JP2010506010A - Isomerization method using metal-modified small crystal MTT molecular sieve - Google Patents

Abstract

The feedstock is dewaxed by isomerizing the hydrocarbon feedstock with a catalyst comprising a small crystal molecular sieve having an MTT structure, wherein the catalyst is 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. A boil above 343 ° C. (650 degrees Fahrenheit) and a line that fits the pour point and viscosity index chart produces a product with a high viscosity index and a low pour point (X axis) with a slope below zero. Low way. A feedstock having a viscosity of at least 2.5 mm ² / sec at 100 ° C. is isomerized and dewaxed on metal modified molecular sieves (SSZ-32 and SSZ-32X) and has a low pour point (X axis) and a high viscosity index. And a dewaxing process comprising producing a product whose line fitting the pour point and viscosity index chart has a slope of zero or less, wherein the yield of such product is high (FIG. 1).

Description

(Field of Invention)
The present invention is a process for isomerizing a feed comprising paraffin having 10 or more carbon atoms with linear and few branches using a catalyst comprising a small crystal MTT molecular sieve loaded with metal. About. The invention also relates to a dewaxing process that produces a product having an improved viscosity index at a low pour point.

(Background of the Invention)
Production of Group II and Group III base oils using hydroprocessing has become increasingly common in recent years. There is a continuing need for catalysts that exhibit improved isomerization selectivity and conversion. As described in US Pat. No. 5,282,958, columns 1-2, intermediate pore molecular sieves in isomerization and shape selective dewaxing, such as ZSM-22, ZSM-23, ZSM-35, SSZ- 32, SAPO-11, SAPO-31, SM-3, SM-6 and the like are well known. Other representative zeolites useful for dewaxing are ZSM-48, ZSM-57, SSZ-20, EU-1, EU-13, ferrietite, SUZ-4, theta-1, NU-10. , NU-23, NU-87, ISI-1, ISI-4, KZ-1 and KZ-2.

  U.S. Pat. Nos. 5,252,527 and 5,053,373 disclose zeolites such as SSZ-32 prepared using N-lower alkyl-N-'isopropyl-imidazolium cation as a template. US Pat. No. 5,053,373 discloses a silica to alumina ratio of greater than 13 and a silica index greater than 20 and less than 40 in the hydrogen form after calcination. . The zeolite of US Pat. No. 5,252,527 is not limited to a constraint index of 13 or higher. U.S. Pat. No. 5,252,527 discloses loading the zeolite with metal to provide a hydrogenation-dehydrogenation function. Exemplary exchange cations can include hydrogen, ammonium, metal cations such as rare earths, Group IIA and Group VIII metals, and mixtures thereof. The production of MTT-type zeolites, such as SSZ-32 or ZSM-23, using small neutral amine compounds is disclosed in US Pat. No. 5,707,601.

  U.S. Pat. No. 5,397,454 discloses a hydroconversion process using zeolites such as SSZ-32 with a small crystal size and post-calcined hydrogen form, and a constraint index of 13 or greater. . The catalyst has a silica to alumina ratio greater than 20 and less than 40. U.S. Pat. No. 5,300,210 also relates to a hydrocarbon conversion process using SSZ-32. The SSZ-32 of US Pat. No. 5,300,210 is not limited to small crystal sizes.

US Pat. No. 7,141,529 uses various metals (metals selected from the group consisting of Ca, Cr, Mg, La, Ba, Pr, Sr, K and Nd, and also Group VIII metals). Discloses a metal-modification method for molecular sieves to obtain a catalyst with improved isomerization selectivity using an nC ₁₆ feed. Among these methods, there is no method for producing a molecular sieve having a small crystal size. No isomerization method has been shown which results in a slope of VI for products boiling at 650 degrees Fahrenheit (343 ° C.) and above for pour points below zero.

  US Patent Publication 2007 / 0041898A1 discloses a method for producing a small crystal MTT catalyst. There is no disclosure of metal modification of such molecular sieves.

(Summary of the Invention)
There is provided a process for dewaxing a hydrocarbon feed comprising paraffins having 10 or 11 carbon atoms having straight and few branches and producing an isomerized product, the process comprising isomerization conditions Contacting the feedstock with a catalyst comprising a molecular sieve having an MTT structural phase and having a crystal diameter of from about 200 to about 400 angstroms in the longest direction in the presence of hydrogen, wherein the catalyst is Ca, Cr And at least one metal selected from the group consisting of Mg, La, Na, Pr, Sr, K and Nd, and at least one Group VIII metal.

A dewaxing process is also provided, wherein the process isomerizes and dewaxes a hydrocarbon feedstock having a content of at least 5 wt% wax over the catalyst and boiles at 343 ° C (650 degrees Fahrenheit) or higher. Producing the above isomerized product,
Each of these isomerization products is
a. A pour point of 0 to −30 ° C., and b. A corresponding viscosity index of 95 or more,
Where the line fitted to the pour point on the x-axis and the viscosity index chart on the y-axis has a slope of zero or less with respect to y.

A dewaxing process is also provided, wherein the process isomerizes and dewaxes a hydrocarbon feedstock having a content of at least 5 wt% wax over the catalyst and boiles at 343 ° C (650 degrees Fahrenheit) or higher. Producing the above isomerized product,
Each of these isomerization products is
a. A pour point of 0 to −30 ° C., and b. A corresponding viscosity index of 95 or more,
Where the line fitted to the pour point on the x-axis and the viscosity index chart on the y-axis has a slope of zero or less with respect to y, and more than 343 ° C. (650 degrees Fahrenheit) The yield of the two or more isomerized products boiling at is 90% by weight or more based on the feed.

FIG. 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”). ') Shows the yield versus pour point for the isomerization of heavy neutral (500N) feedstock using FIG. 2 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”). ]) Shows the viscosity index (VI) versus pour point for the isomerization of heavy neutral (500 N) feeds using. FIG. 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”). )) Shows the gas production (C ₁ -C ₄ product production) vs. pour point for the isomerization of heavy neutral (500 N) feedstocks. FIG. 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”). ') Shows the yield versus pour point of the C ₅ product involved in the isomerization of heavy neutral (500N) feedstocks. FIG. 5 shows a standard MTT-containing catalyst (“Std SSZ-32”), a small crystal MTT-containing catalyst not loaded with metal (“small crystal SSZ-32”), a metal modified standard MTT-containing catalyst (“metal modification”). 2 shows the yield versus pour point for isomerization of a 150N feed using SSZ-32 ")" and a metal modified small crystal MTT-containing catalyst ("Metal Modified SSZ-32X"). FIG. 6 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”). The viscosity index (VI) versus pour point for the isomerization of 150N feed using " FIG. 7 shows a standard MTT-containing catalyst (“Std SSZ-32”), a metal-modified standard MTT-containing catalyst (“metal-modified SSZ-32”) and a small crystalline MTT-containing catalyst (“metal-modified SSZ-32X”). The gas production versus pour point for the isomerization of 150N feedstock using FIG. 8 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”). )) Shows the yield versus pour point of the light naphtha (C ₅ -250 degrees Fahrenheit) product involved in the isomerization of the 150N feedstock. FIG. 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”). ') Shows the yield versus pour point for the isomerization of a medium neutral feedstock using FIG. 10 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”). ') Shows the Viscosity Index (VI) vs. pour point for the isomerization of medium neutral feeds using. FIG. 11 shows a comparison of X-ray diffraction patterns of a standard MTT-containing catalyst (“STANDARD SSZ-32”) and a small crystal MTT molecular sieve (“SSZ-32X”).

(Detailed description of embodiment)
In one embodiment, the catalyst is composed of a molecular sieve having an MTT structural phase. The catalyst used contains 5 to 85% by weight of molecular sieve. As used herein, “molecular sieve” can include “zeolites”. The term “MTT zeolite” or a variant thereof relates to a family of molecular sieve materials and is represented by a framework structure code. The Structure Commission of the International Zeolite Association of the International Zeolite Association (IZA) has given a code consisting of three alphabetic characters for zeolites (molecular sieve types) having a measured structure. Zeolites having the same structure are generally referred to by these three letters. The code MTT is given to the structure of molecular sieves including ZSM-23, SSZ-32, EU-13, ISI-4 and KZ-1. That is, a zeolite having a skeletal structure similar to that of ZSM-23 and SSZ-32 is named MTT-type zeolite.

  Another type of molecular sieve useful for isomerization dewaxing is an intermediate pore size molecular sieve having a structural phase of MTT, TON, AEL or FER

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

Catalyst Preparation In one embodiment, the small crystal MTT molecular sieve is an oxidized or alkali metal hydroxide, an alkylamine (eg, isobutylamine), an organic carbon compound source of quaternary ammonium ions (which is subsequently ion exchanged into the hydroxide form. ), An oxide of aluminum (eg, an aluminum oxide source provides aluminum oxide that is covalently dispersed on silica), and an aqueous solution containing a source of silicon oxide. In one embodiment, the organic carbon compound source of quaternary ammonium ions that are subsequently ion exchanged to the hydroxide form is an N-lower alkyl-N′-isopropyl-imidazolium cation (eg, N, N′-diisopropyl- Imidazolium cation or N-methyl-N′-isopropyl-imidazolium cation). This aqueous solution has a composition that falls within the following ranges in terms of molar ratios:

In Table, Q is Q and the sum of _a and Q _b; M is in an oxidation or an alkali metal hydroxide, and M + is an alkali metal cation derived from the oxidation or the alkali metal hydroxide. Alkali metals are a series of elements that constitute the first group of the periodic table (IUPAC formula): lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium ( Fr).

Q _a is an organic carbon compound source of quaternary ammonium ions, and Q _b is an amine. In one embodiment, Q _a is an N-lower alkyl-N′-isopropyl-imidazolium cation (eg, N, N′-diisopropyl-imidazolium cation or N-methyl-N′-isopropyl-imidazolium cation). Many different _Qb amines are useful. In one embodiment, isobutyl amine, neopentyl amine, monoethyl amine, or mixtures thereof are suitable examples of Q _b. The molar concentration of Q _b is greater than the molar concentration of _{Q a.} In general, the molar concentration of Q _b is 2 to about 9 times the molar concentration of Q _a. US Pat. No. 5,785,947 (incorporated herein by reference) discloses a zeolite synthesis process that uses two organic sources of nitrogen, one of which is carbon. Compared to methods containing 1 to 8 amines, where a quaternary ammonium ion source (eg, imidazolium) is the only source of organic components, it provides exceptional cost savings. By combining these two organic nitrogen sources, the primary template (used in lower amounts) gives the possibility to form the nuclei of the desired zeolite structure and the amine is stable during the crystal growth period. Makes it possible to contribute to filling the pores. The voids in the high silica zeolite are susceptible to redissolution under the synthesis conditions. Amines can also contribute to maintaining increased alkalinity for synthesis.

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

In one embodiment, the quaternary ammonium ion source organic carbon compound source in aqueous solution, Q _a is derived from a compound represented by the formula:

In the above formula, R is lower alkyl containing 1 to 5 carbon atoms, such as -CH3 or isopropyl. Anions (A ⁻ ) that are not detrimental to MTT molecular sieve formation are associated with cations. Examples of anions include halogens (eg, fluoride, chloride, bromide and iodide), hydroxides, acetates, sulfates, carboxylates and the like. Hydroxides are particularly useful anions.

The reaction mixture is prepared using standard zeolite preparation techniques. Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina and aluminum compounds, such as aluminum-coated silica colloids (in one example, Nalco 1056 colloidal sol), Al ₂ (SO ₄ ) ₃ and other zeolites. .

In one embodiment, the aluminum oxide is in a covalently dispersed form on silica. Aluminum oxide in covalently dispersed form allows crystallization of molecular sieves with increased aluminum content. Increased aluminum content in the molecular sieve promotes isomerization. In another approach, a pentasil-structured zeolite and a low silica / alumina ratio (about 10) zeolite can be used as an aluminum oxide source or as a feedstock for the synthesis of small crystal MTT molecular sieves. These zeolites of the organic source, is recrystallized in small crystallite MTT molecular sieve in the presence of Q _a and Q _b.

  Mordenite and ferrierite zeolite serve as two such useful aluminum oxide sources or feedstocks. These latter zeolites have also been used for crystallization of ZSM-5 and ZSM-11 (US Pat. No. 4,503,024).

  When the aluminum oxide is in a co-dispersed form on silica, another means is Nalco Chem. Under the product name of an alumina-coated silica sol, eg 1056 colloidal silica. Co. The use of alumina-coated silica sol (26% silica, 4% alumina) manufactured by In addition to providing a new SSZ-32X with a high aluminum content, the use of this sol produces crystals smaller than 1000A (along the main axis) with a surprisingly high isomerization capacity.

  In one aspect, the catalytic performance associated with the resolution of the MTT molecular sieve (hydroxide form) is manifested by a constraint index value of 13 or greater (defined in J. Catalysis 67, page 218), and in one aspect, MTT molecular sieve (hydrogen form) has a constraint index of 13-22. The measurement of restraint index is also described in US Pat. No. 4,481,177. Generally, the smaller the zeolite crystal size, the less the shape selectivity. This is described in J. Org. It has been demonstrated for ZSM-5 reactions involving aromatic compounds as shown in Catalysis 99, 327 (1986). In addition, zeolite ZSM-22 (US Pat. No. 4,481,177) has been found to be closely related to ZSM-23 (J. Chem. Soc. Chem. 1985, p. 1117). The reference to ZSM-22 above shows that crystal ball milling produces a catalyst with a constraint index of 2.6. This number is surprising for this material given in another study (Proc. Of 7th Intl. Zeolite Conf. Tokyo, 1986, p. 23) showing that it is a highly selective 10-ring pentasil. It is a low number. In view of the fact that ball milling produces smaller crystals, ball milling is expected to lead to poor selectivity and higher activity for the catalyst. Unlike early small crystals with a small constraint index, small crystal MTT molecular sieves loaded with metal possess high selectivity.

  Typical sources of silicon oxide include silicates, silica hydrogels, silicic acid, colloidal silica, fumed silica, tetraalkylorthosilicates, and silica hydroxide. Salts, especially alkali metal halides such as sodium chloride, can be added to the reaction mixture or can be formed in the reaction mixture. These compounds are disclosed in the publication as facilitating crystallization of the zeolite while preventing silica blockage in the lattice.

  The reaction mixture is maintained at an elevated temperature until molecular sieve crystals are formed. The temperature during the hydrothermal crystallization process is typically maintained at about 140 ° C to about 200 ° C, such as about 160 ° C to about 180 ° C, or about 170 ° C to about 180 ° C. The crystallization period is typically longer than 1 day, and in one embodiment, the crystallization period is from about 4 days to about 10 days.

  Hydrothermal crystallization is carried out under pressure, usually in an autoclave so that the reaction mixture is exposed to self-pressurization. The reaction mixture can be stirred while the ingredients are added and during the crystallization period.

  Once molecular sieve crystals are formed, the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration or centrifugation. These crystals are washed with water and then dried at 90 ° C. to 150 ° C. for 8 to 24 hours to obtain synthetic molecular sieve crystals. This drying step can be performed under atmospheric pressure or sub-atmospheric pressure.

  During the hydrothermal crystallization process, the crystals can spontaneously nucleate from the reaction mixture. The reaction mixture can also inoculate MTT crystals directly to promote crystallization and minimize the formation of undesirable aluminosilicate contaminants.

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

  In one embodiment, the small crystal MTT molecular sieve can be used as-synthesized or can be heat treated (fired). This calcination is advantageously performed at a temperature of about 750 degrees Fahrenheit. Usually, desirably, the alkali metal cation is separated by ion exchange and replaced with hydrogen, ammonium, or any desired metal ion. The molecular sieve can be leached with a chelating agent such as EDTA or dilute acid solution to increase the silica alumina molar ratio. Molecular sieves can also be steamed. Steam treatment helps stabilize the crystal lattice against attack from acids.

  The fired molecular sieve is then loaded with at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd. These metals are known for their ability to modify catalyst performance, which reduces the number of strong acid sites on the catalyst, thereby reducing the selectivity of decomposition for isomerization. In one embodiment, the modification includes increased metal dispersion, thereby masking acid or cation sites in the catalyst. In one embodiment, the metal loading is performed by various techniques including impregnation and ion exchange. Typically, the metal is loaded so that the catalyst contains 0.5 to 5 weight percent metal on a dry basis. In one embodiment, the catalyst contains 2-4 wt% metal on a dry basis.

  A typical ion exchange technique involves contacting the extruded article or particle with a salt of the desired exchange cation (one or more). Although a wide variety of salts can be employed, in one embodiment, the salt of the desired exchange cation (one or more) is selected from chloride or other halides, nitrates, sulfates and mixtures thereof. The Representative ion exchange techniques are described in a wide variety of patents, including US Pat. Nos. 3,140,249; 3,140,251; and 3,140,253. Each is incorporated by reference. Ion exchange can be performed before or after firing the extruded article or particle. Firing is performed at a temperature in the range of 400 to 1100 degrees Fahrenheit.

  After contact with the desired exchange ion salt solution, the molecular sieve is dried at a temperature in the range of 140 to about 599 degrees Fahrenheit. The molecular sieve is then further loaded with a Group VIII metal using techniques such as impregnation to enhance the hydrogenation function. In some embodiments, it is desirable to co-impregnate the modifying metal and the Group VIII metal at once, as described in US Pat. No. 4,094,821. In one embodiment, the Group VIII metal is platinum, palladium or a mixture of the two. In one aspect, after metal loading, the product can be calcined in air or inert gas at a temperature of 500-900 degrees Fahrenheit.

Thus, an example of a typical method for producing a catalyst includes the following steps:
(A) synthesizing small crystalline MTT zeolite in aqueous solution;
(B) mixing this small crystalline MTT zeolite with a resistant inorganic oxide support precursor and an aqueous solution to form a mixture;
(C) Extruding or molding the mixture of step (b) to form extruded articles or shaped particles;
(D) drying the extruded article or molded particles of step (c);
(E) firing the extruded article or molded particles of step (d);
(F) The extruded article or molded particle of step (e) is impregnated with at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K, and Nd. Preparing a modified extruded article or shaped particle;
(G) drying the metal modified extruded article or shaped particles of step (f);
(H) preparing a catalyst precursor by further impregnating the Group VIII metal into the metal modified extruded article or shaped particles of step (g);
(I) drying the dried catalyst precursor of step (h); then (j) calcining the dried catalyst precursor of step (i) to produce a finished, constrained catalyst.

  The use of active materials jointly, ie combined with synthetic molecular sieves, tends to improve the conversion and selectivity of the catalyst in certain organic conversion processes. Examples of active substances include hydrogenating components and metals added to affect the overall function of the catalyst. In one embodiment, the overall function of the catalyst includes enhanced isomerization and reduced cracking activity.

  In one aspect, the small crystal MTT molecular sieve can be used in intimate combination with a hydrogenating component in applications where a hydrogenation-dehydrogenation function is desired. Exemplary hydrogenating components can include hydrogen, ammonium, metal cations such as rare earths, Group IIA and Group VII metals, and mixtures thereof. Examples of metal hydrogenating components include tungsten, vanadium, molybdenium, rhenium, nickel, cobalt, chromium, manganese, platinum, palladium (or other noble metal). In one embodiment, the Group VIII metal is a noble metal selected from the group of platinum, palladium, rhenium, and mixtures thereof. In another embodiment, the Group VIII metal is a noble metal selected from the group of platinum, palladium, and mixtures thereof. In one embodiment, the metal hydrogenating component is added to constitute about 0.3 to about 5 weight percent of the catalyst on a dry basis of the catalyst.

  Metals added to affect the overall function of the catalyst (including enhanced isomerization and reduced cracking activity) are magnesium, lanthanum (and other rare earth metals), barium, sodium, praseodymium, strontium, potassium And neodymium. Other metals that can be used to affect the overall function of the catalyst include aene, cadmium, titanium, aluminum, tin, and iron.

  Hydrogen, ammonium and metal components can be exchanged in the molecular sieve. The zeolite can also be impregnated with the metal, or the metal can be physically intimately mixed with the molecular sieve using standard methods known in the art. The metal can also be encapsulated in the crystal lattice by including the desired metal present as ions in the reaction mixture resulting from the preparation of the zeolite.

  In one embodiment, the disclosed molecular sieve zeolite can be converted to its acid form and then mixed with a soluble resistant inorganic oxide support precursor and an aqueous solution to form a mixture. In one embodiment, the aqueous solution is acidic. This aqueous solution acts as an anticoagulant. In one embodiment, the support (also known as a matrix or binder) is selected to be resistant to the temperatures and other conditions employed in the organic conversion process. Such matrix materials include active and inert materials and synthetic or naturally occurring zeolites, as well as inorganic materials such as clays, silica and metal oxides. In one embodiment, the carrier is naturally occurring. In another embodiment, the support is in the form of a gel precipitate, sol, or gel and comprises a mixture of silica and metal oxide.

  In one embodiment, the molecular sieve is a porous matrix material and a mixture of matrix materials, such as silica, alumina, titania, magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, titania. -Zirconia, and ternary compositions such as silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. This matrix can be in the form of a cogel. In one embodiment, the matrix material is alumina and silica.

  The inert material can act appropriately as a diluent to control the amount of conversion in the specified process, thereby obtaining the product economically without using another means of controlling the reaction rate. Can do. In many cases, the zeolitic material is incorporated into naturally occurring clays such as bentonite and kaolin. These materials, such as clays, oxides, etc., function in part as catalyst binders. In oil refining, catalysts are often subjected to rough operations, and it is desirable to provide a catalyst with good crushing strength. Rough operations tend to grind the catalyst into a powder that causes processing problems.

  In the description of the present specification, “metal modification” means that at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K, and Nd and at least one metal molecular sieve is selected. Means containing a Group VIII metal. Group VIII metals are Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt.

  In one embodiment, naturally produced clay is mixed with a synthetic small crystal MTT molecular sieve. Examples of naturally occurring clays include the montmorillonite and kaolin clan, which are kaolins and quasi-bentonites commonly known as Dixie, McNamee, Georgia and Florida clays, or whose main mineral constituents are halloysite, kaolin. Contains other substances that are knight, dickite, nacrite, or anarchite. Fibrous clays such as sepiolite and attapulgite can also be used as supports. Such clays can be used as is as a mine mining material or initially subjected to calcination, acid treatment or chemical modification.

  Mixtures of molecular sieves and binders can be formed into a wide variety of physical forms. Generally speaking, the mixture is sufficient to pass through a powder, granule, or molded article, such as a 2.5 mesh (Tyler) sieve, and retained on a 48 mesh (Tyler T) sieve. It can be in the form of an extruded article having a particle size of If the catalyst is molded, for example if it is extruded with an organic binder, the mixture can be extruded before drying, or it can be extruded after drying or after partial drying. . Small crystal MTT molecular sieves can also be steamed. This steam treatment helps stabilize the crystal lattice against attack from acids. The dried extruded article is then heat treated using a firing process.

  In general, it is desirable for economic reasons to minimize the amount of molecular sieve in the finished catalyst. As long as good activity and selectivity effects are achieved, the amount of molecular sieve in the finished catalyst is desirably low. In one embodiment, the level of this molecular sieve is 5 to 85% by weight, or in another embodiment 5 to 60% by weight. The level of this molecular sieve can be varied according to the type of molecular sieve.

  In one embodiment, the metal modified small crystal MTT catalyst provides excellent yield and exceptional viscosity index (VI) for various feedstocks. By-product selectivity varies significantly compared to catalysts containing standard MTT type zeolite. For example, the catalyst provides very low gas production and naphtha production. As an example, in a wax-containing 500N hydrocracking product feed containing 21% wax with a waxy VI of 122, the product yield was 97% with a pour point of −15 ° C. and a VI of 120-121. It was. Typically, there is a greater drop from the waxy VI to the dewaxed VI. For example, when a catalyst containing standard MTT type zeolite was used, the product VI produced was about 111. The catalyst containing the metal modified standard MTT type zeolite yielded a VI of 115. Both gas production and naphtha production were significantly reduced by the use of small crystal MTT molecular sieves loaded with metal. Such a high yield and product VI very close to the wax-containing feed VI after dewaxing is very surprising. The yield of 700 degrees Fahrenheit + dewaxed lubricant product in this case is as high as 97%. Also, the slope of product VI vs. pour point stands out in that it does not decrease at low pour points.

  The data obtained for the 150N wax-containing hydrocracking product also showed improved product yields compared to conventional MTT type catalysts. In addition, low gas production and naphtha production were found. The MN feed was also tested and improved yield and VI were also found.

When the Fischer-Tropsch wax feed is treated with a catalyst containing a metal-loaded small crystal MTT molecular sieve, the 650 degrees Fahrenheit + product produced is 165--25 ° C. at a pour point of −25 to −30 ° C. It had a special VI value of 170. When a product having a boiling point of 750 degrees Fahrenheit + is further divided into two fractions, the 750-850 degrees Fahrenheit fraction has a kinematic viscosity of 3.8 mm ² / sec at 100 ° C. and a pour point of −18 ° C. Had a very high VI of 151, and the 850 Fahrenheit + fraction had a viscosity of 9.7 mm ² / sec and a VI of 168 at a pour point of -11 ° V. The kinematic viscosity was measured by ASTM D445-06, the pour point was measured by ASTM D5950-02, and VI was measured by ASTM D2270-04.

Feed In one aspect, a method using a catalyst comprising a molecular sieve that has a small crystal MTT phase and is loaded with a metal from relatively light distillation fractions such as kerosene and jet fuel, crude oil, truncated crude oil, vacuum tower Residual circulating oil, synthetic crude oil (eg shale oil, tars and oils), gas oil, vacuum gas oil, waxy lower oil, Fischer-Tropsch derived wax and intermediate products, slack wax, deoiled slack wax, wax Range from high-boiling feedstocks such as containing lubricating oil raffinates, n-paraffin waxes, NAO waxes, waxes produced in chemical factory processes, deoiled petroleum-derived waxes, microcrystalline waxes, other heavy oils, and mixtures thereof Used to dewax various feedstocks.

  In one embodiment, the feedstock is a hydrocarbon having a wax content weight percent of at least 5%.

  The wax weight percentage in the feed is measured by heating the wax-containing sample to a temperature just above its pour point; 100 grams of the heated wax-containing sample is poured into a tar-coated 1 liter beaker. The weight of the heated wax-containing sample is then recorded in 2 decimal places; 400 ml of a 1: 1 mixture of toluene: methyl ethyl ketone (MEK) is added to the beaker and the wax-containing sample is placed on a hot plate. Dissolve with gentle stirring until homogeneous. The beaker is covered with a piece of aluminum foil and then placed in a refrigerator that is preset to the pour point temperature of the feed. Keep the sample stationary overnight. After cooling overnight in the refrigerator, the mixture is filtered using a filter provided in the refrigerator. No. in the Buchner funnel. A 4 Whatman filter (18.5 cm in diameter) is used and the funnel is then covered with a piece of aluminum foil to retain ice crystals from collection in the funnel. The funnel is connected to a high vacuum, the filter paper is rewet with cold MEK, vacuum is applied, the entire mixture in the beaker is quantitatively transferred to the funnel using a spatula, the beaker is rinsed with cold MEK and then rinsed Filtration is performed by filtering the liquid. Close the refrigerator and then wait until the solvent is completely removed through the filter, then lower the refrigerator to the original preset temperature. The wax filter cake is thoroughly washed with cold MEK. The wax cake is dried, the vacuum is removed, and the filter-funnel assembly is then removed from the refrigerator. Using a spatula, transfer as much wax as possible from the filter to the tarred jar. The last traces of filtered wax are removed with hot toluene, and the rinse is then transferred to a tar-coated jar. Toluene is allowed to evaporate and the weight of the wax collected in the tar-coated jar is then measured. The oily filtrate is poured into a tar-coated flask. The solvent is distilled off using a rotary evaporator, the weight of the flask plus the weight of the residual oil is measured, and then the oil weight is determined. The wax percentage is a value obtained by dividing the weight of the wax collected in the tar-coated jar by the weight of the heavy wax-containing sample and then multiplying by 100.

  Linear n-paraffins alone or a mixture with paraffins with only a few branches having 16 or more carbon atoms are sometimes referred to herein as waxes. Because light oils typically do not contain significant amounts of wax components, the feedstock is often a C10 + feedstock that generally boils above about 350 degrees Fahrenheit. However, this method does not include wax-containing distillate feedstocks, such as middle distillate feedstocks including gas oils, kerosenes, and jet fuels, lubricating oil feedstocks, heating fuels and their pour points and viscosities. It is useful for wax-containing distillate feedstocks such as other distillate fractions that need to maintain their limits. Lubricating oil feedstocks generally boil at 230 ° C. (450 degrees Fahrenheit) or higher, and usually 315 ° C. (600 degrees Fahrenheit) or higher. Hydrotreated feedstocks are a convenient source of this and other distillate fractions since they usually contain significant amounts of wax-containing n-paraffins. The feedstock of this process usually contains paraffins, olefins, naphthenes, aromatics and heterocyclic compounds, with a substantial proportion reflected in the wax content of the high molecular weight n-paraffin and the feedstock. C10 + feedstock containing branched paraffins. During processing, n-paraffins and slightly branched paraffins undergo some cracking or hydrocracking to produce a liquid range of material that reflects the low viscosity product. However, the degree of decomposition that occurs is limited so that the yield of products having boiling points below the boiling point of the feedstock is reduced. This retains the economic value of co-feed materials.

  Typical feedstocks are hydrotreated or hydrocracked gas oil, hydrotreated lube raffinate, bright stock, lube oil stock, synthetic oil, waxy lower oil, Fischer-Tropsch synthetic oil, high flow Includes point polyolefins, positive alpha olefin waxes, slack waxes, deoiled waxes, microcrystalline waxes and mixtures thereof.

  Fischer-Tropsch wax may be, for example, a commercial SASOL (registered trade name) slurry face Fischer-Tropsch technique, a commercial SHELL (registered trade name) Middle Distillate Synthesis (SMDS) process, Or it can obtain by well-known methods, such as non-commercial EXXON (trade name) Advanced Gas Conversion (AGC-21) method. These processes and other details are described, for example, in EP-A-776959, EP-A-668342, U.S. Pat. Nos. 4,943,672, 5,059,299, 5,733,839, And RE39073; and US published application no. 2005/0227866, WO-A-9934917, WO-A-9990720 and WO-A-05107935. Fischer-Tropsch synthesis products typically contain hydrocarbons having 1 to 100, or even more than 100, carbon atoms, and typically include paraffins, olefins and oxygenation products. Fischer-Tropsch is a valuable method for producing clean alternative hydrocarbon products including Fischer-Tropsch wax.

Conditions Conditions for performing the isomerization dewaxing operation generally include a temperature falling within the range of about 392 degrees Fahrenheit to about 800 degrees Fahrenheit and a pressure of about 15 to about 3000 psig. Typically, the pressure is from about 100 to about 2500 psig. The liquid space velocity per hour during the contact period is generally from about 0.1 to about 20, for example from about 0.1 to about 5. In one embodiment, this contacting is performed in the presence of hydrogen. The hydrogen to hydrocarbon ratio can fall within the range of about 2000 to about 10,000 standard cubic feet H ₂ / hydrocarbon barrel, such as about 2500 to about 5000 standard cubic feet H ₂ / hydrocarbon barrel.

  In one embodiment, the isomerized dewaxed product is further processed, for example, by hydrogen finishing or adsorbent treatment. This hydrogen finishing treatment can be preferably carried out in the presence of a metal-based hydrogenation catalyst such as platinum on alumina. This hydrogen finishing treatment can be performed at a temperature of about 374 degrees Fahrenheit to about 644 degrees Fahrenheit and a pressure of about 400 psig to about 3000 psig. Hydrogen finishing in this method is described, for example, in US Pat. No. 3,852,207, which is incorporated herein by reference.

(Example)
Another name that can be used to describe a metal-loaded small crystal MTT molecular sieve is “broadlin”. The synthesis of this broadin (see x-ray diffraction pattern) small crystal molecular sieve is actually synonymous with the crystallization of very small crystal examples of zeolite. The expansion of the x-ray diffraction pattern as a crystal is reduced in size. In general, with MTT molecular sieve systems, the smaller the SiO ₂ / Al ₂ O ₃ ratio (the higher the Al weight percent in the zeolite product), the smaller the crystal size.

  Table 2 (a) shows the standard SSZ-32, standard MTT molecular sieve peak relative intensity and peak list. Table 2 (b) shows the relative intensity and peak list of the small crystal MTT molecular sieve peaks before loading with metal. In Table 2 (b), the peak width is expanded so that the main peaks of the small crystal MTT molecular sieve and the standard SSZ-32 can be easily compared.

  FIG. 11 shows the X-ray diffraction pattern of these two types of MTT molecular sieves, clearly demonstrating the wider x-ray diffraction pattern of the small crystal MTT molecular sieve.

Synthesis of small crystal MTT molecular sieves Small crystal MTT molecular sieves were synthesized as follows: A Hastelloy C liner for a 5 gallon autoclave apparatus was used for mixing the reactants and subsequent heat treatment. The following components were added and mixed in the following order over a period of 1/2 hour at a rate of 1500 RPM. 300 grams of a 1 molar solution of N, N'-diisobropirimimidazolium hydroxide was mixed into 4500 grams of water. The chloroiodide was prepared as described in Example 8 of US Pat. No. 4,483,835 and then ion exchanged to the hydroxide form using BioRad AG1-X8 exchange resin. 2400 grams of 1N KOH was added. 1524 grams of Ludox AS-30 (SiO ₂ 30 wt%) was added. 1080 grams of Nalco's 1056 colloidal sol (26 wt% SiO ₂ and 4 wt% Al ₂ O ₃ ) was added. Finally, 181 grams of isobutylamine was mixed into the mixture with stirring. Molar concentration of the amine Q _b is exceeded the molar concentration of the imidazolium compound Q _a.

  When stirring was complete, the autoclave head was closed and the reaction was raised to 170 ° C. with an 8 hour rise time. The reaction system was stirred at 150 RPM. After 106 hours of heating, the reaction was stopped and the product was collected. The solid was collected by filtration (performs very slowly; required for small crystals). The solid was then washed several times and then dried. The dried material was analyzed by x-ray diffraction. The pattern is shown in Table 3. A comparison with the more standard SSZ-32 data shown in Table 2 (a) was made and the new product of Example 1 is related to SSZ-32 but the x-ray diffraction line is exceptional. You can see that it is wide.

In connection with the fact that the product may be a mixture of small crystals and exceptionally amorphous materials, TEM (Transmission Electron Microscopy) analysis was performed. This microscopic analysis showed that the product of Example 1 was a very uniform small crystalline MTT molecular sieve with very little evidence of amorphous material. These crystals are characterized in that small, wide lathe components having a diameter in the longest direction in the range of about 200 to about 400 angstroms are dispersed. The product had a SiO ₂ / Al ₂ O ₃ ratio of 29.

The product of Example 1 was heated at a rate of 1 ° C./minute (1.8 degrees Fahrenheit / minute) and 3 hours residence time at 250 degrees Fahrenheit, 3 hours residence time at 1000 degrees Fahrenheit, then 3 at 1100 degrees Fahrenheit. Baked to 1100 degrees Fahrenheit in air using the time stay. This calcined material retained its x-ray crystallinity. The calcined zeolite was subjected to 2 ion-exchange at 200 degrees Fahrenheit (using NH ₄ NO ₃ ) as previously disclosed in US Pat. No. 5,252,527. The ion exchanged product was refired and then microcavity measurements were made using the test method also described in 5,252,527. The new product, small crystal MTT molecular sieve, had some unexpected differences over conventional SSZ-32.

  The Ar adsorption ratio of small crystal MTT molecular sieve (Ar adsorption at 87 K between 0.001 and 0.1 relative pressure) / (total Ar adsorption up to 0.1 relative pressure) is greater than 0.5. In one embodiment, the Ar adsorption ratio ranges from 0.55 to 0.70. On the other hand, the Ar adsorption ratio of conventional SSZ-32 is smaller than 0.5, typically 0.35 to 0.45. The small crystal MTT molecular sieves of Examples 1 and 2 exhibited an argon adsorption ratio of 0.62.

The external surface area of these crystals jumped from about 50 m ² / g (SSZ-32) to 150 m ² / g (small crystal MTT molecular sieve). This shows the exceptional external surface area as a result of very small crystals. At the same time, the microcavity volume of the small crystal MTT molecular sieve was reduced to about 0.035 cc / gm, compared to about 0.06 cc / gm for standard SSZ-32.

Small crystalline MTT zeolite was synthesized using alumina, extruded, dried and then calcined. This dried and fired extruded article was impregnated with a solution containing both platinum and magnesium, then finally dried and fired. The total platinum load was 0.325%. This metal modified catalyst was then tested for isomerization of a wax-containing 500N hydrocracked product feedstock having a 21% wax content, a kinematic viscosity at 100 ° C. of 10.218 mm ² / sec, and a pour point of + 51 ° C. did. The isomerization operating conditions used were 1.0 / hr LHSV, 4000 scf / bbl gas to oil ratio, and 2300 psig total pressure. After isomerization, the product was hydrofinished at 450 degrees Fahrenheit over a Pt / Pd silica alumina hydrofinishing catalyst. The VI of this wax-containing 500N hydrocracked product feed was 122, and when solvent dewaxed at -18 ° C, the VI of the solvent-dewaxed wax-containing 500 hydrocracked product feed was 106. . The difference between the VI of this wax-containing material and the VI of the catalytic isomerization product was only 2 (122-120). This is exceptional.

Figures 1 and 2 show the yield and product VI versus pour point achieved using a metal modified catalyst comprising a small crystal MTT zeolite catalyst ("metal modified SSZ-32X"). Data at different product pour points and corresponding viscosity indices were obtained by changing the operating temperature of the dewaxing catalyst (eg, lowering the pour point is achieved by increasing the catalyst temperature). These results were compared with two different types of catalysts, a standard MTT containing catalyst (“Std SSZ-32”) and a metal modified standard MTT containing catalyst (“metal modified SSZ-32”). The tests were performed under the same conditions and using the same feed materials. The isomerization yield of products boiling at 700 degrees Fahrenheit and above using metal-modified catalysts containing small crystal MTT zeolite catalysts in the typical product target range of -12 to -15 ° C pour point is unprecedented It was 96 to 97%. This product has an excellent VI of about 120. This is also believed to reflect the amount of isomerized wax retained in the base oil boiling range product. The slope of VI versus pour point for products boiling at 700 degrees Fahrenheit and above was negative, about -0.15. Thus, VI actually increased as the pour point decreased. Example 3 demonstrates that two or more isomerized products boiling above 343 ° C. (650 degrees Fahrenheit) have a corresponding viscosity index of 104, 110 or higher. 3 and 4 show low yields of C ₁ -C ₄ products (“gas generation”) achieved using metal modified catalysts including small crystal MTT zeolite catalyst (“metal modified SSZ-32X”). and _C 5 _{-C 250 degrees Fahrenheit} product (naphtha) is shown in comparison with the two other types of catalyst.

  The same metal modified catalyst from Example 3 was also tested for isomerization against a wax containing 150N hydrocarbon feed having a 10% wax content and a pour point of + 32 ° C. The isomerization operating conditions used were 1.0 / hr LHSV, 4000 scf / bbl gas to oil ratio, and 2300 psig total pressure. After isomerization, the product was hydrofinished at 450 degrees Fahrenheit over a Pt / Pd silica alumina hydrofinishing catalyst.

FIGS. 5 and 6 show the yield and product VI versus pour point achieved using a metal modified catalyst comprising a small crystal MTT zeolite catalyst (“metal modified SSZ-32X”). These results were compared with three different types of catalysts: standard MTT-containing catalyst (“Std SSZ-32”), metal-modified standard MTT-containing catalyst (“metal-modified SSZ-32”) and non-metal-modified standard small crystal MTT. Comparison with a zeolite catalyst (“small crystal SSZ-32X”). A total of 4 catalysts were tested under the same conditions and with the same 150N feed. The isomerization yield of products boiling at 650 degrees Fahrenheit and above using metal-modified catalysts containing small crystal MTT zeolite catalysts in the typical product target range of pour point of -12 to -15 ° C is 94- 95%. The VI of this product was about 108. The slope of VI versus pour point of the product boiling at 650 degrees Fahrenheit and above was negative, about 0.09. This is significantly lower than the value obtained with the comparative catalyst. The VI did not decrease as much as the pour point was reduced by using a metal modified catalyst including a small crystal MTT zeolite catalyst. 7 and 8 show low yields of C ₁ -C ₄ products (“gas generation”) achieved using metal modified catalysts including small crystal MTT zeolite catalyst (“metal modified SSZ-32X”). and _C 5 _{-C 250 degrees Fahrenheit} product (naphtha) is shown in comparison with the two other types of catalyst.

The same metal modified catalyst from Example 3 is also fed with a wax-containing medium natural (220N, MN) having a 12.2% wax content, a kinematic viscosity of 6.149 mm ² / sec at 100 ° C. and a pour point of + 36 ° C. The material was tested for isomerization. The isomerization operating conditions used were 1.6 / hr LHSV, 4000 scf / bbl gas to oil ratio, and 2300 psig total pressure. After isomerization, the product was hydrofinished at 450 degrees Fahrenheit over a Pt / Pd silica alumina hydrofinishing catalyst.

  9 and 10 show the yield and product VI versus pour point achieved using a metal modified catalyst comprising a small crystal MTT zeolite catalyst ("metal modified SSZ-32X"). These results were compared with two different types of catalysts, a standard MTT-containing catalyst (“standard SSZ-32”) and a metal modified standard MTT-containing catalyst (“metal modified SSZ-32”). All three catalysts were tested under the same conditions and with the same 220N feed. The isomerization yield of a product boiling at 650 degrees Fahrenheit and above using a metal modified catalyst containing a small crystal MTT zeolite catalyst in a typical product target range of -15 ° C pour point was about 92%. It was. The VI of this product was 105. The slope of VI of the product boiling at 650 degrees Fahrenheit and above over the pour point over the -12 ° C to -22 ° C pour point range is substantially zero, which is more than that obtained with the comparative catalyst. Significantly lower. This VI did not decrease so much that the pour point was reduced by the metal modified catalyst including the small crystal MTT zeolite catalyst.

The same metal-modified catalyst from Example 3 was also treated with a hydrotreated Fischer with a wax content of 90% or more produced by the SASOL® Slurry Phase Fischer-Tropsch process. Tested for isomerization on Tropsch wax feed. The isomerization operating conditions used were 1.0 / hr LHSV, a gas to oil ratio of 5000 scf / bbl, and a total pressure of 300 psig. After isomerization, the product was hydrofinished at 450 degrees Fahrenheit over a Pt / Pd silica alumina hydrofinishing catalyst. The resulting product boiling at 650 degrees Fahrenheit and above had a VI of 165 to 170 at a pour point of -25 to -30 ° C. The yield of product boiling at 650 degrees Fahrenheit and above was greater than 65 wt% at a pour point of 20 ° C. The product boiling at 650 degrees Fahrenheit and above was divided into two fractions by vacuum distillation. One of these fractions boiled at 750-850 degrees Fahrenheit and the other boiled at 850 degrees Fahrenheit and above. The fraction with the lower boiling point had a kinematic viscosity at 100 ° C. of 3.8 mm ² / sec, a VI of 151, and a pour point of −18 ° C. The fraction with the higher boiling point had a kinematic viscosity at 100 ° C. of 9.7 mm ² / sec, a VI of 168, and a pour point of −11 ° C. A comparative operation performed under the same operating conditions and for the same feed with a metal modified standard MTT containing catalyst gave lower yields and slightly higher VI. Interestingly, the formation of boiling at 650 degrees Fahrenheit and above for the pour point over the pour point range of −20 ° C. to −50 ° C., despite the slight decrease in VI with the metal modified small crystal MTT zeolite catalyst The slope of VI of the product was less than 0.56 and was significantly smaller than the slope of greater than 0.72, which is the slope obtained with the comparative catalyst.

Claims (25)

  A process for dewaxing a hydrocarbon feedstock to produce an isomerized product comprising the step of isomerizing a feedstock comprising paraffins having 10 or 11 or more carbon atoms having linear and few branches Contacting with a catalyst in the presence of hydrogen under conditions, the catalyst comprising a molecular sieve having an MTT structural phase and having a crystal diameter of from about 200 to about 400 angstroms in the longest direction, Ca, Cr, Mg A method comprising at least one metal selected from the group consisting of La, Na, Pr, Sr, K and Nd and at least one Group VIII metal.   The method of claim 1 wherein the MTT molecular sieve is selected from the group consisting of SSZ-32, ZSM-23, EU-13, ISI-4 and KZ-1.   The feed is hydrotreated or hydrocracked gas oil, hydrotreated lube raffinate, bright stock, lube oil stock, synthetic oil, waxy lower oil, Fischer-Tropsch synthetic oil, high pour point The process of claim 1 selected from the group consisting of polyolefins, positive alpha olefin waxes, slack waxes, deoiling waxes, microcrystalline waxes and mixtures thereof.   The method of claim 1, wherein the Group VIII metal is selected from the group consisting of platinum and palladium, and mixtures thereof.   The method of claim 1, wherein the contacting is performed at a temperature of 232-427 ° C. (450-800 degrees Fahrenheit) and a pressure in the range of about 103.4 kPa cage (15 psig) to about 20,685 kPa gauge (3000 psig).   The method of claim 5, wherein the pressure ranges from about 689.5 kPa gauge (100 psig) to about 17237 kPa gauge (2500 psig).   6. The method of claim 5, wherein the liquid hourly space velocity during the contact period is from about 0.1 to about 20.   8. The method of claim 7, wherein the liquid space velocity per hour during the contact period is from 0.5 to about 5.   The process of claim 1, wherein the hydrocarbon feed is hydrotreated at a temperature in the range of 163 to 427 ° C. (325 to 800 degrees Fahrenheit) prior to isomerization.   The method of claim 1 further comprising a hydrofinishing step after isomerization.   The hydrofinishing treatment is performed at a temperature in the range of about 163 to about 310 ° C (325 to about 590 degrees Fahrenheit) and a pressure in the range of about 2068 kPa gauge (300 psig) to about 20,685 kPa gauge (3000 psig). The method described.   The method of claim 1, further comprising hydrofinishing of the isomerized product. A dewaxing process, wherein a hydrocarbon feed having at least 5 wt% wax content is isomerized and dewaxed over a catalyst and boiled at 343 ° C (650 degrees Fahrenheit) or more, or two or more isomerizations Each of the isomerization products comprises producing a product,
a. A pour point of 0 to −30 ° C., and b. A dewaxing method wherein a line having a corresponding viscosity index of 95 or more, wherein the line fits the pour point on the x-axis and the viscosity index on the y-axis has a slope of zero or less with respect to y .   14. A dewaxing process according to claim 13, wherein the hydrocarbon feed has a wax content of at least 10% by weight. The dewaxing method according to claim 13, wherein the hydrocarbon feed has a kinematic viscosity of 2.5 mm ² / sec or more at 100 ° C.   14. The dewaxing method of claim 13, wherein the catalyst comprises a molecular sieve having an MTT structural phase and having a crystal diameter of about 200 to about 400 angstroms in the longest direction.   The dewaxing method according to 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.   The dewaxing method of claim 17, wherein the catalyst further comprises at least one Group VIII metal.   14. The dewaxing method of claim 13, wherein the two or more isomerized products boiling at 343 [deg.] C. (650 degrees Fahrenheit) or higher have a corresponding viscosity index of 104 or higher.   The dewaxing method according to claim 13, wherein the yield of two or more isomerized products boiling at 343 ° C. (650 ° F.) or higher is 90% by weight or more based on the feed.   The dewaxing method according to claim 20, wherein the yield is 94% by weight or more.   The dewaxing method according to claim 13, wherein the slope of the line is smaller than -0.05. A dewaxing process, wherein a hydrocarbon feed having at least 5 wt% wax content is isomerized and dewaxed over a catalyst and boiled at 343 ° C (650 degrees Fahrenheit) or more, or two or more isomerizations Each of the isomerization products comprises producing a product,
a. A pour point of 0 to −30 ° C., and b. A line having a corresponding viscosity index greater than or equal to 95, where the line fits the pour point on the x-axis and the viscosity index on the y-axis has a slope of zero or less with respect to y, A dewaxing process wherein the yield of two or more isomerized products boiling above 343 ° C. (650 ° F.) is 90% by weight or more based on the feed.   24. A dewaxing method according to claim 23, wherein the molecular sieve has an MTT structural phase.   24. The dewaxing method of claim 23, wherein the molecular sieve has a crystal size of about 200-400 Angstroms.