DE69914226T2 - CATALYTIC DEVELOPMENT BY MEANS OF A FERRIERIT REPLACED WITH TRIVALENT RARE EARTH - Google Patents

Description

BACKGROUND THE REVELATION

Territory of invention

The Invention relates to catalytic dewaxing with a with rare earth metal ion exchanged ferrierite. In particular concerns the invention the catalytic dewaxing of a waxy hydrocarbonaceous feed to reduce its Pour point using a dewaxing catalyst, which includes ferrierite in which one or more trivalent rare earth metals occupy at least part of its cation exchange sites.

background the invention

The Catalytic dewaxing of waxy hydrocarbonaceous Materials such as paraffinic feedstocks to reduce their pour point and converting the paraffin into more useful ones Products such as fuel and lubricating oil fractions are known. This Feedstocks have trapped petroleum, that of paraffinic oils, heavy oil fractions and raw paraffin is derived. dewaxing include a catalytic metal component, a natural or synthetic crystalline aluminosilicate or zeolite molecular sieve component and often one or more additional heat-resistant Metal oxide components. Molecular sieves used for dewaxing of petroleum fractions and raw paraffin for have been found to include ferrierite, for example (US-A-4,343,692 and 4,795,623), Mordenite (US-A-3,902,988), ZSM-23 and ZSM-35 (US-A-4 222 885), ZSM-5 and ZSM-11 (US-A-4 347 121) and ZSM-5 (US-A-4 975 177). Have these different catalysts different selectivities for different Products. Although ZSM-5 is used for dewaxing, for example of oil refining is particularly effective, the crack selectivity compared to gaseous products is what results in a low lubricant yield. There is still a need on a dewaxing catalyst and process that is superior to the Manufacture of lubricating oil basics are selective, and especially on premium, high purity and High (VI) oils with low pour points.

SUMMARY THE INVENTION

It it has been found that ferrierite with trivalent rare earth metal ion-exchanged using a hydrothermal ion exchange process can be and that a dewaxing catalyst that the includes rare earth exchanged ferrierite, better overall selectivity for manufacture of lubricating oil fractions with a low pour point and a high VI as the hydrogen form of has either ferrierite or mordenite. The invention therefore relates to a process for the catalytic dewaxing of a waxy hydrocarbonaceous material by reacting the material with hydrogen in the presence of a catalyst comprising ferrierite, in which at least a part, preferably at least 10%, in particular at least 15% and more preferably at least 25% of its cation exchange capacity one or more trivalent rare earth metal cations is / are occupied, under reaction conditions that are effective to the pour point to reduce the material. Rare earth metal means the lanthanoid elements and closes La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and mixtures thereof on. Hereinafter, "RE-ferrierite" means in context with the invention that it is either natural or synthetic Includes ferrierite, in which at least a part, preferably at least 10%, in particular at least 15% and more preferably at least 25% of the cation exchange capacity one or more of these trivalent lanthanoid elements are occupied is / are. In case it is used in catalytic dewaxing is at least one catalytic metal component, which at catalytic dewaxing is effective, RE ferrierite added. These metal components typically close at least a Group VIII metal and preferably at least one Group VIII noble metal. Furthermore, the RE ferrierite can be combined with other known catalytic ones Components are connected, which are described in detail below become. A dewaxing catalyst has been found to the RE ferrierite according to the invention to which a Group VIII noble metal has been added the production of high yields of dewaxed lubricating oil fractions with a reduced pour point made of Fischer-Tropsch wax effective that has been hydroisomerized to a mixture of isoparaffins and n-paraffins. Before of petroleum, shale oil, tar sands and such derived hydrocarbon feedstocks catalytically dewaxed, they are treated with hydrogenation to reduce sulfur and nitrogen compounds, aromatics and other unsaturated compounds to remove.

DETAILED DESCRIPTION

How stated above includes a typical dewaxing catalyst according to the invention RE ferrierite and also at least one catalytic metal component. The dewaxing catalyst according to the invention is a two-function catalyst with both a hydroisomerization as well as a dehydrogenation / hydrogenation function, wherein the RE ferrierite the hydroisomerization function and the catalytic metal component provides the dehydrogenation / hydrogenation function. According to one Embodiment contains the catalyst also one or more heat-resistant catalyst support materials, the one or more additional Include molecular sieve component (s). The heat-resistant catalytic support material can be, for example, any oxide or any mixture of oxides like silicon dioxide, which is not catalytically acidic, and acidic oxides such as silica-alumina, other zeolites, Silicon dioxide-aluminum oxide phosphates, titanium dioxide, zirconium dioxide, Include vanadium oxide and other Group IIIB, IV, V or VI oxides. The Groups referred to herein refer to groups as described in the Sargent-Welch Periodic Table of the Elements 1968 was legally protected by the Sargent-Welch Scientific Company. A catalytic metal component, such as one or more groups VIII metals and preferably at least one noble metal from the group VIII, can be deposited on the RE ferrierite, ion exchanged therein or connected thereto, or it can be coated on one or more heat-resistant catalyst support materials or additional Molecular sieve components are applied using the RE ferrierite connected or mixed. Therefore, that will be catalytic metal and, if present, activator metal with a or more of the other catalyst components connected or mixed, impregnated in it, included or otherwise added to it, either before or after they are all mixed together and extruded or be pilled. According to one Embodiment is have been found to be effective in removing the catalytic metal (e.g. B. preferably a noble metal such as Pt or Pd and preferably Pt) ion exchange in the ferrierite. One or more metal activator components of groups VIB and VIIB can with the one or more catalytic Group VIII metal component (s) be used. Typical catalytic dewaxing conditions, those in the method according to the invention are useful are given in the table below.

On RE ferrierite dewaxing catalyst according to the invention can be used to make any waxy hydrocarbonaceous Feed including light and heavy petroleum, raw paraffin, Fischer-Tropsch wax and the same to dewax. Before those of petroleum, Shale oil, tar sands and such derived hydrocarbon feedstocks catalytically dewaxed, they are treated with hydrogenation to reduce sulfur and nitrogen compounds, aromatics and non-aromatic unsaturated compounds to remove. It is preferred to feed these before Hydrotreatment to an oil content from about 0 to 35% by weight and preferably 5 to 25% by weight. The hydrotreatment step is achieved by reacting the feed with hydrogen in the presence of any well known hydrotreating catalyst effected under hydrotreatment conditions. These include catalysts typically catalytic metal components of Co / Mo, Ni / Mo or Ni / Co / Mo on alumina and are well known to those skilled in the art. typical Close conditions a temperature in the range of 282.2 to 398.9 ° C (540 to 750 ° F), one Space velocity from 0.1 to 2.0 v / v / h, a pressure of 35.5 up to 207.9 bar (500 to 3000 psig) and hydrogen treatment rates from 89 to 890 Nl / l (500 to 5000 SCF / B). Furthermore, the feed material on request also hydroisomerized before catalytic dewaxing become.

It has been found that a dewaxing catalyst comprising RE-ferrierite according to the invention is particularly effective in the production of dewaxed low pour point lubricating oil fractions with high product yield from Fischer-Tropsch wax which has been hydroisomerized over a two-function catalyst to produce a high boiling feedstock which a mixture of Includes isoparaffins and n-paraffins. When this Fischer-Tropsch wax feed is made from a catalyst that includes a catalytic cobalt component via a slurry process, it is very pure, typically having less than 1 ppm by weight of either sulfur or nitrogen and at least 95% by weight. Paraffins and even ≥ 98 to 99 wt .-% paraffins, which can also contain very small (z. B. less than 1 wt .-%) amounts of olefins and oxygen-containing compounds. A waxy feed of this general composition and purity usually does not require pre-hydroisomerization treatment because any unsaturated and oxygen-containing compounds that may be present are present in such small amounts that they are consumed in the hydroisomerization without adversely affecting the hydroisomerization catalyst. However, there are other known Fischer-Tropsch hydrocarbon synthesis processes and catalysts which do not produce a waxy feed of this purity and which may therefore require hydrotreatment prior to hydroisomerization. Fischer-Tropsch wax generally means the product of a Fischer-Tropsch hydrocarbon synthesis process that contains C ₅₊ , preferably C ₁₀₊ , and especially C ₂₀₊ paraffinic hydrocarbons. In a slurry process, the wax comprises the hydrocarbon liquid withdrawn from the slurry reactor. For example, the table below shows the fractionated fresh hydrocarbons (± 10 wt% for each fraction) that were synthesized in a slurry HCS reactor using a catalyst comprising cobalt and rhenium on a titanium dioxide support.

During the Hydroisomerization of the waxy, paraffinic feed in the method according to the invention becomes somewhat heavy feedstock (e.g. 343.3 to 398.9 ° C (650 ° F + to 750 ° F +)) depending of the desired Separation limit and whether dewaxed fuel fractions also desired are or not, converted to lower boiling components, any olefins and oxygenated compounds present be hydrogenated. Fuel fractions are generally dewaxed, for their cloudiness (cloud (or haze)) and freezing points. The hydroisomerization conditions can vary widely. Wide temperature and pressure ranges are typically from 300 to 900 ° F (149 to 482 ° C) and from 1.0 to 173.4 bar (0 to 2500 psig) with preferred ranges from 550 to 750 ° F (288 to 400 ° C) or 21.7 to 83.7 bar (300 to 1200 psig). The range of hydrogen treatment rates is typically from 89 to 890 Nl / l (500 to 5000 SCF / B) and from 8.9 to 89 Nl / l (50 to 500 SCF / B) with preferred ranges from 356 to 712 Nl / l (2000 to 4000 SCF / B) or 8.9 to 89 Nl / l (50 to 500 SCF / B). The hydroisomerization catalyst comprises one or more catalytic metal component (s) based on a acidic metal oxide carrier is / are applied to the catalyst both a hydrogenation / dehydrogenation function to give an acidic hydroisomerization function as well. illustrative, but not restrictive Examples of these catalysts, their preparation and use can for example, found in US-A-5,378,348 and US-A-5,660,714 become. The isomer is fractionated to make the lighter 343 ° C to 400 ° C (650 ° F to 750 ° F) isomerate (dependent on of the desired Separation limit) from the heavier lubricating oil fraction, whereby on request, the lighter material can be used for fuel, which boils in the naphtha and diesel fuel sectors. The lubricating oil fraction will then by reaction with hydrogen using the catalyst according to the invention and process catalytically dewaxed to their pour point further decrease.

Ferrierite is primarily classified as a medium pore size material with pore windows of 5.4☐ × 4.2☐ (p. 106, Atlas of Zeolite Structure Types, 4th edition, Elsevier 1996). Natural and synthetic ferrierite include a zeolite type of ion-exchangeable crystalline aluminosilicate molecular sieve with both 10 and 8 ring pore windows with an atomic ratio of silicon to aluminum of about 5 in natural ferrierite (although this can vary) and a ratio of about 8 to greater than 30 (typically from 10 to 20) in synthetic ferrierite as is known. The manufacture and composition of synthetic ferrierite are well known and are discussed, for example, in US-A-4,251,499 and US-A-4,335,019. Both natural and synthetic ferrierite are commercially available in which the cation exchange sites are typically replaced by alkali metal cations such as Na ⁺ , K ⁺ and mixtures of the same are occupied. The alkali form is easily converted to the hydrogen form or to a hydrogen precursor form, such as the ammonium ion form, for subsequent ion exchange with the desired metal (s) by contacting it with an aqueous solution containing ammonium ions that exchange with the alkali metal cations. Calcination of the ammonium form produces the hydrogen (H ⁺ ) or acid form, which can also be made directly by contacting the ferrierite with a suitable material such as hydrochloric acid. Although ferrierite is known as a dewaxing catalyst both with and without a catalytic metal component, examples of dewaxing using rare earth ion exchanged ferrierite have not been disclosed. This is not surprising since the conventional ion exchange process is ineffective for this purpose. For example, US-A-4,584,286 and US-A-5,288,475, which relate to ZSM-35, both refer to US-A-3 140 249 and US-A-3 140 251 for conventional ion exchange processes and US-A-3 140 253. The '249,' 251 and '253 patents disclose metal ion exchange including rare earth ion exchange using aqueous salt solutions of the metal or metal and ammonia at atmospheric pressure and a temperature which is in the range from room temperature to 82.2 ° C (180 ° F). However, this method has been found to be ineffective in ion exchange of rare earth metals with ferrierite. Although rare earth metal ion exchange is also included in a long list of potential cations, the surprising selectivity to lubricating oil fractions resulting from the use of ferrierite exchanged with trivalent rare earth is not mentioned anywhere. For example, using this method to try ion exchange of lanthanum with ammonium ferrierite from an aqueous solution of lanthanum chloride for 48 hours at 82.2 ° C (180 ° F), followed by washing with water, resulted in a lanthanum content of only 0.31 wt .-%. This means that a maximum of only about 5% of the cation exchange capacity was affected by trivalent lanthanum cations in cation exchange sites. Without wishing to be bound by any particular theory, it is believed that the ion exchange, if it occurred, could only have occurred on the outer surface of the ferrierite and not in the pores where it is necessary to be catalytically active. Therefore, the present invention is unexpected in view of the prior art. In the practice of the invention, the trivalent rare earth metal or trivalent rare earth metals are ion exchanged into the ferrierite using a hydrothermal process in which a hydrogen ferrierite precursor or hydrogen (H +) ferrierite is mixed with an aqueous solution of the desired trivalent rare earth metal or metals is contacted under hydrothermal conditions, which means at a temperature above the boiling point of the solution at normal atmospheric pressure. The time and temperature that is sufficient to achieve the desired degree of exchange is determined experimentally. For example, ammonium ferrierite is immersed in a solution of lanthanum chloride in a sealed vessel at a temperature of 392 ° F (200 ° C) for 24 hours to give a lanthanum exchanged ferrierite containing 1.97% by weight of La. This means that about 28% of the cation exchange capacity available for cation exchange was occupied by lanthanum. The time and temperature that is sufficient to achieve the desired degree of exchange is determined experimentally. After ion exchange, the ion exchanged ferrierite can then be washed, dried, calcined and the ion exchange, washing, drying and calcining steps repeated as often as necessary to achieve the desired level of ion exchange. It is a practical matter that typically a mixture of two or more rare earth metals is ion exchanged. Illustrative but not limiting examples include commercially available mixtures of lanthanum, cerium, praseodymium and neodymium as the main rare earth elements in the mixture. In the catalytic use, the cerium content of the mixture is typically consumed.

As mentioned above, the molar ratio of silica to alumina or the molar ratio of silicon to aluminum of the ferrierite varies. The cation exchange capacity of the ferrierite is determined by the aluminum or alumina content. Each mole of aluminum ion that is substituted in tetrahedral positions on the zeolite framework creates 1 mole of negative charge on the framework. This charge is balanced by exchangeable cations. Since rare earth metal (RE) cations are trivalent, each mole of RE ion installed via ion exchange replaces three moles of alkali metal, ammonium or hydrogen ions. Therefore, the degree or percentage of RE exchange, which is a measure of the cation exchange sites occupied by the trivalent rare earth cations, makes more sense than the weight percentage of the rare earth metal that is incorporated into the ferrierite after ion exchange with solutions containing one or more rare earth metal cations. The rare earth metal (RE) content, the SiO ₂ / Al ₂ O ₃ molar ratio and the degree of exchange are all related by the following expression: % RE exchange = [3 × (Mol RE)] / [(Mol Al) × 100]

These values are determined by any suitable analytical method (such as elemental analysis) which gives the amount of any element present in the dry RE ferrierite, that results after the exchange and washing with water to remove any metal that has not been exchanged inside. As an example, the table below gives examples of the content in% by weight of the rare earth metal La, which is calculated on a dry basis with a change in the Sio ₂ / Al ₂ O ₃ molar ratio in the ferrierite and the% exchanged La. This shows that the elemental analysis at high SiO ₂ / Al ₂ O ₃ molar ratios of the ferrierite shows a low weight% of La even at considerable degrees of La exchange.

With specific reference to waxy feeds made by a Fischer-Tropsch hydrocarbon synthesis (HCS) process, liquid and gaseous hydrocarbon products are obtained by contacting a synthesis gas (syngas) comprising a mixture of H ₂ and CO with a Fischer-Tropsch type of one HCS catalyst is formed in which the H ₂ and CO react to form hydrocarbons under shift or non-shift conditions and preferably under non-shift conditions where there is little or no water gas shift reaction, especially when the catalytic metal Co, Ru or a mixture thereof. Suitable types of Fischer-Tropsch reaction catalysts include, for example, one or more Group VIII catalytic metals such as Fe, Ni, Co, Ru and Re. In one embodiment, the catalyst comprises catalytically effective amounts of Co and one or more of Re, Ru, Fe, Ni, Th, Zr, Hf, U, Mg and La on a suitable inorganic support material, preferably one that is one or more heat resistant Includes metal oxides. Preferred supports for Co-containing catalysts include titanium dioxide, especially when using a slurry HCS process in which predominantly paraffinic liquid hydrocarbon products of higher molecular weight are desired. Useful catalysts and their manufacture are known and illustrative but non-limiting examples can be found, for example, in US-A-4,568,663, US-A-4,663,305, US-A-4,542,122, US-A-4,621,072 and US-A-5 545 674. Fixed bed, fluidized bed and slurry hydrocarbon HCS processes are well known and documented in the literature. In all of these processes, the syngas is reacted in the presence of a suitable Fischer-Tropsch type of hydrocarbon synthesis catalyst under reaction conditions effective to form hydrocarbons. Some of these hydrocarbons are liquid, some are solid (e.g. wax) and some are gaseous at standard room temperature conditions of temperature and pressure of 25 ° C and 1 atmosphere. Slurry HCS processes are often preferred because of their superior heat (and mass) transfer properties for the highly exothermic synthesis reaction and because they can produce relatively high molecular weight paraffinic hydrocarbons using a cobalt catalyst. Because of the removal of sulfur and nitrogen compounds from the syngas feed prior to the synthesis reaction, the purity of the hydrocarbons produced by the process using sulfur and nitrogen sensitive catalysts is exceptionally high, typically with little or no hydrotreatment prior to Isomerization, catalytic dewaxing or other refining procedures. In a slurry HCS process, which is a preferred process in the practice of the invention, a syngas comprising a mixture of H ₂ and CO is bubbled as a third phase by a slurry in a reactor which is one comprises particulate Fischer-Tropsch type hydrocarbon synthesis catalyst dispersed and suspended in a slurry liquid comprising synthesis reaction hydrocarbon products that are liquid at reaction conditions. The molar ratio of hydrogen to carbon monoxide can be in a wide range from about 0.5 to 4, but is typically within the range from about 0.7 to 2.75, and preferably from about 0.7 to 2.5. The stoichiometric mole ratio for a Fischer-Tropsch HCS reaction is 2.0, but it can be increased in the practice of the present invention to obtain the desired amount of hydrogen from the syngas for others other than the HCS reaction , In a slurry HCS process, the molar ratio of H ₂ to CO is typically about 2.1 / 1. Slurry HCS process conditions vary somewhat depending on the catalyst and the desired products. Typical conditions for the formation of hydrocarbons, the predominantly C ₅₊ paraffins (e.g., C ₅₊ -C ₂₀₀ ), and preferably C ₁₀₊ paraffins (and particularly C ₂₀₊ ), are effective in a slurry process using a catalyst comprising a supported cobalt component, e.g., include temperatures , Pressures and hourly gas space velocities (hourly volume throughput) in the range from approximately 160 to 315.5 ° C (320 to 600 ° F), 5.5 to 41.2 bar (80 to 600 psig) or 100 to 40,000 V / h / V, expressed as standard volumes of the gaseous CO and H ₂ mixture (0 ° C, 1 atm), per hour per volume of the catalyst. The hydrocarbons that are liquid under the reaction conditions and are removed from the reactor (using filtration media and optionally a hot separator to extract C ₁₀₊ from the HCS gas) include predominantly (e.g.> 50% by weight and typically 60 wt% or more) hydrocarbons boiling above 343 to 371.1 ° C (650 to 700 ° F) and comprise at least about 95 wt% paraffins with negligible (e.g. less than 1 wppm) Amounts of either nitrogen or sulfur compounds.

The Invention will be further understood with reference to the examples below.

EXAMPLES

example 1

Ammonium ion exchange of alkali metal ferrierite was carried out by suspending 100 g Na ferrierite with a silicon to aluminum ratio of 8.4 in 500 ml of a 5% by weight aqueous NH ₄ Cl solution. The mixture was stirred at 50 ° C for several hours, filtered and washed with distilled and deionized water. The exchange was repeated twice and the resulting NH ₄ ferrierite was dried at 70 ° C in a vacuum oven. Lanthanum ion exchange with the NH ₄ ferrierite was accomplished by enclosing 7 g of NH ₄ ferrierite and 40 ml of a 0.2 M aqueous solution of LaCl ₃ in a Teflon lined stainless steel vessel, followed by heating at 200 ° C for 24 hours occasional shaking. The jar was quenched with cold water and opened immediately. The solid was filtered, washed with hot distilled and deionized water until it was free of chloride according to an AgNO ₃ test, and then dried at 70 ° C in a vacuum oven. Elemental analysis of the NH ₄ ferrierite and the La ferrierite showed Si / Al atomic ratios of 8.1 in both cases. The La ferrierite contained 1.86% by weight of La, indicating that 27% of the available cation exchange sites were occupied by the lanthanum. The preparation of the X-ray powder diffraction data showed orthorhombic cell constants of 18.84, 14.10 and 7.430 for the NH ₄ ferrierite and of 18.94, 14.12 and 7.450 for the La ferrierite. The BET surface area of the NH ₄ ferrierite was 288 m ² / g and that of the La ferrierite was 320 m ² / g.

Comparative example A

A 0.4 g sample of the NH ₄ ferrierite prepared in Example 1 was mixed with 2.4 g of a 5% by weight aqueous LaCl ₃ solution in a sealed glass vial and at 82.2 ° C (180 ° F) heated with occasional shaking. The resulting material was separated from the solution by filtration, washed with distilled and deionized water until it was free of chloride according to an AgNO ₃ test, and then dried in a vacuum oven at 70 ° C. The elemental analysis showed a lanthanum content of only 0.31%, which indicated that only about 5% of the available cation exchange sites could be occupied by lanthanum.

Example 2

Dewaxing catalysts were made by adding 0.5 wt% platinum to both the NH ₄ ferrierite and the La ferrierite prepared in Example 1. The Pt was added by ion exchange with the remaining ammonium sites on the ferrierite using Pt (NH ₃ ) ₄ (OH) ₂ . These platinum-loaded materials were then calcined in air at 400 ° C, pelletized, ground and sieved to a Tyler mesh size of 14/35. The elemental analysis showed Pt contents of 0.57 and 0.54% by weight.

Comparative example B

On additional Catalyst for comparison was impregnated and extrusion, which comprised 0.5 wt% Pt, on a Mixture of 80 wt .-% mordenite and 20 wt .-% alumina applied was that at 400 ° C was calcined in air.

Example 3

A hydrocarbon synthesis gas comprising a mixture of H ₂ and CO with a molar ratio of between 2.11 to 2.16 was reacted in a slurry that comprised bubbles of the synthesis gas and particles of a Fischer-Tropsch hydrocarbon synthesis catalyst that contained cobalt coated on titanium dioxide and rhenium in a hydrocarbon slurry liquid containing the particulate catalyst and bubbles of the synthesis gas. The hydrocarbon slurry liquid comprised synthesis reaction hydrocarbon products that were liquid under the reaction conditions. The reaction conditions included a temperature of 218.3 ° C (425 ° F), a pressure of 21 bar (290 psig) and a linear gas feed rate of 12 to 18 cm / s. The alpha of the synthesis step was 0.92. A fraction boiling at 371.1 ° C + (700 ° F +) was separated from the hydrocarbon product by equilibrium distillation.

Example 4

The synthesized, at 371.1 ° C + (700 ° F +) boiling hydrocarbon fraction from Example 3 comprised at least about 98% by weight paraffins. This material was made by implementing it with hydrogen in the presence of a two-function hydroisomerization catalyst hydroisomerized from impregnated on an amorphous silica-alumina support Cobalt and molybdenum duration. The reaction and reaction conditions were set by 50% by weight conversion of the material at 371.1 ° C + (700 ° F +) to lower boiling Material reached, and included a temperature of 371.1 ° C (700 ° F), one Space velocity of 0.45 v / v / h, a pressure of 70.0 bar (1000 psig) and a hydrogen treatment rate of 445 Nl / l (2500 SCF / B) on. The resulting isomerate was fractionated to boil at 371.1 ° C + (700 ° F +) To win fraction, which is a mixture of n-paraffins and isoparaffins included and had a pour point of 2 ° C.

Example 5

The Entparaffinierungsaktivität and selectivity of the three different catalysts used in Example 2 and Comparative Example B were made by reacting separate proportions the 371.1 ° C + (700 ° F +) isomerate fraction Example 4 with hydrogen in the presence of each catalyst using an upstream 0.9525 cm (3/8 inch) fixed bed reactor under reaction conditions of 52.7 bar (750 psig), 2.0 w / h / w and a hydrogen treatment rate of 445 Nl / l (2500 SCF / B). The reaction temperature varied and was set to have a comparable lubricant product pour point for everyone Reach catalyst. The results of these evaluations related on products and properties are listed in the table below.

As these data show, the Pt / La ferrierite catalyst was more selective than Pt / NH ₄ ferrierite compared to the preparation of the dewaxed lubricant product boiling at 371.1 ° C + (700 ° F +), with lower gas generation and higher lubricant yield equivalent pour point. The Pt mordenite catalyst produced significantly less 371.1 ° C + (700 ° F +) material with significantly higher gas generation than the Pt / La ferrierite catalyst according to the invention.

Claims (18)

Process for dewaxing waxy hydrocarbonaceous feedstock which is implementing the feed with hydrogen in the presence of a catalyst, which includes ferrierite in which one or more trivalent rare earth metal cations occupy at least 10% of its cation exchange sites, at one Temperature in the range of 148.9 to 510 ° C (300 to 950 ° F), one Space velocity from 0.1 to 10 v / v / h, a total pressure of 18.24 to 207.9 bar (250 to 3000 psig) and a hydrogen treatment rate from 89 to 2670 Nl / l (500 to 15000 SCF / B). The method of claim 1, wherein the rare earth containing ferrierite with at least one catalytic metal component is combined. The method of claim 2, wherein the catalytic Metal component comprises a Group VIII noble metal component. The method of claim 1, wherein at least 15% the cation exchange capacity are documented by the rare earth metal cations. The method of claim 3, wherein at least 15% the cation exchange capacity are documented by the rare earth metal cations. The method of claim 5, wherein at least 25% the cation exchange capacity are documented by the rare earth metal cations. The method of claim 1, wherein the hydrocarbonaceous Feedstock includes paraffins. The method of claim 1, wherein the hydrocarbonaceous Feedstock a mixture of n-paraffins and isoparaffins includes. The method of claim 6, wherein the hydrocarbon-containing Feedstock includes paraffins. The method of claim 6, wherein the hydrocarbon-containing Feedstock a mixture of n-paraffins and isoparaffins includes. The method of claim 3, wherein the hydrocarbonaceous Feedstock a mixture of n-paraffins and isoparaffins includes. A hydrocarbon synthesis and upgrading process which comprises (i) contacting a synthesis gas comprising a mixture of H ₂ and CO with a Fischer-Tropsch hydrocarbon synthesis catalyst at reaction conditions effective to convert the H ₂ and CO to form hydrocarbons , at least a portion of which is solid at standard room temperature and pressure conditions, (ii) hydroisomerizing at least a portion of the hydrocarbons, including at least a portion of the solid hydrocarbons, by reacting the hydrocarbons with hydrogen in the presence of a hydroisomerization catalyst under conditions that are effective to form a waxy hydroisomerizate comprising a mixture of paraffins and isoparaffins, and (iii) dewaxing the waxy isomerizate by the method of any one of claims 1 to 11 to form a dewaxed isomerizate. The method of claim 12, wherein the hydrocarbons be treated hydrogenating before the hydroisomerization reaction. The method of claim 12, wherein the catalytic Metal component comprises a Group VIII noble metal component. The method of claim 12, wherein at least 15% the cation exchange capacity are documented by the rare earth metal cations. The method of claim 12, wherein at least 25% the cation exchange capacity are documented by the rare earth metal cations. The method of claim 12, wherein the dewaxed Hydroisomerisate a lubricating oil fraction includes. The method of claim 16, wherein the dewaxed Hydroisomerisate a lubricating oil fraction includes.