11, SAPO-31, SM in the isomerization and shape selective dewaxing process. The use of mesoporous molecular sieves such as -3, SM-6 is well known. Other common zeolites useful for the dewaxing method are ZSM-48, ZSM-57, SSZ-20, EU-1, EU-13, ferrierrite, SUZ-4, theta-1, NU-10, NU-23, NU-87, ISI-1, ISI-4, KZ-1 and KZ-2.

US Pat. Nos. 5,252,527 and 5,053,373 disclose zeolites such as SSZ-32 prepared using N-lower alkyl-N'-isopropyl-imidazolium cations as templates. 5,053,373 discloses a silica to alumina ratio of 20 or more and 40 or less and a constraint index of 13 or more after calcination and in hydrogen form. The zeolites of heading 5,252,527 are not limited to a bond index of 13 or greater. 5,252,527 discloses a zeolite loaded with metal to provide a hydrogenation-dehydrogenation function. Common substituted cations may include hydrogen, ammonium, metal cations, such as rare earth metals, Group IIA and Group VIII metals, and mixtures thereof. A process for preparing MTT-type zeolites such as SSZ-32 or ZSM-23 using small neutral amines is disclosed in US Pat. No. 5,707,601.

U. S. Patent No. 5,397, 454 discloses a hydroconversion method using a zeolite such as SSZ-32 having a small crystal size and post calcination and a bond index of at least 13 in hydrogen form. The catalyst has a silica to alumina ratio of at least 20 and at most 40. U.S. Pat.No. 5,300,210 relates to a hydrocarbon conversion process using SSZ-32. SSZ-32 of US Pat. No. 5,300,210 is not limited to small crystal size.

U.S. Pat.No. 7,141,529 describes a group of different metals (metals or Ca, Cr, Mg, La, Ba, Pr, Sr, K and Nd to provide a catalyst with improved isomerization selectivity with nC ₁₆ feed). A method of modifying the metal of a molecular sieve using a selected metal, and also a Group VIII metal) is disclosed. Processes for producing molecular sieves with small crystal size have not been disclosed. An isomerization method is also disclosed that provides a slope of the VI (viscosity index) to the pour point of the product boiling at 650 ° F. (343 ° C.) above zero.

US Patent Publication No. 2007 / 0041898A1 discloses a process for preparing small crystal MTT catalysts. However, no method of modifying the molecular sieve with a metal has been disclosed.

Summary of the Invention

The present invention relates to a process for deleaving a hydrocarbon feed comprising straight or branched chain paraffins having at least 10 carbon atoms to produce an isomerization product, comprising contacting the hydrocarbon feed with a catalyst in the presence of hydrogen under isomerization conditions. Wherein the catalyst comprises a molecular sieve having an MTT structure phase and a crystal diameter of about 200 to about 400 microns in the longest direction, the catalyst comprising Ca, Cr, Mg, La, Na, Pr, Sr, K and At least one metal selected from the group consisting of Nd and at least one Group VIII metal.

In addition, isomerization decarburization of the hydrocarbon feed with at least 5% by weight of wax to produce at least two isomerization products boiling above 343 ° C. (650 ° F.), each of which isomerization products

a. Pour point from 0 to -30 ° C, and

b. Has a corresponding viscosity index of at least 95;

A line fit to a chart for the flow point on the x-axis and the viscosity index graph on the y-axis provides a dewaxing method with a line slope for y or more than zero.

In addition, isomerization decarburization of the hydrocarbon feed with at least 5% by weight of wax to produce at least two isomerization products boiling above 343 ° C. (650 ° F.), each of which isomerization products

a. Pour point from 0 to -30 ° C, and

b. Has a corresponding viscosity index of at least 95;

The fitted line for the flow point on the x-axis and the viscosity index graph on the y-axis has a line slope for y or greater than zero; A yielding process is provided wherein the yield of isomerization products boiling above at least 243 ° C. (650 ° F.) is at least 90% by weight relative to the feed.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the catalyst consists of molecular sieves having an MTT structural phase. The catalyst used comprises 5 to 85% by weight molecular sieve. As used herein, "molecular sieve" may include "zeolite". "MTT-type zeolites", "MTT molecular sieves" or their modifications represent the framework structure code for a group of molecular sieve materials. The Structural Commission of the International Zeolite Association (IZA) assigns a code of three alphabetic characters to a zeolite (molecular type) having a determined structure. Zeolites with the same topology are generally named with these three letters. The MTT code is given to the structure of molecular sieves including ZSM-23, SSZ-32, EU-13, ISI-4 and KZ-1. As a result, zeolites having structures similar to the framework structures of ZSM-23 and SSZ-32 are named MTT zeolites.

Other molecular sieves useful for isomerization dewaxing are mesoporous sized molecular sieves with MTT, TON, AEL or FER structure phase.

The small crystal MTT zeolite used in one embodiment of the catalyst has a crystal diameter of about 200 kPa to about 400 kPa in the longest direction.

Catalyst preparation

In one embodiment, the small crystal MTT molecular sieve is a source of an alkali metal oxide or hydroxide, an alkylamine (such as isobutylamine), an organic carbon compound source of quaternary ammonium ions, which are subsequently ion exchanged in hydroxide form, aluminum oxide ( For example, an aluminum oxide source is prepared from an aqueous solution comprising silicon oxide covalently dispersed in silica, and silicon oxide. In one embodiment, the organic carbon compound source of quaternary ammonium ions that are subsequently ion exchanged in hydroxide form is an N-lower alkyl-N'-isopropyl-imidazolium cation (e.g., N, N'-diisopropyl). Imidazolium cation or N-methyl-N'-isopropyl-imidazolium cation). The aqueous solution has a molar ratio composition in the following range:

[Table 1]

Mole ratio  Furtherance

Example 1 Example 2 SiO ₂ / Al ₂ O ₃ 20 to 40 or less 30-35 OH- / SiO ₂ 0.10-1.0 0.20-0.40 Q / SiO ₂ 0.05-0.50 0.10-0.25 M + / SiO ₂ 0.05-0.30 0.15-0.30 H ₂ O / SiO ₂ 20-300 25-60 Q / Q + M + 0.25-0.75 0.33-0.67

Where Q is the sum of Qa and Qb; M is an alkyl metal oxide or hydroxide; M + is an alkali metal oxide or hydroxide-derived alkali metal cation. Alkali metals are a series of elements including Group 1 of the periodic table (IUPAC style): lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr).

Qa is a source of organic carbon compounds of quaternary ammonium ions and Qb is an amine. In one embodiment, Qa is N-lower alkyl-N'-isopropyl-imidazolium cation (e.g., N, N'-diisopropyl-imidazolium cation or N-methyl-N'-isopropyl-imi Dazolium cation). Several different Qb amines are useful. In one embodiment, isobutyl amine, neopentyl amine, monoethyl amine or mixtures thereof are suitable examples of Qb. The molar concentration of Qb is greater than the molar concentration of Qa. In general, the molar concentration of Qb is 2 to about 9 times greater than the molar concentration of Qa. U.S. Pat.No. 5,785,947 (incorporated herein by reference) discloses that the method of zeolite synthesis using two organic nitrogen sources (one source is an amine containing from 1 to 8 carbons) is the fourth source of organic components. It describes a method of significantly reducing costs compared to using an ammonium ion source (such as imidazolium). The combination of two organic nitrogen sources allows the primary template (used in smaller amounts) to nucleate the desired zeolitic structure and then allow the amine to fill the pores in a stable manner during the crystal growth period. The hollow pores of the high silica zeolite are likely to be redissolved under synthetic conditions. In addition, amines may contribute to maintaining elevated alkalinity for synthesis.

In one embodiment, the organic carbon compound source of quaternary ammonium ions provides hydroxide ions.

In one embodiment, the organic carbon compound source, Qa, of the quaternary ammonium ions of the aqueous solution is derived from a compound of the formula

Wherein R is lower alkyl including 1 to 5 carbon atoms, for example -CH3 or isopropyl. Anions (Aθ), which are not harmful to the production of MTT molecular sieves, are associated with cations. Examples of anions are halogens (eg fluoride, chloride, bromide and iodide), hydroxides. (hydroxide), acetate, sulfate, carboxylate and the like. Hydroxide is a particularly useful anion.

The reaction mixture is prepared using standard zeolite preparation techniques. Common sources of aluminum oxide for the reaction mixtures include aluminum compounds such as aluminate, alumina, and aluminum coated silica colloids (an example Nalco 1056 colloid sol), Al ₂ (SO ₄ ) ₃ and other zeolites. .

In one embodiment, the aluminum oxide is in the form of covalently dispersed on silica. Covalently dispersed forms of aluminum oxide enable molecular sieves with increased aluminum content to crystallize. Increased aluminum content in the molecular sieve promotes isomerization. In another approach, a pentasil structure and low silica / alumina ratio (approximately 10) zeolite can be used as a source of aluminum oxide or feedstock for the synthesis of small crystal MTT characters. Such zeolites are recrystallized into small crystal MTT molecular sieves in the presence of the organic sources Qa and Qb described above.

Mordenite and ferrierite zeolites consist of two useful aluminum oxide sources or feedstocks. Such ferrite zeolites are used for crystallization of ZSM-5 and ZSM-11 (US Pat. No. 4,503,024).

Another approach, in which aluminum oxide is a covalently dispersed form on silica, is described in Nalco Chem. Alumina coated silica sol such as the trade name 1056 colloidal sol (26% silica, 4% alumina) manufactured by Co. In addition to providing a novel SSZ-32X with a high aluminum content, the use of a sol produces crystals up to 1000 A (along the reference axis) with very high isomerization capabilities.

In one embodiment, the catalytic performance of the MTT molecular sieve (hydrogen) with respect to degradability is evident by a Constraint Index value (defined in J. Catalysis 67, page 218) of at least 13, In the example the MTT molecular sieve (hydrogen) has a bond index of 13 to 22. The determination of the bond index is disclosed in US Pat. No. 4,481,177. In general, smaller crystal sizes of the zeolite reduce form selectivity. This was demonstrated for ZSM-5 reactions involving aromatics as reported in J. Catalysis 99, 327 (1986). Zeolite ZSM-22 (US Pat. No. 4,481,177) is also known to be closely associated with ZSM-23 (J. Chem. Soc. Chem. Comm. 1985, page 1117). In the above reference to ZSM-22, it has been reported that ball milling the crystals produces a catalyst with a bond index of 2.6. This is a very low value for such a substance given in another study that points out that this is a very selective 10-ring pentasil (Proc. Of 7th Intl. Zeolite Conf. Tokyo, 1986, p. 23). Perhaps ball milling lowers selectivity by producing smaller crystals, but increases catalytic activity. Unlike earlier small crystal catalysts with low bond index, smaller crystalline MTT molecular sieves loaded with metal maintain high selectivity.

Common sources of silicon oxide are silicate, silica hydrogel, silicic acid, colloidal silica, fumed silica, tetraalkyl orthosilicate and Silica hydroxide. Salts, in particular alkali metal halides such as sodium chloride, can be added to or formed in the reaction mixture. These are disclosed in the literature to assist in zeolite crystallization while preventing silica occlusion in the lattice.

The reaction mixture is maintained at elevated temperature until molecular sieve crystals form. The temperature during the hydrothermal crystallization step is generally maintained at about 140 ° C. to about 200 ° C., for example about 160 ° C. to about 180 ° C., or about 170 ° C. to about 180 ° C. The crystallization period is generally at least one day, and in one embodiment the crystallization period is from about 4 days to about 10 days.

Hydrothermal crystallization is usually carried out under pressure in an autoclave such that the reaction mixture is subjected to autogenous pressure. The reaction mixture can be stirred while the components are added and during the crystallization.

Once the molecular sieve crystals are formed, the solid product is separated from the reaction mixture through standard mechanical separation techniques such as filtration or centrifugation. The crystals are washed with water and dried at 90 ° C. to 150 ° C. for 8-24 hours to obtain synthetic molecular sieve crystals. The drying step may be carried out at atmospheric pressure or below atmospheric pressure,

During the hydrothermal crystallization step, the crystals can spontaneously nucleate from the reaction mixture. The reaction mixture can be seeded with MTT crystals to direct and accelerate crystallization and to minimize the generation of unwanted aluminosilicate contaminants.

In one embodiment, the small crystal MTT zeolite used in the catalyst has a crystal diameter of about 200 kPa to about 400 kPa in the longest direction.

In one embodiment, the small crystalline MTT type molecular sieve can be used synthetically or can be heat treated (calcined). Calcination is advantageously performed at a temperature of about 750 ° F. In general, it is desirable to remove alkali metal cations by ion exchange and replace them with hydrogen, ammonium, or any desired metal ions. Molecular sieves can be filtered with chelating agents such as EDTA or dilute acid solutions to increase the silica alumina molar ratio. Molecular sieves can be treated with steam. Steam treatment helps to stabilize the crystal lattice from acid attack.

The calcined molecular sieve may then be loaded with at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd. Such metals are known to have the ability to change the catalyst performance by reducing the number of strong acid sites on the catalyst and reducing selectivity for degradation versus isomerization. In one embodiment, the modification also includes increased metal dispersibility such that the acid or cationic positions of the catalyst are blocked. In one embodiment, metal loading is accomplished by various techniques including impregnation and ion exchange. Generally, the metal is loaded so that the catalyst comprises 0.5 to 5 weight percent of the metal on a dry weight basis. In one embodiment, the catalyst comprises 2-4% by weight of metal on a dry weight basis.

Common ion exchange techniques include contacting an extrudate or particle with a solution containing a desired substituted cation or salt of cations. Although various salts may be used, in one embodiment the desired substituted cation or salt of cations is selected from the group consisting of chlorides and other halides, nitrates, sulfates and mixtures thereof. Representative ion exchange techniques are disclosed in several patents, including US Pat. Nos. 3,140,249, 3,140,251, and 3,140,253, each of which is incorporated herein by reference. Ion exchange may occur before or after the extrudate or particles are calcined. Calcination is carried out at a temperature of 400-1100 ° F.

After contact with the salt solution of the desired substituted cation, the molecular sieve is dried at a temperature between 149 ° F. and about 599 ° F. The molecular sieve is then further loaded with Group VIII metals using techniques such as impregnation to enhance hydrogenation. In some embodiments, it is desirable to impregnate the modified metal and the Group VIII metal at once, as disclosed in US Pat. No. 4,094,821. In one embodiment, the Group VIII metal is platinum, palladium or a mixture of both. In one embodiment, the material may be calcined at temperatures between 500 and 900 ° F. in air or in an inert gas after metal loading.

In the end, examples of general methods for preparing catalysts include the following steps:

(a) synthesizing small crystal MTT zeolite in an aqueous solution;

(b) mixing the small crystal MTT zeolite with a refractory inorganic oxide carrier precursor and an aqueous solution to form a mixture;

(c) extruding or shaping the mixture of step (b) to produce an extrudate or shaped particles;

(d) drying the extrudate or shaped particles of step (c);

(e) calcining the dry extrudate or shaped particles of step (d);

(f) impregnating the calcined extrudate or shaped particles of step (e) with at least one metal selected from the group consisting of Ca, Cr, Mg, La, Ba, Na, Pr, Sr, K and Nd Producing water or shaped particles;

(g) drying the metal-formed extrudate or shaped particles of step (f);

(h) further impregnating the metal-formed extrudate or shaped particles of step (g) with a Group VIII metal to prepare a catalyst precursor;

(i) drying the catalyst precursor of step (h); And

(j) calcining the dry catalyst precursor of step (i) to produce a final combined catalyst.

The use of active materials in combination with, or in combination with, synthetic molecular sieves tends to improve the conversion and selectivity of the catalyst in certain organic conversion processes. Examples of active materials are hydrogenation components and metals added to affect the overall function of the catalyst. In one embodiment, the overall function of the catalyst includes improving isomerization and reducing degradation activity.

In one embodiment, small crystal MTT molecular sieves may be used with the hydrogenation component for applications in which the hydrogenation-dehydrogenation function is desired. Common hydrogenation components may include hydrogen, ammonium, metal cations (such as precious earth metals, Group IIA metals and Group VII metals) and mixtures thereof. Examples of metal hydrogenation components include tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, and platinum ), Palladium (or other precious metals). In one embodiment, the Group VIII metal is a precious metal selected from the group consisting of platinum, palladium, rhenium and mixtures thereof. In yet another embodiment, the Group VIII metal is a precious metal selected from platinum, palladium, and mixtures thereof. In one embodiment, a metal hydrogenation component is added to consist of about 0.3 to about 5 weight percent catalyst on a dry weight basis.

Metals added to influence the overall function of the catalyst (improving isomerization and reducing degradation activity) are manganese, lanthanum (and other precious metals), barium, sodium, prasiodymium ( praseodymium, strontium, potassium, and neodymium. Other metals that can be used to affect the overall function of the catalyst include zinc, cadmium, titanium, aluminum, tin and iron.

Hydrogen, ammonium and metal components can be exchanged inside the molecular sieve. Zeolites may also be impregnated with metals, which may be physically intimately mixed with the molecular sieve using standard methods known in the art. The metal can be occluded in the crystal lattice by having the desired metal present as ions in the reaction mixture from which the zeolite is made.

In one embodiment, the molecular sieve zeolites described are converted to their acidic form and then mixed with the poorly soluble inorganic oxide carrier precursor and the aqueous solution to form a mixture. In one embodiment, the aqueous solution is acidic. The aqueous solution acts as a peptizing agent. In one embodiment, the carrier (known as the matrix or binder) is selected that is resistant to the temperature and other conditions used in the organic conversion process. Such matrix materials include active and inert materials, and synthetic or naturally occurring zeolites, and inorganic materials such as clays, silicas, and metal oxides. In one embodiment, the carrier occurs naturally. In another embodiment, the carrier is in the form of a gelatinous precipitate, sol or gel comprising a silica mixture and a metal oxide.

In one embodiment, the molecular sieve is a porous matrix material and silica, alumina, titania, magnesia, silica-alumina, silica-magnesia Matrices such as silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia A mixture of materials and ternary compositions such as silica-alumina-toria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix may be in the form of a cogel. In one embodiment, the matrix material is alumina and silica.

Inert materials are suitably provided as diluents to control the amount of conversion in a given process so that the product is economically obtained without using other means to control the reaction rate. Often, zeolite materials have been mixed into naturally occurring clays such as bentonite and kaolin. Some of these materials, such as clays, oxides, etc., function in part as binders for catalysts. In petroleum refining, it is desirable to provide a catalyst with good compressive strength because the catalyst is often easy to handle roughly. This tends to break the catalyst into powder, which causes problems in processing.

As used herein, "metal-modified" means that the catalyst molecular sieve is at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd and at least one It means containing a Group VIII metal. Group VIII metals are Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt.

In one embodiment, the naturally occurring clay consists of synthetic small crystal MTT molecular sieves. Examples of naturally occurring clays include montmorillonite and kaolin series, which are commonly known as sub-bentonite, commonly known as Dixie, Mcnamee, Georgia, and Florida clays. ) And kaolin, or other clays whose main mineral constituents are halloysite, kaolinite, dickite, nacrite, or anauxite. Fibrous clays such as sepiolite and attapulgite can also be used as support. Such clays can be used as raw materials first discovered, or initially treated with calcination, acid treatment or chemical modification.

Molecular sieve and binder mixtures can be formed in a variety of physical forms. In general, the mixture may be in the form of powder, particles, or a molded product such as an extrudate having a particle size that passes through a 2.5 mesh (Tyler) screen and does not pass through a 48 mesh (Tyler) screen. For example, when the catalyst is cast through extrusion with an organic binder, the mixture may be extruded before drying, or may be extruded after drying or partial drying. Small crystal MTT molecular sieves can be steamed. Steam treatment helps to stabilize the crystal lattice from acid attack. The dry extrudate is then heat treated using the calcination procedure.

In general, it is desirable for economic reasons to minimize the amount of molecular sieve in the final catalyst. If good activity and selectivity results are obtained, lower molecular sieve levels in the final catalyst are preferred. In one embodiment, the molecular sieve level is 5 to 85% by weight, and in another embodiment 5 to 60% by weight. Molecular sieve levels vary with different molecular sieve forms.

In one embodiment, the metal modified small crystal MTT catalyst provides good yield and exceptional viscosity index (VI) for various feeds. By-product selectivity is significantly changed compared to catalysts containing standard MTT type zeolites. For example, the catalyst causes very low gas and naphtha production. For example, on a waxy 500N hydrocrackate feed including 21% wax with a waxy VI of 122, the product yield was 97% under VI of -15 ° C and 120-121. In general, more drops are seen from the waxed VI to the dewaxed VI. For example, when a catalyst comprising a standard MTT zeolite is used, the VI of the resulting product is about 111. The metal modified standard MTT type zeolite catalyst provides VI of 115. Both gas production and naphtha production are significantly reduced through the use of metal loaded small crystal MTT molecular sieves. This high yield and the VI of the product very close to the VI of the waxy feed after dewaxing are very surprising. The yield of the 700 F + desoldering lubrication product in this case is very high, 97%. Also, the slope of the VI to pour point of the product is not so general that it will not be lowered at the pour point.

In addition, data are obtained on a 150N waxy hydrogenate showing improved product yield and VI compared to past MTT type catalysts. In other words, lower gas production and naphtha production were observed. Mn feed was tested and improved yields and VIs were observed again.

When the Fischer-Tropsch wax feed is treated with a catalyst containing a metal loaded small crystal MTT molecular sieve, the resulting 650 ° F. + product is 165-170 at a flow point of -25 to -30 ° C. Has an exceptional VI. If the 750 ° F. boiling product is split into two additional fractions, the 750-850 ° F. fraction has a dynamic viscosity of 3.8 mm ² / s at 100 ° C. and a very high VI of 151 at a pour point of −18 ° C., 850 ° F. The fraction has a 9.7 mm ² / s viscosity, a pour point of −11 ° C. and a VI of 168. Dynamic viscosity was measured by ASTM D445-06, Pour point was measured by ASTM D5950-02, and VI was measured by ASTM D2270-04.

Supply

In one embodiment, a method of using a catalyst comprising a molecular sieve loaded with a metal with a small crystal MTT phase comprises power oil from a relatively light distillate fraction such as kerosene and jet fuel. whole crude petroleum, reduced drude, vacuum tower residua, cycle oil, synthetic crude oil (e.g. shale oil, tar and oil, etc.), gas Gas oils, vacuum gas oils, foots oils, Fischer-Tropsch derived waxes and intermediates, slack waxes, deoiled slack waxes, waxy lubricants feedstocks ranging from high boiling stocks such as raffinate, n-paraffin wax, NAO wax, waxes produced in chemical plant processes, deoiled petroleum derived waxes, microcrystalline waxes, other heavy oils and mixtures thereof It is used to remove lead.

In one example, the feedstock is a hydrocarbon with at least 5% wax by weight.

Weight percent wax in the feed heats the waxy sample to a temperature above the pour point, 100 g of heated waxy sample is poured into a 1 L beaker and the weight of the heated waxy sample is recorded to two decimal places; 400 mL of toluene: methyl ethyl ketone 1: 1 mixture (MEK) is added to the beaker and measured by dissolving the waxy sample by gentle stirring until homogeneous on a hot plate. The beaker is covered with a piece of aluminum foil and placed in a freezer that has been previously set to the feed point of the feed. Allow the sample to stand overnight. After cooling in the freezer overnight, the mixture is filtered using a filter combination installed in the freezer. Whatman filter 4 (18.5 cm in diameter) is used in a Buchner funnel and the funnel is covered with a piece of aluminum foil to allow ice crystals to collect in the funnel. Connect the funnel to a heavy-duty vacuum, prewet the filter paper with cold MEK, quantitatively deliver the entire mixture in the beaker to the funnel with a spatula, wash the beaker with cold MEK, Filtration is carried out by filtering the rinsate. Close the cooler, wait for the solvent to completely exit the filter, then lower the cooler to its original preset temperature. Wash the wax filter cake thoroughly with cold MEK. Dry the wax cake, turn off the vacuum, and remove the filter-funnel combination from the cooler. A snow blower is used to deliver as much wax as possible from the filter into the jar. Trace wax finally filtered off with hot toluene is removed and the cleaning solution is transferred to a jar. Toluene is evaporated and the wax weight collected in the jar is measured. The oil filtrate is poured into a flask. The solvent is removed using a rotary evaporator and the oil is weighed by weighing the flask and residual oil. The wax percentage is obtained by dividing the weight of the wax collected in the jar by the weight of the heated waxy sample and then multiplying by 100.

Straight n-paraffins alone or in combination with weakly branched paraffins having 16 or more carbon atoms are sometimes referred to herein as waxes. Since light oils are generally free of significant amounts of waxy components, the feedstock will often be a C10 + feedstock boiling above about 350 ° F. However, the process is intermediate distillate comprising gas oil, kerosene, jet stock, lubricating oil stock, heating oil and other distillate fractions where the pour point and viscosity need to be maintained within certain specification limits. Particularly useful is the use of waxy distillate stocks such as raw materials. Lubricant feedstocks generally boil above 230 ° C. (450 ° F.), more generally above 315 ° C. (600 ° F.). Hydrotreated raw materials are a convenient source of this kind of raw material and other distillate fractions because they generally contain significant amounts of waxy n-paraffins. The feedstock of the process normally contains paraffins, olefins, naphthenes, aromatics and heterocyclic compounds, and has a substantial portion of high molecular weight n-paraffins and somewhat branched paraffins that contribute to the waxy properties of the feedstock. It is a raw material. During the process, n-paraffins and somewhat branched paraffins undergo some decomposition or hydrocracking to form liquid range materials that contribute to low viscosity products. However, the degree of decomposition that occurs is limited so that the yield of products having a boiling point lower than that of the feedstock is reduced, thereby preserving the economic value of the feedstock.

Common feedstocks are hydrotreated or hydrocracked gas oils, hydrotreated lubricating oil raffinates, bright stock, lubricating oil stocks, synthetic oils, foot oils, Fischer-Tropsch synthetic oils, high boiling polyolefins, normal alpha olefin waxes , Slack waxes, deoiled waxes, microcrystalline waxes and mixtures thereof.

Fischer-Tropsch waxes are well known methods, such as commercial SASOL® slurry phase Fischer-Tropsch technology, commercial SHELL® Middle Distillate Synthesis (SMDS) methods, or non-commercial. It can be obtained using the EXXON® Advanced Gas Conversion (AGC-21) method. Details of such methods and other methods are described, for example, in EP-A-776959, EP-A-668342; US Patent Nos. 4,943,672, 5,059,299, 5,733,839, and RE39073; And US Published Application Nos. 2005/0227866, WO-A-9934917, WO-A-9920720 and WO-A-05107935. Fischer-Tropsch synthesis products generally include hydrocarbons having 1-100, even 100 or more carbon atoms, and generally include paraffins, olefins, and oxygenated products. Fischer Tropsch is a visible method for producing clean alternative hydrocarbon products including Fischer-Tropsch waxes.

Condition

The conditions under which the isomerization dewaxing process is carried out generally include a temperature of 392 ° F. to about 800 ° F., and a pressure of about 15 to about 3000 psig. Typically the pressure is about 100 to about 2500 psig. The liquid hourly space velocity during contact is generally about 0.1 to about 20, for example about 0.1 to about 5. In one embodiment, the contacting is carried out in the presence of hydrogen. Hydrogen to hydrocarbon ratio of about 2000 to about 10,000 standard cubic feet of H _2/1 barrel hydrocarbon, for example, about 2500 to about 5000 standard cubic feet of H _2/1 barrel hydrocarbon.

In one embodiment, the isomerized dewaxed product is further processed, for example via hydrofinishing or adsorption treatment. Hydrogenation can generally be carried out in the presence of metallic hydrogenation catalysts, for example platinum on alumina. The hydrorefining may be performed at a temperature of about 374 ° F. to about 644 ° F. and a pressure of about 400 psig to about 3000 psig. Hydrogenation tablets in this manner are described, for example, in US Pat. No. 3,852,207, which is incorporated herein by reference.

1 shows a standard MTT-containing catalyst ("std SSZ-32"), a metal modified standard MTT-containing catalyst ("metal modified SSZ-32") and a metal modified small crystal MTT-containing catalyst ("metal modified SSZ-32X"). Yield vs. Pour Point for Isomerization of Heavy Neutral (500N) Feed Using.

FIG. 2 shows standard MTT-containing catalyst (“std SSZ-32”), metal modified standard MTT-containing catalyst (“metal modified SSZ-32”), and metal modified small crystal MTT-containing catalyst (“metal modified SSZ-32X”). Viscosity index (VI) versus pour point for isomerization of heavy neutral (500N) feed using.

Figure 3 shows a standard MTT-containing catalyst ("std SSZ-32"), a metal modified standard MTT-containing catalyst ("metal modified SSZ-32") and a metal modified small crystal MTT-containing catalyst ("metal modified SSZ-32X"). Gas production (production of C ₁ -C ₄ products) versus pour point for isomerization of a heavy neutral (500N) feed using).

4 shows a standard MTT-containing catalyst (“std SSZ-32”), a metal modified standard MTT-containing catalyst (“metal modified SSZ-32”) and a metal modified small crystal MTT-containing catalyst (“metal modified SSZ-32X”). C ₅ product yield versus pour point for isomerization of a heavy neutral (500N) feed using).

5 shows a standard MTT-containing catalyst (“std SSZ-32”), a metal-free small crystal MTT containing catalyst (“small crystal SSZ-32”), a metal modified standard MTT-containing catalyst (“metal modified SSZ-”). 32 ") and yield versus pour point for isomerization of a 150N feed using a metal modified small crystal MTT-containing catalyst (" metal modified SSZ-32X ").

FIG. 6 shows standard MTT-containing catalyst (“std SSZ-32”), metal modified standard MTT-containing catalyst (“metal modified SSZ-32”) and metal modified small crystal MTT-containing catalyst (“metal modified SSZ-32X”). The viscosity index (VI) versus pour point for the isomerization of 150N feed using).

7 shows standard MTT-containing catalyst (“std SSZ-32”), metal modified standard MTT-containing catalyst (“metal modified SSZ-32”) and metal modified small crystal MTT-containing catalyst (“metal modified SSZ-32X”). Gas production versus pour point for isomerization of 150N feed with.

FIG. 8 shows standard MTT-containing catalyst (“std SSZ-32”), metal modified standard MTT-containing catalyst (“metal modified SSZ-32”) and metal modified small crystal MTT-containing catalyst (“metal modified SSZ-32X”). ) Shows the hard naphtha (C ₅ -250 ° F.) yield versus pour point for isomerization of the 150N feed.

9 shows a standard MTT-containing catalyst (“std SSZ-32”), a metal modified standard MTT-containing catalyst (“metal modified SSZ-32”) and a metal modified small crystal MTT-containing catalyst (“metal modified SSZ-32X”). Yield versus pour point for isomerization of a medium neutral feed using

10 shows standard MTT-containing catalyst (“std SSZ-32”), metal modified standard MTT-containing catalyst (“metal modified SSZ-32”) and metal modified small crystal MTT-containing catalyst (“metal modified SSZ-32X”). The viscosity index (VI) vs. pour point for isomerization of the intermediate neutral feed using) is shown.

FIG. 11 shows a comparison of the X-ray diffraction patterns of standard MTT molecular sieves (“standard SSZ-32”) and small crystal MTT molecular sieves (“SSZ-32X”).

Another term that can be used to describe small crystal MTT molecular sieves loaded with metal is "broadline." The synthesis of broadline small crystal molecular sieves (with respect to x-ray diffraction patterns) is substantially the same as crystallizing very small crystal samples of zeolite. As the crystal size decreases, the x-ray diffraction pattern broadens. In general, as the SiO ₂ / Al ₂ O ₃ ratio decreases (more than Al weight percent in zeolite products) with respect to the system of MTT molecular sieves, the crystal size also decreases.

Table 2 (a) shows the peak list of the standard SSZ-32, the standard MTT molecular sieve, and the relative intensities of the peaks. Table 2 (b) shows the peak list of the small crystal MTT molecular sieves and the relative intensities of the peaks before the metal is loaded. Table 2 (b) enlarges the peaks to allow easy comparison of the major peaks of the small crystal MTT molecular sieve with the standard SSZ-32.

[Table 2 (a)]

Standard SSZ -32 peak list

2 theta (θ) d-spacing
(A) Relative Strength (%)
(I / Io x 100) 7.9 11.2 19 8.2 10.8 24 8.9 10.0 11 11.4 7.8 20 14.7 6.05 2 15.9 5.59 5 11.4 5.41 4 18.2 4.88 12 19.6 4.52 69 20.1 4.43 11 20.9 4.25 70 21.4 4.15 9 22.8 3.90 100 23.9 3.73 53 24.0 3.70 58 24.7 3.61 50 25.2 3.53 36 26.0 3.43 42 28.2 3.16 11 29.4 3.03 7 31.6 2.83 13

[Table 2 (b)]

Manufacturing Small crystal MTT  Peak of molecular sieve

2 theta (θ) d-spacing
(A) Relative Strength (%)
(I / Io x 100) 8.03 11.0 33 8.83 10.0 6 11.30 7.83 20 15.71 5.64 3 16.34 5.42 3 18.09 4.90 7 19.54 4.54 33 19.67 4.51 20 20.81 4.27 31 21.21 4.18 14 22.74 3.91 63 23.91 3.72 100 24.54 3.62 24 25.09 3.55 34 25.87 3.44 31 26.91 3.31 5 28.10 3.17 4 29.34 3.04 5 31.46 2.84 8 31.94 2.80 3 34.02 2.63 One 35.22 2.55 17 36.29 2.47 16

FIG. 11 shows the x-ray diffraction patterns of these two types of MTT molecular sieves and clearly demonstrates the broader x-ray diffraction peaks of the small crystal MTT molecular sieve.

Example  One

Small crystal MTT  Synthesis of Molecular Sieves

Small crystal MTT molecular sieves were synthesized as follows. Hastelloy C liner for a 5 gallon autoclave device was used for mixing of the formulation and subsequent heat treatment. The following components were mixed for 30 minutes at 1500 RPM in the order described. 300 g of N, N 'diisopropyl imidazolium hydroxide 1 mole solution was mixed with 4500 g of water. Salt iodide was prepared according to Example 8 of US Pat. No. 4,483,835 and then ion exchanged in hydroxide form using BioRad AG1-X8 exchange resin. 2400 g of 1N KOH was added. 1524 g Ludox AS-30 (30 wt.% SiO ₂ ) was added. 1080 g of Nalco's 1056 colloidal sol (26 wt% SiO ₂ and 4 wt% Al ₂ O ₃ ) was added. Finally, 181 g of isobutylamine was stirred in the mixture. The molar concentration of amine Qb exceeded the molar concentration of imidazolium compound Qa.

Once stirring was completed, the autoclave was closed and the reaction was performed for 8 hours to 170 ° C. The system was stirred at 150 RPM. After heating for 106 hours, the reaction was terminated to recover the product. Solid recovered through filtration (very slow progress: indicates small crystals). After washing the solid several times and dried. The dried material was analyzed by x-ray diffraction and the patterns are shown in Table 3. Comparisons were made using the more standard SSZ-32 data described in Table 2 (a) and it can be seen that the new product of Example 1 is associated with SSZ-32 but has a fairly broad x-ray diffraction line.

[Table 3]

2? d-spacing
(A) century Relative Strength (%)
(I / Io x 100) 8.00 11.05 15 26 8.80 10.05 6 10 11.30 7.83 10 17 14.50 6.11 One 2 15.75 5.63 3 5 16.50 5.37 3 5 18.10 4.901 7 12 19.53 4.545 41 71 20.05 4.428 6 shoulder 10 shoulder 20.77 4.277 41 71 21.30 4.171 7 12 22.71 3.915 58 100 23.88 3.726 57 98 24.57 3.623 30 52 25.08 3.551 25 43 25.88 3.443 27 47 26.88 3.317 5 9 28.11 3.174 6 10

TEM (Transmission Electron Microscopy) analysis was performed as to whether the product was a mixture of small crystals and a significant amount of amorphous material. Microscopic work demonstrated little evidence that the product of Example 1 was an amorphous material and was a fairly uniformly small crystal of the MTT molecular sieve. Crystals are characterized by the spread of small, broad lathe-like components having a diameter of about 200 to about 400 mm in the longest direction. The SiO ₂ / Al ₂ O ₃ ratio of this product is 29.

Example  2

The product of Example 1 was calcined at 1100 ° F. in air, increasing temperature at a rate of 1 ° C./min (1.8 ° F./min) and 3 hours at 250 ° F., 3 hours at 1000 ° F. and 3 hours at 1100 ° F. Calcination was carried out. The calcined material retained x-ray crystallinity. The calcined zeolite as described in US Pat. No. 5,252,527 was ion exchanged twice at 200 ° F. (using NH ₄ NO ₃ ). The ion exchanged material was calcined again and then micropore measurements were performed using the test procedure described in US Pat. No. 5,252,527. The new product showed that the small crystal MTT molecular sieve had some unexpected differences compared to the existing SSZ-32.

Ar adsorption ratio for the small crystal MTT molecular sieve: (Ar adsorption at 87K between relative pressures of 0.001 to 0.1) / (total Ar adsorption up to a relative pressure of 0.1) is at least 0.5. In one embodiment, the Ar adsorption ratio is from 0.55 to 0.70. In contrast to the conventional SSZ-32, the Ar adsorption ratio is 0.5 or less, generally 0.35 to 0.45. The small crystal MTT molecular sieves of Examples 1 and 2 demonstrated an argon adsorption ratio of 0.62.

The outer surface area of the crystals increased from about 50 m ² / g (SSZ-32) to 150 m ² / g (small crystal MTT molecular sieve), indicating that the outer surface increased significantly as a result of very small crystals. At the same time the micropore volume for the small crystal MTT molecular sieve was reduced to about 0.035 cc / g compared to about 0.06 cc / g for the standard SSZ-32.

Example  3

Small crystal MTT zeolites consist of extruded, dried and calcined alumina. The dried and uncoated extrudate is impregnated with a solution comprising both platinum and manganese and then finally dried and calcined. The overall platinum loading is 0.325% by weight. This metal formula catalyst was then tested for isomerization on a waxy 500N hydrocrackate feed having 21% wax, 100.degree. C. dynamic viscosity of 10.218 mm ² / s and a pour point of 51.degree. The isomerization process conditions used were LHSV of 1.0 hr ⁻¹ , gas to oil ratio of 4000 scf / bbl, and total pressure of 2300 psig. After isomerization the product was hydropurified at 450 ° F. on a Pt / Pd silica alumina hydrostatic catalyst. The VI of the waxy 500N hydrocrackate feed was 122 and the VI of the solvent dewaxed waxy 500 hydrocrackate feed was 106 when the solvent was dewaxed at -18 ° C. The difference between the waxy VI and the catalytic isomerization product VI was only 2 (122-120), which was exceptional.

1 and 2 show the yield and product VI versus pour point achieved using metal modified catalysts (“metal modified SSZ-32X”) including small crystal MTT zeolite catalysts. Data and corresponding viscosity indices at different product pour points were obtained by varying the working temperature of the dewaxing catalyst (eg, lower pour points were achieved by raising the catalyst temperature). The results were compared with two other catalysts tested with the same feed under the same conditions, standard MTT containing catalyst ("Std SSZ-32") and metal modified standard MTT containing catalyst ("Metal Modified SSZ-32"). . The isomerization yield of the product boiling above 700 ° F using a metal modified catalyst with a small crystal MTT zeolite catalyst under the -12 to -15 ° C pour point in the general product target range was unprecedented 96 to 97%. The product VI was approximately 120, which is also an excellent value and is believed to contribute to the exceptional amount of isomerized wax contained in the base oil boiling range product. The VI was substantially increased as the slope of the VI to pour point of the product boiling above 700 ° F. was negative, approximately -0.15, thus decreasing the pour point. Example 3 demonstrates that at least two isomerization products boiling above 343 ° C. (650 ° F.) have a corresponding viscosity index of 104, 110 or more. 3 and 4 show C ₁ -C ₄ products (“gas generation”) achieved using metal modified catalysts (“metal modified SSZ-32X”) including small crystal MTT zeolite catalysts compared to two other catalysts; Low yields of C ₅ -C _{250 ° F.} product (naphtha) are shown.

Example  4

The same metal modified catalyst from Example 3 was also tested for isomerization on waxy 150N hydrolyzate feed including 10% wax and 32 ° C. pour point. The isomerization process conditions used were an LHSV of 1.0 hr ⁻¹ , a 4000 scf / bbl gas to oil ratio, and a total pressure of 2300 psig. After isomerization the product was hydropurified on a Pt / Pd silica alumina hydrorefining catalyst at 450 ° F.

5 and 6 show the yield and product VI versus pour point achieved using metal modified catalysts (“metal modified SSZ-32X”) including small crystal MTT zeolite catalysts. The result is three different catalysts: a standard MTT containing catalyst ("Std SSZ-32"), a metal modified standard MTT containing catalyst ("metal modified SSZ-32") and a standard metal crystalline MTT zeolite catalyst ("small" Crystal SSZ-32X "). All four catalysts were tested using the same conditions and the same 150N feed. The isomerization yield of products boiling above 650 ° F. using metal modified catalysts including small crystal MTT zeolite catalysts at -12 to -15 ° C. pour point in the general product target range was 94-95%. Product VI was approximately 108. The slope of the VI to pour point of the product boiling above 650 ° F. was approximately 0.09, significantly lower than that obtained using the comparative catalyst. The VI was not reduced as much as the pour point was reduced using metal modified catalysts including small crystal MTT zeolite catalysts. 7 and 8 show C ₁ -C ₄ products (“gas generation”) achieved using metal modified catalysts (“metal modified SSZ-32X”) including small crystal MTT zeolite catalysts compared to two other catalysts; Low yields of C ₅ -C _{250 ° F.} product (naphtha) are shown.

Example  5

The same metal modified catalyst from Example 3 was also present on a waxy neutral neutral (220N, MN) feed including 12.2% wax, 100 ° C. dynamic viscosity of 6.149 mm ² / s, and 36 ° C. pour point. It was tested for isomerization. The isomerization process conditions used were LHSV of 1.6 hr ⁻¹ , 4000 scf / bbl gas to oil ratio, and total pressure of 2300 psig. After isomerization the product was hydropurified on a Pt / Pd silica alumina hydrorefining catalyst at 450 ° F.

9 and 10 show the yield and product VI versus pour point achieved using metal modified catalysts (“metal number formula SSZ-32X”) including small crystal MTT zeolite catalysts. The results were compared with two other catalysts: standard MTT containing catalyst ("Std SSZ-32") and metal modified standard MTT containing catalyst ("metal modified SSZ-32"). All three catalysts were tested using the same conditions and the same 220N feed. The isomerization yield of the product boiling above 650 ° F. using a metal modified catalyst with a small crystal MTT zeolite catalyst under the −15 ° C. pour point of the general product target range was about 92%. Product VI was 105. The slope of the VI of the product boiling above 650 ° F. over the pour point range of −12 ° C. to −22 ° C. was essentially zero, significantly lower than that obtained using the comparative catalyst. The VI was not reduced as much as the pour point was reduced using metal modified catalysts including small crystal MTT zeolite catalysts.

Example  6

The same metal modified catalyst from Example 3 was subjected to isomerization on a hydrotreated Fischer-Tropsch wax feed prepared with a SASOL @ Slurry Phase Fischer-Tropsch process with at least 90% wax. Was tested against. The isomerization process conditions used were LHSV of 1.0 hr ⁻¹ , 5000 scf / bbl gas to oil ratio, and total pressure of 3000 psig. After isomerization the product was hydropurified on a Pt / Pd silica alumina hydrorefining catalyst at 450 ° F. The resulting product boiling above 650 ° F. had 165 to 170 under a pour point of −25 to −30 ° C. The yield of product boiling above 650 ° F. was at least 65% by weight under 20 ° C. pour point. The product boiling above 650 ° F. was further divided into two fractions by vacuum distillation, that is, the fraction boiling at 750-850 ° F. and the one boiling above 850 ° F. The hard boiling fraction had a 100 ° C. dynamic viscosity of 3.8 mm ² / s, VI of 151 and a pour point of −11 ° C. The heavy boiling fraction had a 100 ° C. dynamic viscosity of 9.7 mm ² / s, VI of 168 and a pour point of −11 ° C. Comparative tests performed using a metal modified standard MTT containing catalyst on the same feed under the same process conditions showed lower yields and somewhat higher VI. Interestingly, even if the VI is rather low using a metal modified small crystal MTT zeolite catalyst, the slope of the VI of the product boiling above 650 ° F. versus the slope of the pour point over the pour point range of -20 ° C. to -50 ° C. (less than 0.56) is compared. It was significantly lower than the slope obtained with the catalyst (above 0.72).

Claims (35)

A method of preparing a base oil comprising contacting a hydrocarbon feed having at least 10 carbon atoms with a catalyst and hydrogen under isomerization conditions, The catalyst comprises a molecular sieve having an MTT framework topology and having a crystal diameter of 200 to 400 GPa in the longest direction; At least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd; And at least one Group VIII metal. The method of claim 1, wherein the molecular sieve is selected from the group consisting of SSZ-32, ZSM-23, EU-13, ISI-4 and KZ-1. The feed of claim 1 wherein the feed is hydrotreated or hydrocracked gas oil, hydrotreated lubricant raffinate, bright stock, lubricant stock, synthetic oil, feet. Oil, Fischer-Tropsch synthetic oil, high kneading polyolefin, normal alphaolefin wax, slack wax, deoil wax, microcrystalline wax and mixtures thereof Way. The method of claim 1 wherein the Group VIII metal is selected from the group consisting of platinum, palladium and mixtures thereof. The method of claim 1, wherein the contacting is performed at a temperature of 232-427 ° C. (450-800 ° F.) and a pressure of 103.4 kPa gauge (15 psig) to 20,685 kPa gauge (3,000 psig). 6. The method of claim 5, wherein the pressure ranges from 689.5 kPa gauge (100 psig) to 17,237 kPa gauge (2,500 psig). 6. The method of claim 5, wherein the liquid hourly space velocity during contact is between 0.1 and 20. 8. The method of claim 7, wherein the fluid space velocity is between 0.5 and 5. The method of claim 1, wherein the hydrocarbon feed is hydrotreated at a temperature of 163-427 ° C. (325-800 ° F.) prior to isomerization. The method of claim 1 further comprising a hydrofinishing step involving isomerization. The method of claim 10, wherein the hydrorefining is performed at a temperature of 163 to 310 ° C. (325 to 590 ° F.) and a pressure of 2,068 kPa gauge (300 psig) to 20,685 kPa gauge (3,000 psig). The method of claim 1 further comprising the hydropurification step of the isomerization product. Isomerizing dewaxing the hydrocarbon feed with at least 5 wt.% Wax on the catalyst to produce two or more isomerization products, each boiling above 343 ° C. (650 ° F.), Each isomerization product is a. Pour point from 0 to -30 ° C, and b. Has a corresponding viscosity index of at least 95; A line fit to a chart with a flow point on the x-axis and a viscosity index graph on the y-axis has a line slope for y or more than zero. The method of claim 13 wherein the hydrocarbon feed has at least 10 wt% wax. The method of claim 13 wherein the hydrocarbon feed has a dynamic viscosity of at least 2.5 mm ² / s at 100 ° C. The dewaxing method according to claim 13, wherein the catalyst has an MTT structure phase and a crystal diameter of 200 to 400 kPa in the longest direction. The method of claim 16 wherein the catalyst further comprises at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd. 18. The method of claim 17 wherein the catalyst further comprises at least one Group VIII metal. The method of claim 13 wherein the isomerization product has a corresponding viscosity index of at least 104. 15. The method of claim 13 wherein the yield of isomerization product is at least 90% by weight relative to the feed. The method of claim 20, wherein the yield is 94% by weight or more. The dewaxing method according to claim 13, wherein the inclination of the line is -0.05 or less. Isomerizing dewaxing the hydrocarbon feed with at least 5 wt.% Wax on the catalyst to produce two or more isomerization products, each boiling above 343 ° C. (650 ° F.), Each isomerization product is a. Pour point from 0 to -30 ° C, and b. Has a corresponding viscosity index of at least 95; The fitted line for the flow point on the x-axis and the viscosity index graph on the y-axis has a line slope for y or greater than zero; Wherein the yield of the isomerization product is at least 90% by weight relative to the feed. 24. The method of claim 23 wherein the catalyst has an MTT structural phase. 24. The dewaxing process of claim 23 wherein the catalyst has a crystal size of 200-400 kPa. The method of claim 1, wherein the contact comprises a temperature of 200-427 ° C. (392-800 ° F.), a pressure of 103.4 kPa gauge (15 psig) to 20,685 kPa gauge (3,000 psig), and a fluid space velocity of 0.1-20. liquid hourly space velocity). The method of claim 1, wherein the hydrocarbon feed having 10 or more carbon atoms is a heavy neutral feed. 28. The method of claim 27, wherein said base oil is a Group III base oil. The method of claim 27, wherein the method has a base oil yield of at least 97% at a pour point of −15 ° C. 29. The method of claim 1, wherein the hydrocarbon feed having 10 or more carbon atoms is a medium neutral feed. 31. The method of claim 30, wherein said base oil is a Group II base oil. 31. The method of claim 30, wherein the base oil yield is at least 92% at a pour point of -15 ° C. The method of claim 1 wherein the hydrocarbon feed having at least 10 carbon atoms is a light neutral feed. 34. The method of claim 33, wherein the base oil is a Group II base oil. 34. The method of claim 33, wherein the method has a base oil yield of at least 94% at a pour point of -15 ° C.

Images