KR0139090B1 - A crystalline silicoaluminophosphate molecular sieve and process for preparation of the same - Google Patents

Abstract

Silicoaluminophosphate molecular sieves have been published, the molar ratio of P ₂ O ₅ to alumina at the surface is less than about 0.80, the volume molar ratio of P ₂ O ₅ to alumina is at least 0.96, and the silicon content at the surface is greater than the volume. It is characterized by.

Description

[Name of invention]

Crystalline Silicoaluminophosphate Molecular Weight and Method for Preparing the Same

[Brief Description of Drawings]

1 is a ternary diagram showing the compositional parameters of the silicoaluminophosphate of the present invention in terms of fractions along silicon, aluminum and moles thereof.

2 is a ternary diagram showing the preferred compositional parameters of the silicoaluminophosphate of the present invention in terms of mole fractions of silicon, aluminum and phosphorus.

Detailed description of the invention

[Background of invention]

The present invention relates to novel crystalline silicoaluminophosphate molecular sieves and their synthesis. More specifically, the present invention relates to a surface P ₂ O ₅ / Al ₂ O ₃ molar ratio and a surface SiO ₂ / Al ₂ O ₃ molar ratio corresponding to the volume molar ratio and other volumes P ₂ O ₅ / Al ₂ O ₃ molar ratio and volume SiO ₂ / It relates to the synthesis of crystalline silicoaluminophosphate molecular sieves having an Al ₂ O ₃ molar ratio.

Silicoaluminophosphate is shown by way of example in US Pat. No. 4,440,871. The silicoaluminophosphate material is microporous and crystalline, has a three-dimensional crystal structure of PO2 ⁺ , AlO ₂ ^- and SiO ₂ tetrahedral units and is synthesized, except for any alkali metal or other cation that may optionally be present. And has the chemical composition of the following empirical formula on the basis of anhydride:

mR: (Si _x Al _y P _z ) O ₂

Wherein R represents at least one organic template present in the internal crystalline pore system;

m has a value from 0 to 0.3 indicating the number of moles of R present per mole of (Si _x Al _y P _z ) O ₂ , the maximum in each case being the molecular dimension of the template and the specific silicoaluminophosphate species involved. Depends on the useful porosity of the pore system;

X, Y and Z represent the mole fractions of silicon, aluminum and phosphorus present as tetrahedral oxides, respectively. The minimum value for each X, Y and Z is 0.01 and preferably 0.02. The maximum value for X is 0.98; The maximum value for Y is 0.60; The maximum value for Z is 0.52.

Seed crystals of SAPO species or morphologically similar aluminophosphates or aluminosilicate compositions that are not essential for the synthesis of SAPO compositions but generally stir the reaction mixture or otherwise suitably stir the reaction mixture and / or produce the reaction mixture. Seeding is disclosed in US Pat. No. 4,440,871, which has been found to facilitate the crystallization process. These silicoaluminophosphates exhibit a variety of physical and chemical properties that are characteristic of aluminosilicate zeolites and aluminophosphates.

Silicoaluminophosphate SAPO-11 and its conventional method of preparation are described in US Pat. No. 4,440,871.

[Summary of invention]

The present invention relates to a novel synthetic crystalline silicoaluminophosphate molecular sieve (hereinafter referred to as SM-3). In general, SM-3 silicoaluminophosphate is a silico having an essential X-ray diffraction pattern of SAPO-11 with phosphorous, silicon and aluminum concentrations in the volume of the molecular sieve and phosphorus, silicon and aluminum concentrations in other molecular sieve surfaces. As aluminophosphate, it can be characterized by its distinction from all other silicoaluminophosphate forms.

More particularly, the present invention relates to a synthesized crystalline silicoaluminophosphate molecular sieve having a composition represented by the following empirical formula (I) in terms of the molar ratio of oxides on the basis of anhydrides.

mR: Al ₂ O ₃ : nP ₂ O ₅ : qSiO ₂ (I)

Wherein R represents at least one organic template present in the internal crystalline pore system;

m represents the number of moles of R present and m has a value such that 0.02 to 2 moles of R per mole of aluminum can be present;

n has a value between 0.96 and 1.1;

q has a value from 0.1 to 4.

The silicoaluminophosphate has a unique X-ray powder diffraction pattern comprising at least the d-spacings of Table I, wherein the molar ratio of P ₂ O ₅ to alumina on the surface of the silicoaluminophosphate is about 0.80 or less, and the silicoaluminoin The molar ratio of P ₂ O ₅ to alumina in volume of the acid salt is at least 0.96, and the SiO ₂ to alumina molar ratio at the surface of the silicoaluminophosphate is greater than the SiO ₂ to alumina molar ratio at the volume of silicoaluminophosphate.

In addition, the method of the present invention

(a) it said composition is represented by alumina, and the source in a molar ratio of oxides, such as, to the proportional by silicon source and formulation with an organic primary molded product and the mixture produced was blended under substantial absence of the silicon source is continuously Genie, SiO ₂ aluminum Preparing a complete aqueous reaction mixture containing isopropoxide, phosphoric acid and a reactive source of organic template;

(b) adjusting the pH of the reaction mixture to about 6.0 to 8.5;

(c) the reaction mixture is heated to a temperature in the range of 170 ° C. to 240 ° C. until crystals of silicoaluminophosphate are formed;

(d) retrieving the SM-3 crystalline silicoaluminophosphate characterized in that the crystals are recovered:

aR: Al ₂ O ₃ : 0.9-1.2 P ₂ O ₅ : 0.1 -4.0 SiO ₂ : bH ₂ O

Wherein R is an organic template;

a has a value large enough to constitute an effective amount of R, preferably having a value such that 0.20 to 2 moles of R per mole of aluminum oxide are present;

b has a value such that 10 to 40 moles of H ₂ O per mole of aluminum oxide are present.

Among other factors, the present invention is based on the inventors' finding that novel silicoaluminophosphate molecular sieves can be produced having a surface composition of the molecular sieve and another volume composition by controlling the reaction conditions. Controlling the distribution and position of silicon on the surface of the silicon aluminophosphate increases the activity of the silicon aluminophosphate as a catalyst while maintaining the option as a catalyst.

The silicoaluminophosphate materials of the present invention exhibit unique and useful catalytic properties and have shape selection properties. Activity is generally determined by comparing the temperatures at which the various catalysts must be used under different constant reaction conditions with the conversion rates of the same hydrocarbonaceous feedstock and the same product. The lower the reaction temperature for a given reaction range, the more active the catalyst for the particular process. The present invention silicoaluminophosphate, an ASPO-11-form silicoaluminophosphate, exhibits superior activity compared to SAPO-11 prepared by conventional methods as set forth in US Pat. No. 4,440,871 and at the same time known SAPO-11 It has the same or improved advantageous selectivity as silicoaluminophosphate. Selectivity is a measure of the yield of the desired product.

The novel SM-3 silicoaluminophosphate as synthesized has a crystal structure in which the X-ray powder diffraction form of the crystal structure shows the following characteristic line.

TABLE I

m = 20-70

s = 70-90

vs = 90-100

X-lane powder diffraction pattern is determined by standard techniques. The radiation is a K-alpha / 2 duplex of copper and uses a scintillation spectrometer with a strip-chart pen recorder. The positions are read from the spectrometer chart as the peak heights I and θ are functions of the Bragg angle 2θ. These are from the measured value of I _O to compute the liner or inner plane distance in the peak relative intensity 100 O / I _O Å and corresponding to the recorded lines d. The X-ray diffraction forms of Table I are X-ray diffraction forms for SAPO-11, such as those disclosed in US Pat. No. 4,440,871, which is characteristic of the novel SM-3 silicoaluminophosphate and is incorporated by reference herein in its entirety. Matches

After calcining, SM-3 silicoaluminophosphate has a crystal structure in which the X-ray powder diffraction pattern of the crystal structure shows a characteristic line as shown in Table II below.

TABLE II

As synthesized, the SM-3 silicoaluminophosphate molecular sieve is composed of [SiO ₂ ], [AlO ₂ ], and [PO ₂ ] of three-dimensional micropores having a composition relating to the molar ratio of oxides of the anhydride basic phase represented by the following general formula (I). Features the crystal structure of tetrahedral units:

mR: Al ₂ O ₃ : nP ₂ P ₅ : qSiO ₂

Wherein R is one or more organic template (hereinafter referred to as template) present in the internal crystal pore system;

m represents the moles of R present and has a value equal to 0.02 to 2 moles R per parent of alumina;

n has a value of 0.096 to 1.1, preferably 0.96 to 1 and q has a value of 0.1 to 4, preferably 0.1 to 1.

As synthesized, the SM-3 silicoaluminophosphate molecular sieve can be expressed in terms of its unit empirical formula. It is represented by the following general formula (II) on the anhydride base:

mR: (Si _x Al _y P _z ) O ₂ (II)

Wherein R and m are as defined above;

XY and Z represent the mole fractions of silicon, aluminum and phosphorus, respectively, represented as tetrahedral oxide units, the mole fractions being shown in FIG. 1 of the figure in which points A, B, C and D are represented by the following values for X, Y and Z: It lies within the tetrahedral composition area defined by points A, B, C and D of the three-dimensional composition diagram indicated by.

In a preferred embodiment the values for X, Y and Z in general formula (II) are present in the tetrahedral composition area defined by points a, b, c and d of the three-dimensional diagram, FIG. b, c and d are represented by the following values for X, Y and Z.

The SM-3 silicoaluminophosphate of the present invention also has a P ₂ O ₅ to alumina molar ratio at the surface of the silicoaluminophosphate of about 0.80 or less, preferably in the range of 0.80 to 0.55 and the volume of P ₂ of the silicoaluminophosphate. The molar ratio of O ₅ to alumina is at least about 0.96, preferably 0.96 to 1.1, most preferably in the range of 0.96 to 1, and the SiO ₂ to alumina molar ratio at the surface of the silicoaluminophosphate is SiO in the volume of the silicoaluminophosphate. _It is characterized by greater than _two to alumina molar ratios.

The content of silicon as determined by the silica to alumina molar ratio at the surface of the silicoaluminophosphate in the molecular sieve of the invention is greater than in the volume of the molecular sieve.

The term silicon content at the surface of a molecular sieve refers to the amount of silicon at the surface of a sample, such as can be measured using X-ray photoelectron spectroscopy surface analysis (ESCA); This silicon content may include any amorphous silica present. The molecular sieves of the present invention have a higher silicon content at the surface than in volume. This comparison can compare either the silica content itself or the silica / alumina ratio.

The term unit formula is used herein to describe silicon, aluminum and phosphorus atoms which form [PO ₂ ], [AlO ₂ ] and [SiO ₂ ] tetrahedral units in the molecular sieve of silicoaluminophosphate and form the molecular structure of the SM-3 composition. It is used with respect to the general meaning of the simplest expression of relative numbers.

The unit empirical formula may be present as a product of manufacture or in the presence of other impurities or substances in a volume composition which is expressed in terms of silicon, aluminum and phosphorus as shown in the general formula (II) above and does not include the tetrahedral units described above as molecular structure. It does not contain compounds, cations or anions. The amount of template R is part of the composition given the unit empirical formula as synthesized and water can also be recorded unless defined in the form of their anhydrides. For convenience, the coefficient m for template R is reported as standardized by dividing the number of moles of R by the total number of moles of alumina. When moles of water are recorded, the moles of water are normalized by dividing the moles of water by the total moles of alumina. The values for X, Y and Z are determined by dividing the moles of silicon, aluminum and phosphorus by the total moles of silicon, aluminum and phosphorus, respectively.

The composition of the empirical formula (I) as well as the unit empirical formula (II) for the SM-3 silicoaluminophosphate can be given to the base phase as synthesized, and the synthesized SM-3 composition can be applied to any post-treatment process, such as calcination. Can be given after. The term synthesized herein may be used with respect to the SM-3 composition formed as a result of the crystallization of hydrothermal water, but may be used with respect to the SM-3 composition formed before the SM-3 composition removes any volatile components present therein. have.

The actual value of m for the post-treated SM-3 depends on a number of factors, including the mold, the severity of the post-treatment on the performance of the mold to remove the mold from the SM-3, and the application of the proposed SM-3 composition. Can be influenced. The amount of template for the post-treated SM-3 may be in the range as defined for the SM-3 composition as synthesized but is generally less. The SM-3 composition present in the calcined or otherwise post-treated form is generally except that the value of m is generally in the range of 0 to 0.3 moles per mole of alumina, most preferably 0 to 0.1 and generally less than about 0.02 And a composition represented by an empirical formula represented by formula (I) or formula (II).

Under sufficiently strong post-treatment conditions, for example, roasting for a long time (more than 1 hour) at high temperature in air, the value of m may be zero or in some cases template R may not be detected by conventional analytical processes.

In synthesizing the SM-3 composition of the present invention, the reaction mixture is essentially free of alkali metal cations and thus the preferred reaction mixture composition expressed in terms of the molar ratio of oxides is as follows;

aR: Al ₂ O ₃ : 0.9-1.2 P ₂ O ₅ : 0.1-4.0 SiO ₂ : bH ₂ O

Wherein R is an organic template;

a has a value large enough to constitute an effective concentration of R and preferably has a value such as about 0.20 to 2 moles of R per mole of alumina and most preferably a value of 0.8 to 1.2;

b has a value such as 10 to 40 moles of H ₂ O per mole of aluminum oxide, and preferably has a value of 15 to 36.

The aqueous reaction mixture in the synthetic process of the present invention is prepared by combining a reactive aluminum and phosphorus source in the substantial absence of a silicon source and then combining the resulting reaction mixture containing aluminum and phosphorus sources with a silicon source and then combining the mixture with a mold. do. If alkali metal cations are present in the reaction mixture, these cations should be present at sufficient low concentrations that do not interfere with the formation of the SM-3 composition.

Certain inorganic cations and anions that may be present in the reaction mixture are generally not provided by the components added separately. Moreover, these cations and anions can often arise from compounds added to the reaction mixture to provide other essential ingredients such as silicon sources or organic template or any PH regulator that may be used.

More detailed synthesis method

(a) preparing an aqueous reaction mixture comprising aluminum isopropoxide and phosphoric acid and then combining the resulting mixture with a silicon oxide source and combining the mixture with an organic template to form a complete reaction mixture in the relationship set forth above;

(b) adjusting the pH of the reaction mixture to about 6.0 to 8.5 at the beginning of the reaction and preferably in the range of 6.0 to 8.0;

(c) the reaction mixture is heated to a temperature in the range from 170 ° C. to 240 ° C., preferably from 180 ° C. to 225 ° C., usually from 5 hours to 500 hours and preferably from 24 to 500 hours, until crystals are formed;

(d) recovering crystalline SM-3 silicoaluminophosphate.

Crystallization is carried out under hydrothermal conditions under pressure in a pressurized reactor, preferably without stirring, so that the reaction mixture is usually spontaneous.

After crystallization of the SM-3 material, the reaction mixture contained equally is filtered and the recovered crystals are dried, for example, washed with water and then heated at 25 ° C. to 150 ° C. under atmospheric pressure. Preferably the supernatant on the crystals is removed before the initial filtration of the crystals.

SM-3 produced by the present invention is advantageously heat treated to remove the organic template. This heat treatment is generally carried out by heating at a temperature of from 300 ° C. to 1000 ° C. for at least 1 minute and generally less than 20 hours. Pressures below atmospheric pressure can be used for heat treatment while atmospheric pressure is preferred for reaction for convenience. Thermally treated products are particularly useful in the catalysts of certain hydrocarbon conversion reactions.

The aluminum and phosphorus components are mixed well and the silicon component is added at the end to produce a high purity SM-3-form material.

SM-3 silicoaluminophosphate has a low pH ranging from about 6.10 to about 8.5 and preferably ranging from 6.0 to 8.0 and prepared at a molar ratio of from 15 to 36 H ₂ O / Al ₂ O ₃ and preferably from 10 to 40 do. Under these conditions, SiO ₂ depolymerization is slow and nucleation is fast. Under the conditions of the present invention crystallization is generally completed in less than 5 hours.

While not wishing to be bound by theory, in the early phase of the reaction, SiO ₂ enters the structure until delayed in crystallization, such as near aluminophosphate, which is surrounded by a SiO ₂ rich amorphous phase under the conditions of the process of the present invention. It doesn't seem to go. The pH of the mixture rises from about 10 to about 10.5 as PO ₄ ^-3 is consumed by the reaction with the Al ⁺³ species.

This increases the solubility of SiO ₂ allowing silica incorporation into a structure such that a silicoaluminophosphate shell is formed around the aluminophosphate nucleus. Molecular sieves can be thought of as almost crystalline aluminophosphates because the P ₂ O ₅ to alumina molar ratio in the volume of SM-3 silicoaluminophosphate at the macromarket is at least 0.96 and preferably 0.96 to 1.

The surface silica rich phase of the outer phase of the molecular sieve comprises a SiO ₂ / alumina ratio higher than the volume. Materials with higher surface silica to alumina ratios appear to exhibit increased acidity and increased activity.

The thickness of the SM-3 shell can be controlled by adjusting the pH and H ₂ O / Al ₂ O ₃ ratio of the mixture. For example, one method for reducing the thickness can be by additionally adding H ₃ PO ₄ to the mixture. This is to lower the final pH, for example by adjusting the acidity so that Si is not incorporated until the synthesis is complete.

What is needed is an acid such as HCl or H ₃ PO ₄ to lower the PH into the correct zone. A slight excess of PO ₄ ^-3 may be desirable because the concentration of PO ₄ ^-3 is very low and the alumina and silica components do not react with each other.

Excess water over the stated ranges tends to quickly incorporate silica into the product. Excess water also leads to larger crystals that can reduce activity due to diffusion limitations. Crystal sizes of less than 1 micron in the present invention are prepared using an average size of less than 0.5 micron.

The activity of SM-3 silicoaluminophosphate is improved because the synthesis temperature can be increased to at least 240 ° C or less. Fines seem to improve crystal growth and thus improve the degree of crystallinity of the product. There is a tendency to provide more complete Si incorporation leading to more active sites.

The organic template or direct agent is selected from di-n-propylamine and di-isopropylamine or mixtures thereof.

Useful sources of silicon oxide include any form of silicic acid or other compounds of silicon dioxide, alkoxy- or silicon. Preferably a form of silicone known as Cab-O-Sil is used.

Specific properties of the catalyst arise from the surface composition of the catalyst as measured by X-ray photoelectron spectroscopy surface analysis (ESCA). Lucchesi, E. A. et al., Jour, Chem. Ed. 50 (5): A 269 (May 1973) and Kelley, M. J., Chemtech, 99-105 (Feb, 1982). The term surface refers to the outermost layer of atoms and to a volume extending about 50 mm 3 below the outermost layer. ESCA measurements are the weighted average of the concentrations in these layers and the weights decrease logarithmically to the interior.

The atomic ratios of phosphorus, silicon, aluminum and oxygen are measured using a Hewlett packard 5950 A ESCA spectrometer.

The instrument alternately scans the band of target and oxygen 1s bands. This scan method takes into account linear standardization of all band intensities relative to oxygen 1s by correcting for a decrease in the sensitivity of the detector over the time needed to analyze the sample.

Relative intensity is corrected using the following response factor rather than the theoretical scofield cross section. These reaction factors are determined by correction using amorphous aluminum phosphate, alumina, silica, sodium hydrogen phosphate and aluminum phosphate and are similar to those shown in the literature [Wagner et al., Surf. Inter. Alal., 3, 211 (1981) and S. Evans et al., J. Electron Spectros. Rel. Phenom. 14, 341 (1978).

For each element (silicon, aluminum and phosphorus) the amount of element at the surface is calculated based on the intensity of both weighted 2s and 2p bands using the square root of the reaction factor for each of these bands. When the amount of each element is generally determined, the atomic ratio and mass ratio and molar ratio are easily calculated.

The observed change in each element concentration is about 10%. However, the ratio of elements can typically be measured more accurately within 5%.

The volume element measurement of silicon, aluminum, and phosphorus is performed using the following method. This method first melts a molecular sieve sample with lithium metaborate (LiBO ₂ ) and then dissolves the molten molten granules in nitric acid solution. The resulting solution is analyzed by inductively coupled plasma (ICP) using matrix-matched standards. Use Model 3580 ICP sold by the Melt Research Laboratory (ARL), California.

Analytical solutions are prepared by mixing 0.1 g of sample with 1.4 g of LiBO ₂ in a pre-ignited carbon crucible. This mixture is melted in a muffle incinerator at 1000 ° C. for 14 minutes. The crucible is immediately removed from the ash and the molten granules are poured into 60 ml of 4% v / v HNO ₃ acid solution in a polyethylene beaker in a uniform operation. After the molten salt is vibrated until dissolved, a 5 ppm scandium internal standard diluted from 1% concentrate purchased from the laboratory (VHG Laboratories, Andover, Massachusetts) is added. The resulting solution is diluted to 1 l.

By adjusting the sample mass to the percent loss of ignition (LOI), the sample mass is corrected and calculated for specific water and residue organisms. The dry crucible containing the mass of the known sample is heated at 1000 ° C. for 2 hours and then cooled to room temperature in a desiccator. The% LOI is calculated as follows.

Sample weight is corrected for% LOI.

Based on the modified sample mass, the weight percent of silicon, aluminum, and ligament ICP is based on the radix response of the sample compared to the correction curve for each element and dilution factor (total volume / modified sample mass) associated with each sample. Measure

The correction curve for each element is measured by making an aqueous correction standard (metrics-methodized) by the method described above for sample preparation except adding a sample. Instead, known amounts of aqueous Al, P and Si standards purchased from VHG are added just prior to dilution to 1 liter. Once the amount of each element is measured, the atomic ratio, mass ratio and molar ratio are easily calculated.

The SM-3 synthesized so far is on, tungsten, vanadium, molybdenum, rhenium, chromium, magnesium or Group VIII metals, preferably a metal component such as platinum or palladium by performing a hydrogenation-hydrocarbonation or oxidation function. It can be used as a catalyst which is directly bonded with. These components can be ion exchanged into the composition and can be impregnated into the composition or physically mixed with the composition directly. These components can be impregnated into the composition like platinum, for example by treating the crystals with a solution containing platinum metal-containing ions in the case of platinum. Suitable platinum compounds thus include various compounds containing chloroplatinic acid, platinum chloride and platinum amine complexes.

The cations or anions of SM-3 as organic ions, for example as synthesized, can be at least partially substituted by ion exchange with other cations or anions according to methods known in the art. Preferred substituted cations include metal ions, hydrogen i, hydrogen precursors such as ammonium ions and mixtures thereof. Particularly preferred cations include hydrogen rare earth metals and group IIA, IIIA, IVA, IB, IIB, IIIB, IVB, and VIB group metals of the periodic table.

A typical ion exchange technique is to contact the synthesized crystalline SM-3 with the salt of the desired substituted ion. Examples of salts of these cations include halide compounds (eg chlorides, nitrates and sulfur oxides).

In addition, the present SM-3 must be at least partially dehydrated when used as an adsorbent, an ion exchanger or as a catalyst in organic compound conversion. This can be done by heating to an inert atmosphere such as air or nitrogen and at a temperature in the range of 200 ° C. to 600 ° C. for 30 minutes to 48 hours at atmospheric pressure, atmospheric pressure below atmospheric pressure or above atmospheric pressure. Dehydration can also be carried out in vacuum only at room temperature but a longer time is required to obtain a sufficient amount of dehydrate. Therefore, it can be carried out by heating for 1 minute to 48 hours at a temperature of 200 ℃ to 1000 ℃ according to the range of dehydration or the desired heat treatment for SM-3.

The crystals of SM-3 prepared according to the present invention may have various particle sizes. Generally speaking, the particles may be in the form of particles, powders or molten products, such as extrudates having a particle size sufficient to pass through a two-mesh (tiler) screen and may be maintained on a 400-mesh (tyler) screen. When the composition is shaped as in extrusion, the crystals are dried or in particular extruded before drying.

For many catalysts it is desirable to incorporate SM-3 using the conditions used in other heat resistant and organic conversion methods. These materials include active and non-active materials and synthetic or natural zeolites as well as inorganic materials such as clay, silica and / or metal oxides. The latter may be in the form of gel precipitates or gels containing natural acids or mixtures of silica and metal oxides. The use of materials as conjugates of SM-3 with activity (i.e. associated with them) tends to increase the selectivity of the conversion and / or catalyst in any organic conversion process. Inactive materials are provided as diluents to control the amount of conversion in the provided method so that the product can be obtained economically without using other methods to control the reaction rate. These materials can be incorporated into natural clays (eg bentonite and kaolin) to increase the grinding strength of the catalyst under commercial operating conditions. The material (ie clay, oxide, etc.) functions as a binder for the catalyst. In commercial applications it is desirable to provide a catalyst having good grinding power since it is desirable to prevent the catalyst from being broken into a powdery material. These clay binders are generally used only for the purpose of improving the grinding power of the catalyst.

Natural clays that can be mixed with the new crystals include montmorillonite and kaolin and dixies, mcnames, georgia, and subbentonites, whose main minerals are halosite, kaolinite, dickite, oaklite or anauxite. Kaolin, also known as Florida clay, and the like. These clays may use raw or initial roasted, acid treated or chemical variants. Binders that can be used to mix with the present crystals also include inorganic oxides (usually alumina or silica).

In addition to the materials described above, the SM-3 produced is not only pore matrix materials such as aluminum phosphate, silica-alumina, silica-magnesia, silica-zirconia, silica-toria, silica-berilia, silica-titania, but also silica-alumina. It can be mixed with tertiary compositions such as -toria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The relative proportions of the finely divided crystalline SM-3 material and the inorganic oxide gel matrix can be changed to a crystal content in the range of 1 to 90% by weight when the mixture is prepared in the form of particles in the range of 2 to 80% by weight of the mixture. Can be.

According to the present invention, the prepared crystalline material can be easily converted into a material having catalytic activity for various organic compound (eg, hydrocarbon compound) conversion methods. SM-3 catalysts containing hydrogenated promoters can be used as a method of selectively producing intermediate distillate hydrocarbons by hydrogenation cracking hydrocarbonaceous feedstocks having a boiling point of at least 90% of the feedstock of at least about 600 ° F. Hydrogen cracking conditions generally include a reaction temperature of at least about 500 ° F (260 ° C.), usually at least about 600 ° F (316 ° C.) and preferably from 500 ° F (316 ° C.) to 900 ° F (482 ° C.). do.

The hydrogenation rate is above about 400 ° C. and is usually about 1000 to 15000 standard cubic feet per barrel. The reaction pressure is at least 200 psig (13.7 bar) and is usually in the range of about 500 to about 3000 psig (32.4 to 207 bar). The liquid hourly space velocity is less than about 15 and preferably about 0.2 to 10.

The conditions are chosen such that the total conversion rate is at least about 40% and preferably at least about 50% of the product of about 725 ° F (385 ° C.) and preferably at least about 300 ° F and less than about 725 ° F. Should be. The intermediate barrel selectivity should be such that the middle distillate range is at least about 40%, preferably at least about 50%, of the product and preferably is in the middle distillate range of about 720 ° F or less and about 300 ° F or more. The process may maintain at least about 50% inversion at a selectivity of at least 60% for intermediate distillate products boiling at 300 ° F. (149 ° C.) to 725 ° F. (385 ° C.). The pour point of the middle distillate effluent obtained by this process is about 0 ° F or less and preferably -20 ° F or less.

The process can be operated in a single stage hydrogenation process zone. It may also be the second stage of a two stage hydrogenation cracking process where nitrogen and sulfur are removed from the feedstock prior to contacting the intermediate distillation-producing catalyst in the first stage. The catalyst can also be used in the first stage of a multistage hydrogenation cracking process. In the work as the first step, the intermediate distillation-producing zone also denitrates and desulfurizes the high grade raw materials; In addition, it works more efficiently in the second stage using the same catalyst or conventional hydrocracking catalysts, allowing more intermediate distillation to be produced than in other process arrangements.

In the process of the present invention the hydrocarbon feedstock is heated with the catalyst under inverting conditions suitable for hydrocracking. Aromatic and naphthenic compounds present in the feedstock during the conversion undergo hydrogenation cracking reactions such as dealkylation, ring-opening, and cracking after hydrogenation. The long chain paraffins present in the feedstock produce a non-wax product of higher molecular weight than that obtained with the product obtained using prior art deleaving a zeolite catalyst such as ZSM-5 and at the same time cracking isomerization as described above. In addition to the reduced pour point due to the reaction, n-paraffins isomerize to isoparaffins to form a liquid range of material that provides a low viscosity (lower induction point) product.

Feedstocks for the process of the present invention include heavy hydrocarbon oils such as gas oil, coker top bottom fraction, reduced crude residue, vacuum bottom residue, deasphalted vacuum residue oil, FCC top bottom or cycle oil. do.

Oils derived from coal, shale or tar sands are also treated in this way. The present invention is also useful for oils having a low initial boiling point, such as 436 ° F (260 ° C.) but this type of oil is usually boiling above 600 ° F (316 ° C.) and most preferably about 90% of the feedstock. This boils at 700 ° F. (371 ° C.) to about 1200 ° F. (649 ° C.) or more. Preferably at least 90% of the feedstock may boil at about 600 ° F. (316 ° C.). These heavy oils include high molecular weight long chain paraffins and high molecular weight cyclic compounds having a high proportion of molten cyclic compounds. The molten cycloaromatic and naphthenic and paraffinic compounds in this process are degraded by SM-3 containing catalysts for middistillate range products. A substantial fraction of the paraffinic component of the initial feedstock is also converted to isoparaffins.

The present invention is particularly useful for very high paraffin feedstocks because of the greatest improvement in pour point using this kind of feedstock.

However, most feedstocks may contain specific amounts of polycyclic compounds.

The present invention more selectively converts a heavy feedstock, such as gas oil, boiling at about 600 ° F. into a medium distillate range product with improved pour point compared to prior methods using macroporous catalysts such as zeolite Y.

Hydrocracking catalysts contain an effective amount of one or more hydrogenation catalyst components of the type used in the hydrogenation cracking catalyst. The hydrogenation component is generally selected from the group of hydrogenation catalysts consisting of one or more Group VIB and Group VIII metals, which are generally included in salts, complexes and solutions containing them. The hydrogenation catalyst is preferably a metal, salt of a group consisting of one or more platinum, palladium, rhodium, iridium and mixtures thereof, or a group consisting of one or more nickel, molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof and salts thereof Selected from the group of complexes. Catalytically active metals include metals in elemental state or in the form of oxides, sulfides, halogens, carboxylates, and the like.

The hydrogenation catalyst is present in an effective amount to provide the hydrogenation function of the hydrogenation cracking catalyst and is preferably in the range of 0.05 to 25% by weight.

SM-3 may use a binder of any aluminosilicate used as a component in conventional hydrogenation catalysts, such as hydrogenation cracking catalysts.

Representatives of zeolite aluminosilicates that can be used as components of the hydrocracking catalysts disclosed so far include zeolite Y (including steam stabilized ones such as, for example, ultra-stable Y), zeolite X, zeolite beta (US) Patent 3,3,08,069), Zeolite ZK-20 (U.S. Patent 3,445,727), Zeolite ZSM-3 (U.S. Patent 3,415,736), Pausite, LZ-10 (June 9, 1982) US Patent No. 2,014,970), ZSM-5-form zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM35, ZSM-38, ZSM-48), crystals such as silicates St. silicate (US Pat. No. 4,061,724), erionite, mordenite, opretite, carbazite, Fu-1-form zeolite, NU-form zeolite, LZ-210-form zeolite and theirs Mixture. Conventional cracking catalysts containing an amount of Na ₂ O of less than about 1% by weight are generally preferred. An effective amount of SM-3 is used in all cases, although the relative amounts of XM-3 components and conventional hydrogenation cracking components depend at least in part on the hydrocarbon feedstock selected and on the desired product distribution. When using a conventional hydrocracking catalyst (THC) component, the relative weight ratio of THC to SM-3 is generally about 1: 10 to about 500: 1 and about 1: 10 to about 200: 1, preferably about 1: 2 to about 50: 1 and most preferably about 1: 1 to about 20: 1.

Hydrocracking catalysts include amorphous catalyst organic oxides (e.g., catalytically active silica-alumina, clay, silica, alumina, silica-alumina, silica-zirconia, silica-magnesia, alumina-boria, alumina-titania, and the like, and these Is used in conjunction with an inorganic oxide matrix component, which may be an inorganic oxide matrix component used in the formation of a hydrogenation cracking catalyst. Conventional hydrogenation cracking catalyst and SM-3 can be separately mixed with the matrix component and then mixed or prepared after mixing the THC component and SM-3 with the matrix component.

SM-3 is used in the process to degrease the hydrocarbonaceous feedstock. Catalytic dewaxing conditions generally depend on the feedstock used and on the desired pour point. Generally, the temperature may be about 200 ° C. to about 475 ° C., preferably about 250 ° C. to 450 ° C. The pressure is typically about 15 psig to about 3000 psig and is preferably about 200 psig to about 3000 psig. The liquid hourly space velocity (LHSV) may be between 0.1 and 20, preferably between 0.2 and 10.

Hydrogen is present in the reaction zone during the catalyst dewaxing process. The ratio of hydrogen to feedstock is typically from about 500 to about 30,000 SCF / bb 1 (standard stereofit per barrel) and preferably from about 1000 to about 20,000 SCF / bb 1. Hydrogen can generally be circulated in the reaction zone which can be separated from the product.

It has been found that the present invention selectively converts waxy n-paraffins to non-waxing paraffins. In-process waxy paraffins are subjected to a gentle cracking reaction to produce a higher molecular weight, non-waxing product compared to the product obtained using prior art zeolite catalysts. At the same time, isomerization occurs to reduce the pour point in the cracking reaction described above, as well as the n-paraffins to isomerize to isoparaffins to produce a liquid range material that provides a low viscosity and low flow point product.

Crude crude oil, reduced crude residue oil, vacuum tower residue oil, circulating oil, synthetic crude oil (eg, shale oil, tar sand oil, etc.), gas oil, vacuum gas oil, feedstock in a relatively light distillate using the present invention Various feedstocks can be degreased, ranging from high-boiling stocks such as oils and other heavy oils. Lighter oils are generally free of significant waxy components, so the feedstock may be a 10 ₁₀₊ feedstock that typically boils above about 350 ° F. However, the present invention is directed to the storage of waxy distillates such as gaseous oils, kerosene and jet fuels, intermediate distillate stocks containing lubricating oil stocks, which heat oils and other distillates where the pour point and viscosity need to be maintained within a certain range. Especially useful for water. Lubricant stocks generally boil at about 230 ° C. (450 ° F.) and more generally at about 350 ° C. (600 ° F.). Hydrogenated feedstocks, including those that have been hydrogenated and / or hydrocracked to lower metal, nitrogen and sulfur concentrations, are common sources of this type of feedstock and they generally produce significant amounts of waxy n-paraffins. It is a source of other distillates because it contains. The feedstock of the present invention may be a C ₁₀₊ feedstock comprising paraffins, olefins, naphthenes, aromatic and heterocyclic compounds and slightly branched chain paraffins which impart substantial proportions and wax properties of the feedstock in high molecular weight n-paraffins. have. In-process n-paraffins and slightly branched paraffins undergo a cracking or hydrogenation cracking to produce a liquid range material that provides a low viscosity product. However, the degree of cracking that can occur is limited to maintain the economic value of the feedstock as the gas yield is reduced.

Typical feedstocks include light gas oil, heavy gas oil and reduced crude oil boiling at about 350 ° F.

The process herein can be usefully performed when the feedstock contains organic nitrogen (nitrogen containing impurities) while the organic nitrogen content of the feedstock is less than 50 and more preferably less than 10 ppmW.

When used in the present invention, SM-3 is used in admixture with one or more Group VIII metals, such as precious metals such as platinum and palladium, and any other catalytically active metals such as molybdenum, vanadium, zinc, etc. do. The amount of metal is in the range of about 0.01% to 10% by weight of the molecular sieve and is preferably in the range of 0.2 to 5% by weight.

The Group VIII metal used in the process of the present invention may mean one or more metals in elemental form or in the form of sulfides or oxides and mixtures thereof. When referring to active metals as is common in the art of catalysis, it means that these metals are present in elemental form or in the form of oxides or sulfides as mentioned above, Regardless of the concentration present in the elemental state, the concentration can be calculated.

SM-3 silicoaluminophosphate molecular sieves may be mixed using other heat resistant materials and other conditions used in the dewaxing process. These matrix materials include clays, silica, alumina and metal oxides as well as active or non-active materials and synthetic or natural zeolites. Examples of zeolites include synthetic and natural faujasite (e.g. X and Y), erionite, mordenite and ZSM-based zeolites (e.g. ZSM-5). A combination of zeolites can also be mixed in the pore inorganic matrix.

SM-3 can be used in this process to prepare lubricants. The process comprises (a) hydrocracking a hydrocarbonaceous feedstock in a hydrocracking zone to produce an effluent containing hydrocracked oil; (b) catalytically dewaxing the hydrocracked oil of step (a) in a catalyst dewaxing zone using a catalyst containing crystalline silicoaluminophosphate SM-3 and a Group VIII metal, preferably platinum or palladium. It is characterized by.

Another aspect of the invention includes adding a catalytic hydrofinishing step to stabilize the dewaxed hydrocrackate.

Hydrocarbonic feedstocks from which lubricating oils have been prepared include aromatics as well as very long chain normal and branched paraffins. These feedstocks generally boil within the gas oil range. Preferred feedstocks are vacuum gas oils which generally boil in the range of 350 ° C. to 600 ° C. and deasphalted residue oil boils in the range of about 480 ° C. to 650 ° C. Reduced top crude oil, shale oil, liquefied coal, coke petroleum fraction, flask or pyrolysis oil, atmospheric residue oil and other heavy oils may also be used. The first step in the process diagram is the hydrocracking step. In commercial processes, hydrocracking can take place in a single step process or in a multistage process using well-known initial denitrification or desulfurization steps.

Typically hydrocracking conditions include temperatures ranging from 250 ° C. to 500 ° C., pressures ranging from about 400 to 15000 SCF / bbl of hydrogen in the range from about 425 to 3000 psig, and LHSV (v / v / hr) from 0.1 to 50.

At least 10% conversion occurs with the product boiling below 350 ° C. during the hydrocracking step. Catalysts used in hydrocracking zones include cracking carriers having hydrogenation-dehydrogenation activity. The carriers are sometimes silica-alumina, silica-alumina-zirconia and silica-alumina-titania compositions, acid-treated clays, crystalline aluminosilicate zeolite molecular sieves (zeolite A, pauzite, zeolite X and zeolite Such as light Y) and combinations of the above.

Hydrogenation-dehydrogenation components of hydrogenation cracking catalysts generally include metals selected from Groups VIII and VIBs of the periodic table and compounds containing them. Preferred Group VIII components include oxides and sulfides of cobalt, nickel, platinum and palladium and especially cobalt and nickel. Preferred Group VIB components are oxides and sulfides of molybdenum and tungsten. Thus, an example of a preferred hydrogenation cranking catalyst for use in the hydrogenation cranking step is a combination of nickel-tungsten-silica-alumina.

Particularly preferred hydrogenation cracking catalysts for use in the present invention are nickel sulfide / tungsten sulfide on silica-alumina bases comprising specific metal phosphate particles, which are described in US Pat. No. 3,493,517 and incorporated herein by reference.

The nitrogen component of the hydrocracked product is low enough to be consistent with economical purification processes but is preferably less than 50 ppm (w / w), more preferably less than about 10 ppm (w / w) and most preferably about 1 ppm (w / w) Is less than.

The hydrocracking step has two significant advantages. Firstly, the efficiency of the catalyst dewaxing step is increased and facilitated by lowering the nitrogen content. Secondly, the viscosity index increases significantly as the aromatic components present in the feedstock, in particular polycycle aromatics, are ring-opened and hydrogenated. An increase of at least 10 VI units in the hydrocracking stage may occur in the lubricating oil fraction (ie, oil boiling above 230 ° C.).

Preferably, the hydrocrackate is distilled by conventional methods and the product boiling at 230 ° C. or lower and more preferably at 315 ° C. or lower is removed to produce at least one lubricating oil boiling range airflow. Depending on the specific lubricating oil of interest, for example light lubricating oil, isolubricating oil or heavy lubricating oil, the dehydrogenated decomposition products can be distilled into light oil, kerosene oil or heavy oil. The low boiling product removed is a light nitrogen containing compound such as NH ₃ . This produces a lubricating organic stream with a reduced nitrogen concentration so that the SM-3 crystalline silicoaluminophosphate molecular sieve in the dewaxing catalyst reaches maximum activity in the dewaxing stage. Other boiling ranges of lubricating oil can be prepared by the process of the invention. This may include neutral, intermediate neutral, heavy natural acids and hard stocks and neutral oils are made from distillates and light stocks are made from residues.

The good efficiencies of the present invention result in extremely low nitrogen, high viscosity index deposits that are extremely de-leaded, resulting in very low pour points and increased viscosity and viscosity indexes from the combination of hydrocracking. It can be seen that the higher the activity of the dewaxing catalyst, the lower the reaction tower temperature required to achieve a specific degree of dewaxing. Significant advantages are therefore greater energy storage and generally longer cycle life from using improved efficiency catalysts. Furthermore, since SM-3 crystalline silicoaluminophosphate delead catalysts are morphologically selective, raw materials of alkyl-substituted cycloparaffins containing not only high kinetics (ie normal pallaffins) but also slightly branched paraffins and so-called microcrystalline waxes Preferentially react with components of the waxy feedstock.

When used in this process, SM-3 silica aluminophosphate is used with one or more of metals with precious metals such as platinum, palladium and optionally other catalytically active such as molybdenum, nickel, vanadium, cobalt, tungsten, zinc, and mixtures thereof. Preference is given to using in mixtures of. The amount of metal is from about 0.01% to about 10% by weight of the molecular sieve and preferably from 0.02 to 5% by weight.

The metal used in the process of the present invention may mean one or more metals in elemental form or in the form of sulfides or oxides and mixtures thereof. When referring to active metals as is common in the art of catalysis, it means that these metals are present in elemental form or in the form of oxides or sulfides as mentioned above, and where the metal components are present in the design Irrespective of the concentration, the concentration can be calculated if it is present in the elemental state.

The dewaxing step may be performed in the same reaction tower as the hydrocracking step, but is preferably performed in a separation reaction tower.

Catalyst loading conditions generally depend on the feedstock used and on the desired flow point. Generally the temperature is about 200 ° C to about 475 ° C and preferably about 250 ° C to 420 ° C. The pressure is typically about 15 psig to about 3000 psig and is preferably about 200 psig to about 3000 psig. The liquid hourly space velocity (LHSV) may be between 0.1 and 20, preferably between 0.2 and 10.

Hydrogen is present in the reaction zone during the catalytic dewaxing process. The ratio of hydrogen to feedstock is typically from about 500 to about 30,000 SCF / bb 1 (standard stereofit per barrel) and preferably from about 1000 to about 20,000 SCF / bb 1. In general, hydrogen can be separated from the product and circulated in the reaction zone.

The SM-3 crystalline silicoaluminophosphate catalyst used in the dewaxing step selectively converts the wax component into a non-wax component. In-process waxy paraffins undergo a mild cracking reaction to produce a higher molecular weight, non-waxing product compared to the product obtained using prior art zeolite catalysts. At the same time, isomerization takes place to reduce the pour point with the cracking reaction described above, as well as the n-paraffins to isomerize to isoparaffins to produce a liquid range material that provides a low viscosity and low flow point product.

SM-3 silicoaluminophosphate molecular sieves can be mixed using other heat resistant materials and other conditions used in the dewaxing process. These matrix materials include clays, silica, alumina and metal oxides as well as active and non-active materials and synthetic or natural zeolites. Examples of zeolites include synthetic and natural faujasite (e.g., X and Y), erionite, mordenite and ZSM-based zeolites (e.g., ZSM-5, etc.). A combination of zeolites can also be mixed in the pore inorganic matrix.

Preference is given to using mild hydrogenation (sometimes called a hydrogenation finishing process) to produce a more stable lubricant.

The hydrogenation finishing step may be carried out before or after the dewaxing step, preferably after the dewaxing step. The hydrogenation finishing step is typically performed at a temperature of about 190 ° C. to about 340 ° C., a pressure of about 400 psig to about 3000 psig, a space velocity (LHSV) of about 0.1 to 20 and a hydrogen circulation rate of 400 to about 1500 SCF / bb 1. The hydrogenation catalyst used should not only hydrogenate olefins, diolefins and colorants in the lubricating oil fraction, but also have sufficient activity to reduce aromatic components. The hydrofinishing step is advantageous in producing an acceptable and stable lubricating oil because lubricating oils prepared from hydrocracked stocks tend to be unstable and light in the air and form sludge spontaneously and quickly.

Suitable hydrogenation catalysts include conventional metal hydrogenation catalysts, in particular Group VIII metals such as cobalt, nickel, palladium and platinum. Metals are typically associated with carriers such as bauxite, alumina, cinchica gel, silica-alumina composition and crystalline aluminosilicate zeolite. Palladium is a particularly preferred metal hydride. Nonmetallic Group VIII metals can be used with molybdenum if necessary. Metal oxides or sulfides may be used. Suitable catalysts are described, for example, in US Pat. Nos. 3,852,207; 4,157,294; 3,904,153; And 4,673,487, all of which are incorporated herein by reference.

The inventive process is now illustrated in the Examples and is not intended to limit the invention as described herein, including the appended claims.

EXAMPLE

Example 1-5

Five SM-3s, having a volume SiO ₂ / Al ₂ O ₃ but having a different surface ratio of 0.375 ± 0.005, are prepared. They are prepared as follows:

Example 1

231.2 g of 85% H ₃ PO _{4 is added} to 118 g of distilled H ₂ O in a Teflon beaker using a beaker in an ice bath. Add 408.4 g of aluminum isopropoxide (Al [OC ₃ H ₇ ] ₃ ) slowly while mixing and mix until uniform. 38 g of fused silica (Cabosil M-5) in 168 g of distilled water are added while mixing. 91.2 g of di-n-propylamine (Pr ₂ NH) is then added and mixed using polytron. The mixture has a composition expressed as a pH of 6.0 and the molar ratio of oxides of the formula:

0.9 Pr ₂ NH: 0.6 SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 18H ₂ O

The mixture is placed in a Teflon bottle in a stainless steel pressurized container and heated to 200 ° C. for 5 days at spontaneous pressure without stirring. The supernatant is removed and the product is filtered, washed with water, dried overnight at 127 ° C. and roasted for 8 hours at 538 ° C. in air. The average crystallite size is less than 0.5 micron.

Example 2

462.4 g of 85% H ₃ PO _{4 is added} to 236 g of distilled water in a Teflon beaker using a beaker cooled in an ice bath. Add 816.8 g of Al (OC ₃ H ₇ ) ₃ slowly while mixing and mix until uniform. 120 g of Carbosyl HS-5 added to 480 g of distilled water are added while mixing and mixed for 15 minutes. 182.4 g of di-n-propylamine is then added and mixed for about 15 minutes. The mixture has a composition expressed in pH of 6.4 and molar ratio of the following oxides:

0.9 Pr ₂ NH: SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 22H ₂ O

The mixture is placed in a Teflon bottle in a stainless steel pressurized container and heated to 200 ° C. for 5 days at spontaneous pressure without stirring. The supernatant is removed and the product is filtered, washed with water, dried overnight at 127 ° C. and roasted for 8 hours at 538 ° C. in air. The average crystallite size is less than 0.5 micron.

Example 3

231.2 g of 85% H ₃ PO _{4 is added} to 238 g of distilled H ₂ O in a Teflon beaker using a beaker in an ice bath. Add 408.4 g of aluminum isopropoxide (Al [OC ₃ H ₇ ] ₃ ) slowly while mixing and mix until uniform. Add 60 g of Cabosil M-5 with mixing until homogeneous.

Then 91.2 g of di-n-propylamine (Pr ₂ NH) are added. Using acetic acid adjusts the pH of the mixture to 6.5. The mixture has a composition expressed in molar ratio of oxides of the formula:

0.9 Pr ₂ NH: SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 15H ₂ O

The mixture is placed in a Teflon bottle in a stainless steel pressurized container and heated to spontaneous pressure at 200 ° C. for 8 days without stirring. The supernatant is removed and the product is filtered, washed with water, dried overnight at 121 ° C. and roasted for 8 hours at 593 ° C. in air. The average crystallite size is less than 0.5 micron.

Example 4

472.4 g of 85% H ₃ PO _{4 is added} to 1208 g of distilled water in a Teflon beaker using a beaker cooled in an ice bath. Add 816.8 g of Al (OC ₃ H ₇ ) ₃ slowly while mixing and mix until uniform. Add 120 g of Carbosyl M-5 with mixing and mix for 15 minutes. Add 182.4 g of di-n-propylamine and mix for about 15 minutes. 9.6 g of 85% H ₃ PO _{4 is} then added with mixing. The mixture has a composition expressed in pH of 6.4 and molar ratio of the following oxides:

0.9 Pr ₂ NH: SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 36H ₂ O

The mixture is placed in a Teflon bottle in a stainless steel pressurized container and heated to 200 ° C. for 5 days at spontaneous pressure without stirring. The supernatant is removed and the product is filtered, washed with water, dried overnight at 121 ° C. and roasted for 8 hours at 566 ° C. in air. The average crystallite size is less than 0.5 micron.

Example 5

472.4 g of 85% H ₃ PO _{4 is added} to 1208 g of distilled water in a Teflon beaker using a beaker cooled in an ice bath. Add 816.8 g of Al (OC ₃ H ₇ ) ₃ slowly while mixing and mix until uniform. Add 120 g of Carbosyl M-5 with mixing and mix for 15 minutes. 182.4 g of di-n-propylamine is then added and mixed for about 15 minutes. 30 g of 85% H ₃ PO ₄ is added while mixing. The mixture has a composition expressed as a pH of 6.5 and the molar ratio of the following oxides:

0.9 Pr ₂ NH: SiO ₂ : Al ₂ O ₃ : 1.09P ₂ O ₅ : 36H ₂ O

The mixture is placed in a Teflon bottle in a stainless steel pressurized container and heated to 200 ° C. for 5 days at spontaneous pressure without stirring. The supernatant is removed and the product is filtered, washed with water, dried overnight at 121 ° C. and roasted for 8 hours at 566 ° C. in air. The average crystallite size is less than 0.5 micron.

X-ray diffraction patterns for each of Examples 1 to 5 as synthesized and roasted are described in US Pat. No. 4,440,871 with the properties of SAPO-11 as described in Tables I and II, respectively.

The molecular sieves of Examples 1 to 5 were impregnated with 1% by weight by a pore filling method using an aqueous solution of Pt (NH ₃ ) ₄ (NO ₃ ) ₂ . The molecular sieves are dried overnight at 121 ° C., roasted for 4 hours at 204 ° C. in air and for 4 hours at 454 ° C. They are then tested in the C ₈ activity test and performed as follows:

0.5 g of 24 × 42 mash catalyst is loaded using the remaining space filled with pickled and neutralized 24-mesh alundom in a 3/16 cognitive-ID stainless steel reaction column. The reaction tower is placed in a calm shell incinerator of a high pressure continuous flow pilot plant equipped with a Wheeler Packard 5880 gas chromatograph using sampling valves and capillary columns. The catalyst is tested at 1000 psig, 2.8 WHSV and 16H ₂ / HC using a feedstock consisting of 50/50 weight 2,2,4-trimethylpentane and n-octane. The column temperature was adjusted to provide 40% nC ₈ conversion.

The C ₈ activity test provides the same information as for the activity of the catalyst.

ESCA analysis of the molecular weights of Examples 1-5 prior to incorporation into platinum is given in Table III.

In addition, the results of activity tests on molecular sieves after incorporation and roasting with platinum are given in Table III.

TABLE III

ESCA analysis and C ₈ activity test

(1) molar ratio

Example 6-9

The preparations of the examples of Examples 6, 7, and 8 below are prepared in reaction mixtures having a molar composition represented by the following oxides:

0.9 Pr ₂ NH: 0.6 SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : bH ₂ O

In which b changes. The product SiO ₂ / Al ₂ O ₃ volume ratio is 0.20 ± 0.02. Example 9 below is consistent with US Pat. No. 4,440,877.

Example 6

115.6 g of 85% H ₃ PO _{4 is added} to 59 g of distilled H ₂ O in a Teflon beaker using a beaker in an ice bath. Slowly add 204.2 g of Al [OC ₃ H ₇ ] ₃ while mixing and mix until uniform. 19 g of Cabosil M-5 in 42 g of distilled water are added while mixing. 45.6 g of di-n-propylamine (Pr ₂ NH) is added and then mixed using polytron. The mixture has a pH of 6.0 and a H ₂ O / Al ₂ O ₃ molar ratio of 13. The mixture is placed in a Teflon bottle in a stainless steel pressurized vessel and heated to 200 ° C. for 5 days at spontaneous pressure without stirring. The supernatant is removed and the product is filtered, washed with water, dried overnight at 121 ° C. and roasted for 8 hours at 538 ° C. in air. The average crystallite size is less than 0.5 micron.

Example 7

SM-3 was prepared as in Example 6, but sufficient distilled water was added to H ₃ PO ₄ to bring the molar ratio of the mixture H ₂ O / Al ₂ O ₃ to 33 or less. The pH of the reaction mixture is 6.1. The average crystal size is about 0.5 microns.

Comparative Example 8

A molecular sieve is prepared as in Example 6 but sufficient distilled water is added to H ₃ PO ₄ to bring the mixture to a H ₂ O / Al ₂ O ₃ molar ratio of 62 or less and outside the scope of the present invention. The pH of the reaction mixture (9.5) is reduced to 6.5 by adding concentrated HCl. Average crystal size is in the range of 0.5 micron.

Comparative Example 9

SAPO-11 silicoaluminophosphate is prepared according to the following method of Example 17 of US Pat. No. 4,440,871 using two quantifications of material as described herein. The reaction mixture pH is 10.7. The average crystal size is less than about 1 micron. As synthesized and roasted, the X-ray diffraction patterns for each of Examples 6-9 are characteristic of SAPO-11 as described in Table I and Table II, respectively, and are included in US Pat. No. 4,440,871.

The molecular sieves of Examples 6-9 are combined and roasted with platinum as in Examples 1-5.

ESCA molecular sieve analysis for Examples 6-9 prior to incorporation into platinum is given in Table IV. The activity test data for the molecular sieves of Examples 6-9 after incorporation and roasting with platinum are also given in Table IV.

Table IV

ESCA analysis and C ₈ activity test

(1) molar ratio

(2) 24 Methanol / Al ₂ O _{3 added}

The molecular sieves of Examples 6 and 7 which fall within the scope of the present invention in terms of P ₂ O ₅ / Al ₂ O ₃ molar ratio and SiO ₂ / Al ₂ O ₃ molar ratio in volume and at the surface are outside of the scope of the present invention in Example 8 And improved activity compared to 9.

Claims (63)

P ₂ O ₅ to alumina molar ratio of 0.80 or less on the surface of the silicoaluminophosphate, having a specific X-ray powder diffraction pattern including at least the d-spacing of Table 1, and the volume of P ₂ O ₅ of the silicoaluminophosphate A crystalline silicoaluminophosphate molecular sieve having a molar ratio of to alumina greater than or equal to 0.96 and a greater SiO ₂ to alumina molar ratio on the surface of the silicoaluminophosphate than in the volume. It has a composition represented by the following proportional formula by the molar ratio of oxide based on anhydride, and has a unique X-ray powder diffraction form including at least the d-spacings of Table I, and the surface ratio of P ₂ O ₅ to alumina is 0.80. or less, and the P ₂ O ₅ to alumina mole ratio of at least 0.96 volume, the SiO ₂ to alumina mole ratio at the surface more than a crystalline silico-alumina molar ratio SiO ₂ in the volume of aluminum phosphate molecular sieve aged: mR: Al ₂ O ₃ : nP ₂ O ₅ : qSiO ₂ Wherein R represents at least one organic template present in the internal crystalline pore system; m represents the number of moles of R present and has a value that allows 0.02 to 2 moles of R per mole of aluminum; n has a value between 0.96 and 1.1; q has a value from 0.1 to 4. The compound of claim 2, wherein m has a value of 0.4 to 1.5; n has a value between 96 and 1; A crystalline silicoaluminophosphate molecular sieve, wherein q has a value between 0.1 and 1. 4. The crystalline silicoaluminophosphate molecular sieve according to claim 2 or 3, wherein the organic template is selected from the group consisting of di-n-propylamine and diisopropylamine or mixtures thereof. 4. The crystalline silicoaluminophosphate powder according to claim 2 or 3, wherein the molar ratio of P ₂ O ₅ to alumina at the surface is in the range of 0.80 to 0.55 and the molar ratio of P ₂ O ₅ to alumina in the volume is in the range of 0.96 to 1. itself. A crystalline silicoaluminophosphate molecular sieve produced from the heat treatment of the silicoaluminophosphate of claim 1. A crystalline silicoaluminophosphate molecular sieve produced from the heat treatment of the silicoaluminophosphate of claim 2. The Sicco aluminophosphate molecular sieve produced from the heat treatment of the silicoaluminophosphate of Claim 3. 7. The crystalline silicoaluminophosphate molecular sieve having the specific X-ray powder diffraction form given in Table II. 8. The crystalline silicoaluminophosphate molecular sieve according to claim 7, further comprising a rare earth metal, a Group IIA metal, a Group VI or Group VIII metal. 8. The crystalline silicoaluminophosphate molecular sieve according to claim 7, which is ion-exchanged with hydrogen, aluminum, rare earth metals, group IIA metals, group VI or group VIII metal ions. 8. The crystalline silicoaluminophosphate molecular sieve according to claim 7, wherein the rare earth metal, the Group IIA metal, the Group VI or the Group VIII metal is adsorbed in the silicoaluminophosphate. 8. The crystalline silicoaluminophosphate molecular sieve according to claim 7, wherein the rare earth metal, the Group IIA metal, the Group VI or the Group VIII metal is impregnated in the silicoaluminophosphate. A silicoaluminophosphate composition comprising the silicoaluminophosphate of claim 1, 2, 3, 5, 7, or 8 and an inorganic matrix. (a) combining the alumina and phosphorus sources in the substantial absence of a silicon source and then combining the resulting mixture with a silicon source and then blending the mixture with an organic template to produce a reactive source of SiO ₂ , aluminum isopropoxide, Preparing a complete aqueous reaction mixture containing phosphoric acid and an organic template and having a composition expressed by the molar ratio of oxides of the following proportional formula; (b) adjusting the pH of the reaction mixture to 6.0 to 8.5; (c) heating the reaction mixture to a temperature in the range of 170 ° C. to 240 ° C. until crystals of silicoaluminophosphate are formed; (d) recovering the crystals; Process for preparing the crystalline silicoaluminophosphate according to claim 1: aR: Al ₂ O ₃ : 0.9-1.2 P ₂ O ₅ : 0.1-4.0 SiO ₂ : bH ₂ O Wherein R is an organic template; a has a value large enough to constitute an effective amount of R, b has a value that allows for the presence of 10 to 40 moles of H ₂ O per mole of aluminum oxide. The method of claim 15, wherein b has a value capable of allowing 15 to 36 moles of H ₂ O per mole of alumina. 16. The method of claim 15, wherein a has a value such that 0.2 to 2 moles of R per mole of alumina are present. The method of claim 15, wherein a has a value such that 0.8 to 1.2 moles of R per mole of alumina are present. The method of claim 15, wherein the organic template is selected from the group consisting of di-n-propylamine and diisopropylamine or mixtures thereof. The method of claim 15, wherein the organic template is di-n-propylamine. The method of claim 15 wherein the pH is in the range of 6.0 to 8.0. The method of claim 15, wherein the crystal size of the recovered crystal is less than 1 micron. 16. The method of claim 15, wherein the average crystal size of the recovered crystals is less than 0.5 microns. The method of claim 15, wherein the temperature is in the range of 200 ° C. to 225 ° C. 16. A process for converting hydrocarbons, characterized by contacting the hydrocarbonaceous feedstock with the crystalline silicoaluminophosphate dispersion of claim 1 under hydrocarbon conversion conditions. 26. The crystalline silicoaluminophosphate molecular sieve according to claim 1 and (a) a hydrocarbonaceous feedstock having a boiling point of at least 90% of the feedstock having a boiling point of at least 600 ° F. (315.6 ° C.) under hydrogenation cracking conditions. Contacting with a catalyst containing the above hydrogenated reactive component; (b) recovery of hydrocarbonaceous effluents having a effluent of at least 40% by volume boiling above 300 ° F (148.8 ° C) to below 725 ° F (385 ° C) and having a pour point below 0 ° F (-17.8 ° C) Wherein the hydrocarbonaceous feedstock is hydrocracked and isomerized to selectively produce a middle distillate hydrocarbon. 27. The method of claim 26, wherein the hydrogenated reactive component is platinum. 27. The method of claim 26, wherein the hydrogenated reactive component is palladium. 27. The method of claim 26, wherein the hydrogenated reactive component is present in the range of 0.01% to 10% by weight based on the weight of the molecular sieve. 27. The method of claim 26, to a temperature of 260 ℃ 482 ℃, 200psig to pressure 3,000psig, 0.1hr ^-1 to the process is carried out at a liquid hourly space velocity and 400 to 15,000SCF / bb1 hydrogen circulation rate of the 20hr ^-1. 27. The method of claim 26, wherein the catalyst further contains an inorganic oxide matrix. 27. The method of claim 26, wherein the matrix is alumina. 27. The method of claim 26, wherein the catalyst further contains a nickel, cobalt, molybdenum or tungsten component or mixtures thereof. 27. The method of claim 26, wherein the feedstock is gas oil. 27. The method of claim 26, wherein the feedstock contains up to 10 ppmw of nitrogen-containing impurities, calculated in nitrogen. 27. The process of claim 26, wherein the hydrocarbon feedstock is selected from the group consisting of crude distillates, solvent deasphalted residues, and sail oils. 27. The method of claim 26, wherein at least 50% by weight of the converted product boils below 300 ° F (148.8 ° C) to 725 ° F (385 ° C). 27. The process of claim 26, wherein the catalyst is treated in a lower stream of the reaction zone where the hydrocarbon feedstock is contacted with hydrogen and a hydrodenitrification catalyst that is active under process conditions. 39. The process of claim 38, wherein the hydrodenitrification catalyst is treated with a catalyst in a single reaction tower. 26. The crystalline silicoaluminophosphate molecular sieve according to claim 1 and at least one Group VIII metal according to claim 25, comprising a hydrocarbon oil feedstock containing hydrocarbons which are boiled at least at 350 ° F. (176.7 ° C.) and containing straight and slightly branched hydrocarbons. And catalytically dewaxing the hydrocarbon oil feedstock, characterized in that it is contacted with a catalyst containing. 41. The method of claim 40, wherein the Group VIII metal is selected from the group consisting of platinum and palladium. 42. The method of claim 41 wherein the metal is platinum. 41. The method of claim 40, wherein the Group VIII metal is present in the range of 0.01% to 10% by weight of the molecular sieve. 41. The method of claim 40, to a temperature of 200 ℃ 475 ℃, 15psig to pressure 3,000psig, 0.1hr ^-1 to the process is carried out at a liquid hourly space velocity and 500 to 30,000SCF / bb1 hydrogen circulation rate of the 20hr ^-1. 41. The method of claim 40, wherein the feedstock is a middle distillate oil. 41. The method of claim 40, wherein the feedstock is lubricating oil. 41. The method of claim 40, wherein the feedstock contains less than 50 ppm nitrogen. 41. The method of claim 40, wherein the feedstock contains less than 10 ppm nitrogen. (a) hydrocracking the hydrocarbonaceous feedstock in the hydrocracking zone to obtain an effluent containing the hydrocracked oil; (b) catalytically dewaxing the hydrogenated cracked oil in the catalytic dewaxing zone using a catalyst containing the crystalline silicoaluminophosphate molecular sieve according to claim 1 and one Group VIII metal. How to prepare. The method of claim 49, wherein the metal is platinum or palladium. 50. The process of claim 49, wherein the hydrogenated cracked oil to be deleased contains less than 50 ppm by weight of nitrogen. 50. The process of claim 49, wherein the hydrogenated cracked oil to be deleased contains less than 10 ppm by weight of nitrogen. The method of claim 49, wherein the metal is present in the range of 0.01% to 10% by weight of the molecular sieve. The process of claim 49 wherein the hydrocracking step is carried out at a temperature of 250 ° C. to 500 ° C., a pressure of 425 psig to 3,000 psig, a liquid hourly space velocity of 0.1 hr ⁻¹ to 50 hr ⁻¹ and a hydrogen circulation rate of 400 to 15,000 CF / bb 1. How is it done. 50. The method of claim 49 wherein the dewaxing step is to a temperature of 200 ℃ ℃ 457, to a pressure of 15psig 3,000psig, performed at 0.1hr ^-1 to 20hr ^-1, and a liquid hourly space velocity of 500 to 30,000CF / bb1 hydrogen circulation rate of the How to be. 50. The process of claim 49, wherein the de-leaded product is further hydrogenated on a hydrogenation catalyst under hydrogenation conditions. The method of claim 1, wherein on the surface P ₂ O ₅ and dae alumina mole ratio in the range of 0.80 to 0.55 volumes of P ₂ O ₅ to alumina mole ratio is determined in the range of 0.96 to 1 St. silico alumino phosphate molecular sieve aged. 8. The crystalline silicoaluminophosphate molecular sieve according to claim 7, having a specific X-ray powder diffraction form given in Table II. 9. The crystalline silicoaluminophosphate molecular sieve according to claim 8, having a specific X-ray powder diffraction form given in Table II. 9. The crystalline silicoaluminophosphate molecular sieve according to claim 8, further comprising a rare earth metal, a Group IIA metal, a Group VI, or a Group VIII metal. 9. The crystalline silicoaluminophosphate molecular sieve according to claim 8, which is ion exchanged with hydrogen, ammonium, rare earth metals, group IIA metals, group VI or group VIII metal ions. 9. The crystalline silicoaluminophosphate molecular sieve according to claim 8, wherein the rare earth metal, the Group IIA metal, the Group VI or the Group VIII metal is adsorbed in the silicoaluminophosphate. 9. The crystalline silicoaluminophosphate molecular sieve according to claim 8, wherein the rare earth metal, the Group II, the metal, the Group VI or the Group VIII metal is impregnated in the silicoaluminophosphate.