JP3045541B2 - Synthesis of crystalline silicoaluminophosphate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a crystalline silicoaluminophosphate molecular sieve and its synthesis. The invention is particularly applicable to bulk P ₂ O ₅ / Al ₂
O ₃ molar ratio and the body SiO ₂ / Al ₂ O ₃ molar ratio, their corresponding surface _{P 2 O 5 / Al 2 O} 3 and the surface SiO ₂ / Al ₂ O ₃ molar ratio crystalline differs from the silicoaluminophosphate It relates to the synthesis of phosphate molecular sieves.

(Background technology)

Silicoaluminophosphates are described, for example, in U.S. Pat.
In the specification. Silicoaluminophosphate materials are both microporous and crystalline, with PO ₂ ⁺ , AlO ₂ ^- and S
having a three-dimensional crystal skeleton structure composed of iO ₂ tetrahedral units,
It has the following as-synthesized experimental chemical composition on an anhydrous basis, excluding any optionally present alkali metals or other cations: mR: (Si _x Al _y P _z ) O ₂ , wherein “ "R" stands for intracrystalline porosity
esystem) represents at least one organic templating agent; "m" stands for (Si _x Al _y
P _z ) represents the number of moles of “R” present per mole of O ₂ ,
Having a value of ~ 0.3, the maximum value in each case depending on the molecular size of the template agent and the effective pore volume of the pore system of the particular silicoaluminophosphate material involved; "x",
"Y" and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides]. The minimum value of each of "x", "y" and "z" is 0.01, preferably 0.02. The maximum value of “x” is 0.98, the maximum value of “y” is 0.60, and the maximum value of “z” is 0.52.

U.S. Pat. No. 4,440,871 discloses that although not essential for the synthesis of SAPO compositions, generally the stirring of the reaction mixture or other gentle stirring and / or alumino of the SAPO material or similar crystalline form to be produced It is disclosed that placing seed crystals of the phosphate or aluminophosphate composition into the reaction mixture facilitates the crystallization process. These silicoaluminophosphates exhibit some physical and chemical properties characteristic of aluminosilicate zeolites and aluminophosphates.

Silicoaluminophosphate SAPO-11 and its conventional method of manufacture are taught in U.S. Pat. No. 4,440,871.

(Summary of the present invention)

The present invention relates to a novel synthetic crystalline silicoaluminophosphate molecular sieve, hereinafter designated as SM-3. In general, SM-3 silicoaluminophosphate has a different concentration of phosphorus, silicon, and aluminum in the main molecular sieve from phosphorus, silicon,
And having an aluminum concentration and having an essential X-ray diffraction image of SAPO-11, can be characterized as distinct from all other silicoaluminophosphate forms.

In particular, the present invention relates to as-synthesized crystalline silicoaluminophosphate molecular sieves having the following formula in molar ratio of oxides on an anhydrous basis: mR: Al ₂ O ₃ : nP ₂ O ₅ : qSiO ₂ (1) [wherein, “R” represents at least one organic template agent present in the intracrystalline pore system; “m” represents the number of moles of “R” present;
Has a value such that ２2 moles of R are present; n is 0.96-1.1.
Wherein q has a value of 0.1 to 4, and the silicoaluminophosphate has a characteristic powder X-ray diffraction image including at least the d interval shown in Table I, and P ₂ O on the surface of the silicoaluminophosphate. _Five
Alumina mole ratio is about 0.80 or less, P ₂ O ₅ to alumina mole ratio of the main body of the silicoaluminophosphate salt is about 0.96 or more, SiO ₂ to alumina mole ratio of the surface of the silicoaluminophosphate salt, SiO body of silicoaluminophosphate salt Greater than the ₂ to alumina molar ratio].

Synthesis of SM-3 crystalline silicoaluminophosphate salt also given, the method comprising, (a) SiO ₂ reactive sources, to prepare the aluminum isopropoxide, phosphoric acid, and the aqueous reaction mixture containing an organic template agent, the The reaction mixture is expressed as a molar ratio of oxides and has the following composition: aR: Al ₂ O ₃ : 0.9-1.2P ₂ O ₅ : 0.1-4.0SiO ₂ : bH ₂ O (where R is an organic template agent) "A" has a value large enough to constitute an effective amount of R, preferably such that there is between 0.20 and 2 moles of R per mole of aluminum oxide; b "has a] values such that there are of H ₂ O aluminum oxide per mole 10 to 40 mol, the reaction mixture is combined alumina and phosphorus source the silicon source without substantially present The resulting mixture is then sequentially combined with a silicon source and an organic templating agent. And
(B) adjusting the pH of the reaction mixture to about 6.0-8.5, (c) bringing the reaction mixture to a temperature in the range of 170-240 ° C., the silicoaluminophosphate Heating until the formation of the crystals, and (d) recovering the crystals.

The present invention is based on the discovery that, among various factors, by controlling the reaction conditions, a novel silicoaluminophosphate molecular sieve having a body composition different from the surface composition can be formed. By controlling the distribution and location of silicon on the surface of the silicoaluminophosphate, the activity of the silicoaluminophosphate as a catalyst is increased while maintaining its selectivity.

[Brief description of drawings]

FIG. 1 is a ternary chart showing the composition parameters of the silicoaluminophosphate of the present invention expressed in terms of mole fractions of silicon, aluminum and phosphorus.

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

(Detailed description of the present invention)

The silicoaluminophosphate materials of the present invention exhibit unique and useful catalytic and shape selectivity. The activity is determined by comparing the temperatures at which different catalysts must be used under constant reaction conditions other than temperature using the same hydrocarbonaceous feedstock and the same product conversion rate. The lower the reaction temperature for a given degree of reaction, the greater the activity of the catalyst for that particular step. SAPO-11 type silicoaluminophosphate of the present invention is a silicoaluminophosphate,
Shows superior activity compared to SAPO-11 produced by conventional methods as taught in U.S. Pat.No. 4,440,871, while at the same time improving or improving on the known SAPO-11 silicoaluminophosphate Has a favorable selectivity.
Selectivity is a measure of the yield of the desired product.

The novel SM-3 silicoaluminophosphate, as synthesized, has a crystal structure whose powder X-ray diffraction image shows the following characteristic lines.

X-ray powder diffraction images were determined by standard methods. The radiation was copper _Kα / double wire, using a scintillation counter spectrometer equipped with a pen recorder with strip recording paper. From the spectrometer recording paper, the peak heights I and their locations were read as a function of 2θ, with θ as the Bragg angle. The relative intensity I ₀ from the measured values as the intensity of the strongest line peak 100I
The plane spacing d (Å) corresponding to / I ₀ and the recorded line was calculated. The X-ray diffraction images in Table I are characteristic of the novel SM-3 silicoaluminophosphate and are described in US Pat. No. 4,440,871.
X-ray diffraction image of SAPO-11, as described in the specification (the description of which is incorporated herein by reference in its entirety).

After calculation, SM-3 silicoaluminophosphate is converted to powder X
It has a crystal structure whose X-ray diffraction image shows characteristic lines as shown in Table II below: SM-3 silicoaluminophosphate salt molecule sieve, while synthesized, [SiO _2], characterized as having a [AlO _2], and [PO _2] three-dimensional microporous crystal framework structure of tetrahedral units, It has the composition represented by the following formula, expressed as a molar ratio of oxides on an anhydrous basis: mR: Al ₂ O ₃ : nP ₂ O ₅ : qSiO ₂ (1) wherein “R” is a crystal Represents at least one organic templating agent present in the inner pore system (hereinafter referred to as "template");"m" represents the number of moles of "R" present, 0.02 to 2 moles of R per mole of alumina Has a value such that is present; n is between 0.96 and 1.1, preferably 0.96
And q has a value of 0.1 to 4, preferably 0.1 to 1].

The SM-3 silicoaluminophosphate molecular sieve, as synthesized, can also be represented by its unit empirical formula. On an anhydrous basis,
It is represented by the following _{formula: mR: (Si x Al y} P z) O 2 (II) wherein, R and m are as defined above; "x",
"Y" and "z" represent the mole fractions of silicon, aluminum, and phosphorus, respectively, present as tetrahedral oxide units]. The mole fraction is within the rectangular composition range defined by points A, B, C, and D of the ternary composition diagram depicted in FIG. 1 of the drawing, where points A, B, C, And D are represented by the following values for "x", "y", and "z": As a preferred embodiment, “x” in the above formula (II),
The values for "y" and "z" are within the square composition range defined by points a, b, c, and d in the ternary chart of FIG. 2, where points a, b, c, and d are represented by the following values for "x", "y", and "z": SM-3 silicoaluminophosphate salts of the present invention further P ₂ O ₅ to alumina mole ratio of the surface of the silicoaluminophosphate salt about 0.80
Or less, preferably in the range of from 0.80 to 0.55, P ₂ O ₅ to alumina mole ratio of the main body of the silicoaluminophosphate salt 0.96
Or more, preferably in the most preferably from 0.96 to 1 in the range of .96-1.1, SiO ₂ to alumina mole ratio of the surface of the silicoaluminophosphate salt, from SiO ₂ to alumina mole ratio in the body of the silicoaluminophosphate salt Is also large.

In the molecular sieves of the present invention, the silicon content is greater than in the main body of the molecular sieve, as evidenced by the silica to alumina molar ratio on the surface of the silicoaluminophosphate.

The term "silicon content on the surface of the molecular sieve" means the amount of silicon on the surface of the sample that can be measured using X-ray photoelectron spectroscopy surface analysis (ESCA). This silicon content will include the amorphous silica present. The silicon content of the molecular sieve of the present invention is greater at the surface than in the body. For this comparison, the silica content itself may be compared, or the silica / alumina ratio may be compared.

As used herein, the term "unit empirical formula", according to its general meaning, refers to [P] in a silicoaluminophosphate molecular sieve.
O ₂ ], [AlO ₂ ], and [SiO ₂ ] to form tetrahedral units, SM
The relative number of silicon, aluminum, and phosphorus atoms that form a molecular skeletal structure having a −3 composition indicates the simplest formula. The unit empirical formula is given for silicon, aluminum and phosphorus as shown in the above formula (II), and as a result of its production or as the presence of other impurities or materials, the tetrahedral unit cell of the molecular framework structure is It does not contain other compounds, cations or anions which may be present in the body composition without it. The amount of template R is part of the composition given the as-synthesized unit empirical formula, and water may also be reported unless it is defined as an anhydrous form. For simplicity, the coefficient "m" for the template "R" is reported as a value normalized by dividing the number of moles of R by the total number of moles of alumina. When reporting the number of moles of water, the number of moles of water is reported as a value normalized by dividing the number of moles of water by the total number of moles of alumina. The values for x, y, and z are
It is determined by dividing the moles of silicon, aluminum and phosphorus by the total moles of silicon, aluminum and phosphorus, respectively.

The formula (I) and unit empirical formula (II) compositions for SM-3 silicoaluminophosphate are given on an "as-synthesized" basis or as "as-synthesized"
The SM-3 composition is provided after some post-processing steps, such as calcination. As used herein, the term "as-synthesized" refers to an SM-3 composition formed as a result of hydrothermal crystallization, prior to being subjected to a post-treatment to remove volatile components present therein. Will be used to refer to the SM-3 composition.

The actual value of "m" for post-treated SM-3 depends on several factors (template, severity of post-processing with respect to ability to remove template from SM-3, proposed use of SM-3 composition). Etc.). Post-processed SM
The amount of template for -3 was calculated as SM
-3 is within the range of values defined for the composition, but is generally less. The calcined or other post-treated form of the SM-3 composition generally has a composition represented by an empirical formula represented by Formula (I) or Formula (II), except that "m Values are generally in the range of 0 to 0.3 moles of template per mole of alumina, most preferably 0 to 0.1 moles.
And is generally less than about 0.02. Under sufficiently severe post-treatment conditions, such as roasting at a high temperature in air for a long time (1 hour or more), the value of “m” may be 0, or anyway, the template, R, may not be used in ordinary analysis methods. Not detectable.

When synthesizing the SM-3 composition of the present invention, the reaction mixture is preferably essentially free of alkali metal cations, and therefore the preferred reaction mixture composition, expressed in terms of oxide molar ratio, is as follows: : AR: Al ₂ O ₃ : 0.9-1.2P ₂ O ₅ : 0.1-4.0 SiO ₂ : bH ₂ O (where “R” is an organic template agent; “a” is an effective concentration of “R” "B" has a value large enough to constitute "a", preferably 0.20 to 2 moles, more preferably about 0.8 to 1.2 moles of R per mole of alumina; Is 10 per mole of aluminum oxide
4040 mol, preferably 15-36 mol of H ₂ O are present].

In the synthesis method of the present invention, the reactive aluminum and phosphorus sources are combined substantially without the presence of a silicon source, and then
The resulting reaction mixture containing the aluminum and phosphorus sources is formed by combining the silicon source, and then combining the mixture with the template. If alkali metal cations are present in the reaction mixture, they are SM-
3 Should be present at a low enough concentration to not interfere with the formation of the composition.

The inorganic cations and anions that may be present in the reaction mixture are generally not provided by separately added components. Rather, these cations and anions will often come from the silicon source or other essential components, such as an organic templating agent, or compounds added to the reaction mixture to provide a pH modifier that may be used. .

In particular, the synthetic method comprises: (a) preparing an aqueous reaction mixture comprising aluminum isopropoxide and phosphoric acid, then combining the resulting mixture with a silicon oxide source, and then combining the mixture with an organic templating agent. (B) at the start of the reaction, to raise the pH of the reaction mixture to about 6.0-8.5,
(C) adjusting the reaction mixture to 170 ° C to 240 ° C, preferably 180 ° C.
Heating to a temperature in the range of 225225 ° C. until the formation of crystals, usually for 5 hours to 500 hours, preferably for 24 to 500 hours, and (d) recovering the crystalline SM-3 silicoaluminophosphate Become.

The crystallization is carried out under hydrothermal conditions under pressure, usually in an autoclave in which the reaction mixture is subjected to spontaneous pressure, preferably without stirring. Following crystallization of the SM-3 material, the reaction mixture containing it is passed, and the recovered crystals are washed, for example, with water, and then dried, such as by heating to 25 ° C to 150 ° C at atmospheric pressure. . The supernatant on the crystal is preferably removed before the first pass of the crystal.

The SM-3 produced by this method is advantageously subjected to a heat treatment to remove the organic template. This heat treatment is generally performed at room temperature between 300 ° C. and 1000 ° C. for at least one hour.
It is carried out by heating for minutes, generally not more than 20 hours. Reduced pressure can be used for the heat treatment, but atmospheric pressure is preferred for convenience. The heat-treated product is particularly useful as a catalyst for certain hydrocarbon conversion reactions.

By thoroughly mixing the aluminum and phosphorus components, and finally adding the silicon component, a high-purity SM-3 type substance can be obtained.

SM-3 silicoaluminophosphate salt is from about 6.0 to about 8.5, preferably at low pH in the range of 6.0 to 8.0, about 10 to 40, are preferably manufactured in H ₂ O / Al ₂ O ₃ molar ratio of 15 to 36 You. Under these conditions, SiO ₂ depolymerization is slow and nucleation is fast. Crystallization under the reaction conditions of the present invention is generally completed in less than 5 hours.

Since Without being limited by theory, under the conditions of the process of the present invention, approximately aluminophosphate phase surrounded by amorphous phase rich in SiO ₂ is produced in the initial stage of the reaction, after crystallization SiO ₂ until towards the seem to not enter into the structure. The pH of the mixture rises to about 10 to about 10.5 as PO ₄ ^-3 becomes depleted by reaction with Al ⁺³ . This is as a silica to increase the solubility of SiO ₂ is incorporated into the structure, the shell of the silicoaluminophosphate salt is formed around the aluminophosphate core. From a macro perspective,
The molecular sieve could be considered almost crystalline aluminophosphate. This is because the molar ratio of P ₂ O ₅ to alumina in the main body of the SM-3 silicoaluminophosphate is 0.96 or more, preferably 0.96 to 1.

The silica-rich surface phase on the outside of the molecular sieve has a higher SiO ₂ / alumina ratio than the body. Materials with a large surface silica to alumina ratio appear to exhibit increased acidity and increased activity.

By adjusting the pH and H ₂ O / Al ₂ O ₃ ratio of the mixture, it is possible to adjust the thickness of the SM-3 shell. For example,
One way to reduce its thickness is to add additional H ₃ to the mixture.
PO ₄ is added. This keeps the final pH low, that is, controls the acidity, so that no Si is taken up until the end of the synthesis.

If necessary, it is possible to lower the pH within the proper range using acid such as HCl or H ₃ PO _4. The latter will be preferred. This is because having a slight excess of PO ₄ ^-3 helps to ensure that the concentration of PO ₄ ^-3 is never so low that the components of alumina and silica do not react with each other. is there.

Excess water beyond the stated range tends to lead to rapid incorporation of silica into the product. Excess water also results in larger crystals, which can reduce activity due to diffusion constraints. In the present invention, 1
A crystallite size smaller than μ results in an average particle size smaller than 0.5μ.

The activity of the SM-3 silicoaluminophosphate improves as the synthesis temperature increases to at least 240 ° C. Higher temperatures appear to increase crystal growth, and thus the crystallinity of the product. It gives more complete Si incorporation, which tends to give more active points.

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

Useful sources of silicon dioxide include those in any form of silicon or silicon dioxide, alkoxy of silicon or other compounds. Preferably Cab-O-Sil (Cab-
Silicon dioxide in the form known as o-Sil) is used.

A special property of the catalyst is its X-ray photoelectron spectroscopy
A) [Jour.Che by Lucchesi EA and others
m.Ed.50 (5): A269 (May 1973): and Kelley
y) Derived from its surface composition as determined by CHEMTECH, 99-105 by MJ (Feb. 1982)]. The term “surface” refers to both the outermost atomic layer and the volume up to about 50 ° below the outermost layer. The ESCA determination is a weighted average of the concentrations in these layers, the weighting factor of which decreases exponentially inwards.

Hewlett-Packard (Hewlett-Packard) to measure the atomic ratio of elemental phosphorus, silicon, aluminum and oxygen.
Packard) 5950A ESCA spectrophotometer was used.

The apparatus was operated to alternately scan the zone of interest and the oxygen 1s zone. This scanning method allows all band intensities to be linearly normalized to 1 s of oxygen, thereby compensating for the loss of detector sensitivity over the time required to analyze the sample. Was completed.

Relative intensities were corrected using the following response factors, rather than the theoretical Scofield cross section. These response factors were determined by calibration with amorphous aluminum phosphate, alumina, silica, sodium hydrogen phosphate, and aluminum sulfate, and were analyzed by Wagner (Wagner).
r) Surf.Inter.Anal., 3,211 (1981) and others
J. Electron Spectro by S. Evans and others
Similar to that found in s. Rel. Phenom. 14, 341 (1978).

For each of the elements silicon, aluminum and phosphorus,
The amount of surface elements was calculated based on the intensity of both the 2s and 2p bands and they were weighted by taking the square root of the response factor for each of those bands. Once the amounts of each element have been determined, the atomic and weight ratios and molar ratios can be easily calculated.

The observed variation in individual element concentrations is about 10%. However, the proportions of the elements can be determined more precisely, typically within 5%.

Elemental element determinations for silicon, aluminum and phosphorus were performed using the following procedure. This method first melts a sample of lithium metaborate, LiBO ₂ molecular sieve, and then dissolves the molten beads in a nitric acid solution. The resulting solution was analyzed using an inductively coupled plasma (ICP) method using matrix matching criteria. Applied Research Laborator, California
ies) (ARL).

An analysis solution was prepared as follows. 0.1g sample and
Mix with 1.4 g LiBO ₂ in a pre-burnt graphite crucible. This mixture was melted in a muffle furnace set at 1000 ° C. for 14 minutes. The crucible was immediately removed from the furnace and the molten beads were poured in a uniform motion into 60 ml of a 4% by volume HNO ₃ acid solution in a polyethylene beaker. The molten salt was stirred until dissolved, and then 5 ppm scandium, an internal standard diluted from a 1% concentrate purchased from VHG Laboratory, Andover, Mass., Was added. The resulting solution was diluted to 1.

Sample weight was corrected for water and residual organics by adjusting the sample weight for% Loss on Burn (LOI). The dried crucible containing the sample of known weight was heated at 1000 ° C. for 2 hours and cooled in a desiccator to room temperature. LOI% was calculated.

Sample weight was corrected for% LOI.

Using the corrected sample weights and comparing with the calibration curve for each element and the dilution factor associated with each sample (total volume / corrected sample weight), based on the instrument response of the sample, the weight percentage of silicon, aluminum and phosphorus by ICP It was determined.

The calibration curve for each element was determined by creating an aqueous calibration standard (matrix match) in the manner described above for sample preparation. However, without adding the sample, instead of immediately before diluting to 1, aqueous Al and P purchased from VHG
And a standard aqueous solution of Si were added in known amounts. Once the amounts of each element were determined, the atomic ratios, weight ratios and molar ratios were easily calculated.

If the previously synthesized SM-3 is to perform a hydrogenation-dehydrogenation or oxidation function, for example, silver, tungsten, vanadium, molybdenum, rhenium, chromium,
It can be used as a catalyst in intimate combination with a metal component such as manganese or a Group VIII metal, preferably platinum or palladium. Such components can be ion-exchanged into the composition, or impregnated therein, or can be physically intimately mixed therewith. Such components, for example, as in the case of platinum,
The crystals can be impregnated in or on the composition by treating the crystals with a solution containing platinum metal-containing ions. For example, suitable platinum compounds include various compounds including chloroplatinic acid, stannous chloride, platinum amine complexes.

The original ions of the as-synthesized SM-3, ie, cations or anions, can be obtained according to methods well known in the art.
It can be replaced at least in part by ion exchange with other cations or anions. Preferred replacement cations include metal ions, hydrogen ions, hydrogen precursors such as ammonium ions, and mixtures thereof. Particularly preferred cations include hydrogen, rare earth metals,
And IIA, IIIA, IVA, IB, IIB, of the Periodic Table of the Elements
Includes metals from Groups III B, IV B, VI B, VIII.

A typical ion exchange method would be to contact synthetic crystalline SM-3 with a salt of the desired replacement ion (s). Examples of such cationic salts include halides such as chlorides, nitrates, and sulfates.

Further, when the SM-3 of the present invention is used as an absorbent, an ion exchange agent, or a catalyst in an organic compound conversion method, it should be at least partially dehydrated. This is between 200 ℃ and 600 ℃
By heating in air or an inert atmosphere such as nitrogen at atmospheric pressure, reduced pressure, or high pressure for 30 minutes to 48 hours. Dehydration can also be performed at room temperature by simply placing the crystalline material in a vacuum, but it takes a long time to perform a sufficient amount of dehydration. Therefore, depending on the degree of dehydration or heat treatment desired for SM-3,
It will be subjected to heating at a temperature of 200 ° C. to 1000 ° C. for a time of 1 minute to 48 hours.

The crystals of SM-3 produced according to the present invention can be formed into a wide variety of particle sizes. Generally speaking, the particles pass through a 2 mesh (Tyler) mesh and form a shaped product such as an extrudate having a sufficient particle size to be retained on a 400 mesh (Tyler) mesh. Can be in the form of When the composition is shaped, such as by extrusion, the crystals may be extruded before drying, or may be partially dried and then extruded.

For many catalysts, it is desirable to incorporate SM-3 with other materials that are resistant to the temperatures and other conditions used in the organic conversion process. Such materials include active and inert materials and synthetic or natural zeolites, as well as inorganic materials such as clays, silicas and / or metal oxides. The latter may be naturally occurring or in the form of a gelatinous precipitate or gel, including mixtures of silica and metal oxides. The use of an active material in combination with, ie, with, SM-3 tends to increase the conversion and / or selectivity of the catalyst in certain organic conversion steps. The inert material acts as a diluent, regulating the amount of conversion in a given process and allowing the product to be obtained economically without any other means of regulating the rate of the reaction. Is appropriate. Formulating these materials in naturally occurring clays, such as bentonite and kaolin,
At commercial operating conditions, the breaking strength of the catalyst may be improved. Such materials, ie, clays, oxides, etc., serve as binders for the catalyst. It is desirable to provide a catalyst with good breaking strength because it is desirable to keep the catalyst from breaking down into powdered material in commercial applications. These clay binders have been commonly used only for the purpose of improving the breaking strength of the catalyst.

Natural clays that can be complexed with the novel crystals include montmorillonite and kaolin based, including sub-bentonite and kaolin commonly known as Dixie, McNamee, Georgia, and Florida clay. Or the main mineral component is halloysite,
Includes kaolinite, decite, nacrite, or others that are anauxites. Such clays may be used in the raw state as originally mined or may be used after first being calcined, acidified, or chemically modified. Binders useful for complexing with the crystals of the present invention include inorganic oxides, especially alumina or silica. .

In addition to the materials described above, the SM-3 produced is aluminum phosphate, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryria, silica-titania, as well as silica-alumina-tria, Can be complexed with a porous matrix material such as alumina-zirconia, silica-alumina-magnesia, and ternary compositions such as silica-magnesia, zirconia. The relative proportions of the finely crystalline SM-3 material and the inorganic oxide gel matrix vary widely, and the crystal content is in the range of 1-90% by weight, especially when the composite is produced in the form of beads. More usually 2 to 80% by weight of the complex
In the range.

The crystalline material produced by the process of the present invention can be easily converted to various organic, for example, catalytically active materials for hydrocarbon compound conversion processes.

The SM-3 catalyst, if it contains a hydrogenation promoter, can be used to carbonize the middle distillate by hydrocracking a hydrocarbonaceous feed where at least 90% of the feed has a boiling point above about 600 ° F. It can be used in a method for selectively producing hydrogen. Under hydrocracking conditions, it generally exceeds about 260 ゜ (500 ゜ F), usually above about 316 ℃ C (600 ゜ F),
Preferably, a reaction temperature of 316 ° C (600 ° F) to 482 ° C (900 ° F) is included. The hydrogenation rate should be at least about 400 standard cubic feet / barrel, typically about 1,000 to about 1
5,000 standard cubic feet / barrel. Reaction pressure is 13.
Over 7 bar (200 psig), typically about 32.4 bar (500 psig)
g) to about 207 bar (3000 psig). The liquid hourly space velocity is less than about 15, preferably about 0.2 to about 10.

The conditions are that the total conversion is about 385 ° C (725 ゜
F) less than about 725 ° F, preferably less than about 300 ° F
It should be selected to correspond to at least about 40%, preferably at least about 50%, of the product having the higher boiling point. Middle distillate selectivity is such that at least about 40%, preferably at least about 50%, of the product is in the middle distillate range, preferably below about 725 ° F and above about 300 ° F. There should be. The method is 149
Approximately 50% per pass with a selectivity of over 60% for middle distillate products boiling between 300 ° C (300 ° F) and 385 ° C (725 ° F)
Above the conversion level. The pour point of the middle distillate effluent obtained by the process will be below about 0 ° F, preferably below -20 ° F.

The process can be operated as a single stage hydroconversion zone. It can also be a second stage of a two-stage hydrocracking scheme in which nitrogen and sulfur are removed in a first stage from the feed before contacting with the middle distillate production catalyst. A catalyst can also be used in the first stage of the multi-stage hydrocracking system. In operation as a first stage, the middle distillate production zone may denitrify and desulfurize the feedstock and operate the second stage more effectively using the same catalyst or a conventional hydrocracking catalyst. So that an overall higher fraction can be produced than in other modes of operation.

In the process of the present invention, the hydrocarbon feed is heated with the catalyst at conversion conditions suitable for hydrocracking. During conversion, the aromatics and naphthenes present in the feed undergo a hydrocracking reaction such as dealkylation, ring opening, and cracking, followed by hydrogenation. The long chain paraffins present in the feed undergo a mild decomposition reaction and ZSM-5
As a result, a non-waxy product having a higher molecular weight is obtained as compared with a product obtained using a conventional dewaxed zeolite catalyst such as the above, and at the same time, an appropriate isomerization is carried out and the pour point due to the above decomposition reaction is lowered. Not only that, but also n-paraffins are isomerized to isoparaffins to form materials in the liquid range, which contribute to give low viscosity, low pour point products.

The feedstock for the process of the present invention comprises gas oil, bottoms fraction of coke forming column, reduced crude,
Vacuum bottom oil, deasphalted vacuum residual oil, FCC bottom oil,
Or a heavy hydrocarbon oil such as cycle oil. coal,
Oil derived from shale or tar sands can also be treated in this way. This type of oil is generally 316 ° C
Boiling at a higher temperature (600 ゜ F)
It is also useful with oils having a low initial boiling point, such as 436 ° F. Preferably at least 90% of the feed is 31
Boils at a temperature above 6 ° C (600 ° F), most preferably at least about 90% of the feed is from 371 ° C (700 ° F) to about 649 ° C
(1200 ゜ F) will boil. These heavy oils consist of high molecular weight long chain paraffins and high molecular weight cyclic compounds which contain a large proportion of fused cyclic compounds.
During processing, the fused cyclic aromatic and naphthenes and paraffin compounds are both decomposed by the SM-3 containing catalyst to yield middle distillate range products. A substantial portion of the paraffin component of the initial feed also undergoes conversion to isoparaffin.

The method has particular utility for highly paraffinic feeds. This is because this type of feed provides the greatest pour point improvement. However, most feeds will contain polycyclic compounds at some content.

The process uses a heavy feedstock, such as a gas oil having a boiling point above 600 ° F., as a middle distillate having an improved pour point, in contrast to the conventional process using a large pore catalyst such as zeolite Y. It can be more selectively converted to a range of products.

The hydrocracking catalyst comprises at least one hydrogenation catalyst (component) of the type commonly used in hydrocracking catalysts
In an effective amount. The hydrogenation component is generally selected from the group of hydrogenation catalysts consisting of one or more Group VIB and Group VIII metals, including salts, complexes and solutions containing them. The hydrogenation catalyst is of the group consisting of at least one platinum, palladium, rhodium, iridium, and mixtures thereof, or of the group consisting of at least one nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof. It is preferably selected from the group consisting of metals, their salts and complexes.
References to catalytically active metal (s) are intended to include some form of metal (s), such as elemental or oxide, sulfide, halide, carboxylate, and the like.

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

SM-3 may be used with a conventional hydrocracking catalyst, for example, any of the alumina silicates heretofore used as a component in the hydrocracking catalyst. Representative of the disclosed zeolite aluminosilicates that can be used as a component part of the hydrocracking catalyst include zeolite Y (including steam-stabilized, for example, ultrastable Y), zeolite X, and zeolite β. (US Patent No. 3,30
No. 8,069), zeolite ZK-20 (US Pat. No. 3,445,727).
No.), zeolite ZSM-3 (U.S. Pat. No. 3,415,736),
Faujasite, LZ-10 (UK Patent No. 2,014,970 published June 9, 1982), ZSM-5 type zeolite, such as ZSM
-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-3
8, ZSM-48, crystalline silicates such as silicalite (U.S. Pat. No. 4,061,724), erionite, mordenite, offretite, chabazite, FU-1 type zeolite, NU type zeolite, LZ-210 type zeolite, and the like. It is a mixture. Conventional cracking catalyst containing Na ₂ O in smaller amount than about 1 wt% is generally preferred. The relative amounts of the SM-3 component and the conventional hydrocracking component, if present, will depend, at least in part, on the selected hydrocarbon feedstock and the desired product distribution obtained therefrom. In each case, an effective amount of SM-3 is used. When a conventional hydrocracking catalyst (THC) component is used, the relative weight ratio of THC to SM-3 is generally from about 1:10 to about 500: 1, desirably from about 1:10 to about 200: 1. , Preferably from about 1: 2 to about 50: 1, most preferably from about 1: 1 to about 20: 1.

Hydrocracking catalysts are typically used with inorganic oxide matrix components, which are any of the inorganic oxide matrix components conventionally used in formulating hydrocracking catalysts. Catalytic inorganic oxides include, for example, catalytically active silica-alumina, clay, silica, alumina, silica-alumina, silica-zirconia, silica-magnesia, alumina-boria, alumina-titania, and the like, and mixtures thereof. The conventional hydrocracking catalyst and SM-3 may be separately mixed with the matrix component and then combined, or the THC component and the SM-
3 may then be mixed and then formed together with the matrix components.

SM-3 can be used in a process for dewaxing hydrocarbonaceous feeds. Catalytic dewaxing conditions are highly dependent on the feed used and the desired pour point. Generally, the temperature is about 200 ° C
To about 475 ° C, preferably from about 250 ° C to about 450 ° C. The pressure is typically between about 15 psig and about 3000 psig, preferably between about 200 psig and 3000 psig. Liquid space velocity (LHS
V) will be from 0.1 to 20, preferably from about 0.2 to about 10.

Preferably, hydrogen is present in the reaction zone during the catalytic dewaxing step. The ratio of hydrogen to feed is typically about
500 to about 30,000 SCF / bbl (standard cubic feet / barrel),
Preferably it is about 1000 to about 20,000 SCF / bbl. Generally, hydrogen will be separated from the product and recycled to the reaction zone.

The process of the present invention has been found to provide selective conversion of waxy n-paraffins to non-waxy paraffins. During processing, waxy paraffins undergo a mild cracking reaction to yield higher molecular weight non-waxy products as compared to products obtained using conventional zeolite catalysts. At the same time, some isomerization takes place,
Not only is the pour point lowered due to the decomposition reaction, but also n-paraffins are isomerized to isoparaffins to form materials in the liquid range, which give low viscosity, low pour point products. Contribute.

The method of the present invention comprises the steps of starting from relatively light fractions to untreated crude oil, untreated crude oil, vacuum tower bottoms, cycle oil, synthetic crude oil (shale oil, tar sands oil, etc.), gas oil, vacuum gas oil, wax It can be used to dewax various feedstocks, ranging from oils and other high-boiling feedstocks such as heavy oils. The feed will typically be a C ₁₀ + feed that typically boils above 350 ° F. This is because lighter oils usually do not contain significant amounts of waxy components. However, the process involved gas oils, kerosene and jet fuels, lubricating oil feedstocks, heating oils and other distillate fractions whose pour point and viscosity needed to be maintained within certain ranges. It is particularly useful for waxy distillate feedstocks such as middle distillate feedstocks. Lubricating oil feedstocks will generally boil above 230 ° C (450 ° F) and more usually will boil above 315 ° C (600 ° F).
Hydrotreated feedstocks, including those that have been hydrotreated and / or hydrocracked to reduce the amounts of metals, nitrogen, and sulfur, are a convenient source of this type of feedstock, and they have significant amounts. It is also a convenient source of other fractions, as it usually contains waxy n-paraffins. The feedstock of the process of the present invention typically comprises paraffins, olefins, naphthenes, aromatics, heterocycles and a substantial proportion of high molecular weight n-paraffins and slightly branched paraffins that contribute to the waxiness of the feedstock. Would be a C ₁₀ + feedstock.
During processing, n-paraffins and slightly branched paraffins undergo some cracking or hydrocracking to form liquid range materials that contribute to low viscosity products. However, the degree of decomposition that occurs is limited such that gas production is reduced, thereby maintaining the economic value of the feedstock.

Typical feedstocks include light gas oils, heavy gas oils, and top crudes that boil at temperatures above 350 ° F.

The process here can be effectively carried out even when the feed contains organic nitrogen (nitrogen-containing impurities), but the organic nitrogen content of the feed is preferably less than 50 ppmw, more preferably less than 10 ppmw .

When used in the present method, SM-3 is used in admixture with at least one Group VIII metal, for example, noble metals such as platinum and palladium, and optionally other catalytically active metals such as molybdenum, vanadium, zinc, and the like. Can be The amount of metal ranges from about 0.01 to 10%, preferably 0.2 to 5% by weight of the molecular sieve.

Group VIII metal used in the method of the present invention means one or more of the metals in elemental state or in some form of metal, such as sulfides, oxides, and mixtures thereof. As is customary in the field of catalysis, references to the active metal (s) include the elemental state, or the presence of some form of such metals, such as oxides or sulfides, as described above. The concentration is calculated assuming that they exist as elemental states, irrespective of the state in which the metal components actually exist.

The SM-3 silicoaluminophosphate molecular sieve can be paired with other materials that are resistant to the temperatures and other conditions used in the dewaxing process. Such matrix materials include active and inert materials, synthetic or naturally occurring zeolites, and also inorganic materials such as clays, silica, alumina, and metal oxides. Examples of zeolites include:
Synthetic and natural faujasites (eg, X and Y), erionite, mordenite, and those of the ZSM series, such as ZSM-5, are included. Combinations of zeolites can also be composited as porous inorganic matrices.

SM-3 can be used in a method for producing a lubricating oil. The process comprises the steps of (a) hydrocracking a hydrocarbonaceous feedstock in a hydrocracking zone to obtain an effluent consisting of hydrocracked oil; and (b) performing a step (a) in a catalytic dewaxing zone.
Of hydrocracked oil from crystalline silicoaluminophosphate
Catalytic dewaxing with a catalyst comprising SM-3 and a Group VIII metal, preferably platinum or palladium.

Another aspect of the method includes an additional step of stabilizing the dewaxed hydrocracked product by catalytic hydrofinishing.

The hydrocarbonaceous feed from which the lubricating oil is made usually comprises aromatics and straight and branched chain paraffins of very long chain length. These feeds usually boil in the gas oil range. Preferred feedstocks have a normal boiling range of 350 ° C
Vacuum gas oil in the range of 600600 ° C. and deasphalted resid in the normal boiling range of about 480 ° C. to 650 ° C. Crude crude oil, shale oil, liquefied coal, coke fractions, flask or pyrolysis oils, atmospheric resids, and other heavy oils can also be used. The first step in the treatment scheme is hydrocracking. As a commercial operation, hydrocracking is carried out as a single-step method or as a multi-step method, initially using a denitrification or desulfurization step, all of which are well known.

Typically, hydrocracking conditions include 250 ° C to 500 ° C.
° C, a pressure in the range of about 425-3000 psig or more, a hydrogen recycle rate of 400-15,000 SCF / bbl, and
0.1 to 50 LHSV (v / v / hr) is included.

During the hydrocracking step, at least 10% conversion to a product with a boiling point below 350 ° C. takes place. Catalysts used in the hydrocracking zone (s) include those having hydrogenation / dehydrogenation activity and active cracking supports. Supports are often silica-alumina, silica-alumina-zirconia, and silica-alumina-titania composites, acid-treated clays, crystalline aluminosilicate zeolite molecular sieves (such as zeolite A, faujasite, zeolite X, and zeolite Y) ), And combinations thereof.

The hydrogenation / dehydrogenation component of the hydroconversion cracking catalyst usually comprises a metal selected from Groups VIII and VIB of the periodic table and a compound containing the same. Preferred Group VIII components include cobalt, nickel, platinum, and palladium, especially oxides and sulfides of cobalt and nickel.
Preferred Group VIB components are molybdenum and tungsten oxides and sulfides. Examples of preferred hydrocracking catalysts for use in the hydrocracking step are combinations of nickel-tungsten-silica-alumina and nickel-molybdenum-silica-alumina.

A particularly preferred hydrocracking catalyst for use in the process of the present invention is nickel sulfide / tungsten sulfide on a silica-alumina substrate containing discrete metal phosphate particles [US Pat. No. 3,493,517, which is incorporated by reference. Which are included here for reference).

The nitrogen content of the hydrolyzate is low, consistent with economic purification operations, but is preferably less than 50 ppm (w / w), more preferably less than about 10 ppm (w / w), and most preferably Less than about 1 ppm (w / w).

The hydrocracking step offers two important advantages. First, reducing the nitrogen content dramatically increases the efficiency and ease of the catalytic dewaxing process. Second, the viscosity index increases significantly as aromatics present in the feed, especially polycyclic aromatics, are opened and hydrogenated. In the hydrocracking step, at least 10
An increase in VI units will occur in the lubricating oil fraction, ie, the fraction boiling above 230 ° C, more preferably above 315 ° C.

The hydrocrackate is distilled, preferably by conventional means, to remove products boiling below 230 ° C., more preferably below 315 ° C., resulting in one or more lube oil boiling range streams. The particular lubricating oil desired, for example,
Depending on the light, intermediate, or heavy lubricating oil, the feed hydrocracked product can be distilled into a light, intermediate, or heavy oil fraction. Some of the removed low-boiling products are lighter nitrogen-containing compounds such as NH _3. This results in a lubricating oil stream with reduced nitrogen content, and the SM-3 crystalline silicoaluminophosphate molecular sieve in the dewaxing catalyst achieves maximum activity in the dewaxing step. Lubricating oils of different boiling ranges can be produced by the process of the present invention. These include light neutral, neutral neutral, and heavy natural (n
atural), and bright stock, with neutral oil being prepared from a distillate fraction and bright stock being prepared from a resid fraction.

The great efficiency of the present invention is due in part to a high viscosity index hydrogenolysis product with a very low nitrogen content, which is then very efficiently dewaxed with a very low pour point and improved It is obtained from a combination of hydrocracking that achieves viscosity and viscosity index. It has been observed that the greater the activity of the dewaxing catalyst, the lower the reactor temperature required to achieve a particular degree of dewaxing. Thus, an important advantage is greater energy savings by using catalysts with increased efficiency, typically with longer process life. In addition, because the SM-3 crystalline silicoaluminophosphate dewaxing catalyst has morphological selectivity, it is a slightly branched paraffin and an alkyl-substituted cycloparaffin, having a high pour point, similar to that of so-called microcrystalline wax. Reacts preferentially with the waxy components of the causative feedstock, ie, normal paraffins.

When used in the method of the present invention, the SM-3 silicoaluminophosphate comprises at least one noble metal, platinum, palladium, and optionally other catalytically active metals, such as molybdenum, nickel, vanadium, cobalt, tungsten,
It is preferably used by mixing with zinc or the like and a mixture thereof. The amount of metal is in the range of about 0.01-10%, preferably 0.2-5% by weight of the molecular sieve.

Metals used in the method of the invention means one or more of these metals in elemental form or in some form, such as sulfides, oxides, and mixtures thereof. As is customary in the field of catalysis, when reference is made to the active metal (s), it may be in its elemental state or in some form, such as an oxide or sulfide as described above. The concentration is calculated assuming that they exist as their elemental states, irrespective of the state in which the metal components actually exist.

The dewaxing step may be performed in the same reactor as the hydrocracking step, but is preferably performed in a separate reactor. Catalytic dewaxing conditions are highly dependent on the feed used and the desired pour point. Generally, the temperature will be from about 200C to about 475C, preferably from about 250C to about 450C. The pressure is typically about
15 psig to about 3000 psig, preferably about 200 psig to 300 psig
0 psig. Preferably, the liquid hourly space velocity (LHSV) is 0.1 to
20, preferably from about 0.2 to about 10.

Preferably, hydrogen is present in the reaction zone during the catalytic dewaxing step. The ratio of hydrogen to feed is typically about
500 to about 30,000 SCF / bbl (standard cubic feet / barrel),
Preferably it is about 1000 to about 20,000 SCF / bbl. Generally, hydrogen will be separated from the product and recycled to the reaction zone.

The SM-3 crystalline silicoaluminophosphate used in the dewaxing step provides a selective conversion of the waxy component to a non-waxy component. During processing, waxy paraffins undergo a mild cracking reaction to yield higher molecular weight non-waxy products as compared to products obtained using conventional zeolite catalysts. At the same time, a certain degree of isomerization is performed, not only the pour point is lowered due to the decomposition reaction, but also the waxy component is isomerized into a liquid range substance to form a liquid range substance, which is excellent. And low viscosity pour point products with improved VI properties.

The SM-3 crystalline silicoaluminophosphate molecular sieve can be complexed with other materials that are resistant to the temperatures and other conditions used in the dewaxing process. Such matrix materials include active and inert materials, synthetic or naturally occurring zeolites, and also inorganic materials such as clays, silica, alumina, and metal oxides. Examples of zeolites include synthetic and natural faujasites (eg, X and Y), erionite, mordenite, and those of the ZSM series, such as ZSM-5. Combinations of zeolites can also be composited as porous inorganic matrices.

In order to produce a more stable lubricating oil, it is often desirable to use mild hydrogenation (sometimes referred to as hydrofinishing).

The hydrofinishing step can be performed before or after the dewaxing step, and is preferably performed after. Hydrofinishing is typically performed at a temperature in the range of about 190 ° C to about 340 ° C, for about 400p
At pressures from sig to about 3000 psig, space velocities (LHS
V), and typically at a hydrogen circulation rate of 400 to about 1500 SCF / bbl. The hydrogenation catalyst used must have sufficient activity not only to hydrogenate olefins, diolefins and colorants in the lubricating oil fraction, but also to reduce aromatics. The hydrogenation finishing process
It is advantageous to produce lubricating oils with acceptable stability. This is because lubricating oils prepared from hydrocracked oils tend to be unstable to air and light and tend to form sludge naturally and quickly.

Suitable hydrogenation catalysts include conventional metal hydrogenation catalysts, especially VIII VIII such as cobalt, nickel, palladium, and platinum.
Including group metals. The metal is typically associated with a support such as bauxite, alumina, silica gel, silica-alumina composite, crystalline aluminosilicate zeolite. Palladium is a particularly preferred metal hydride. If desired, non-noble Group VIII metals can be used with molybdate. Metal oxides or sulfides can be used. Suitable catalysts are described, for example, in U.S. Pat.
Nos. 207, 4,157,294, 3,904,153, and 4,673,4
No. 87, the description of which is incorporated herein by reference.

The improved methods of the present invention will now be illustrated by examples, which do not limit the invention described herein, including the claims.

〔Example〕

Has a body SiO ₂ / Al ₂ O ₃ ratio of Examples 1 to 5 0.375 ± 0.005, and the five SM-3 with different surface ratios were prepared. These were carried out as follows: of 85% H ₃ PO ₄ of Example 1. 231.2g, was added in a Teflon beaker in an ice bath to distilled of H ₂ O 118 g. 408.4 g of aluminum isopropoxide (Al [OC ₃ H ₇ ] ³ ) was added slowly with stirring and then mixed until homogeneous. Next, 38 g of fumed silica [Cab Osyl (Cab
ocil) M-5] in 168 g of distilled water was added with stirring. Next, 91.2 g of di-n-propylamine (pr ₂ NH) was added and then mixed with a Polytron. The mixture had a pH of 6.0 and had the following composition, expressed as a molar ratio of oxides: 0.9Pr ₂ NH: 0.6SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 18H ₂ O The mixture was made of stainless steel It was placed in a Teflon bottle in a pressure vessel and heated at 200 ° C. for 5 days at a spontaneous pressure without stirring. Remove the supernatant, remove the product, wash with water,
Dried at 127 ° C. overnight and calcined in air at 538 ° C. for 8 hours.
The average grain size was smaller than 0.5μ.

Of 85% H ₃ PO ₄ of Example 2 462.4g, it was added in a Teflon beaker and cooled in an ice bath of distilled water 236 g. 816.8g
Al (OC ₃ H ₇ ) ₃ was added slowly with stirring and then mixed until homogeneous. Next, 120g of Cabosil HS-5
Was added with stirring in 480 g of distilled water,
Mix for 15 minutes. Next, 182.4 g of di-n-propylamine was added and mixed for about 15 minutes. The mixture had a pH of 6.4 and had the following composition, expressed as a molar ratio of oxides: 0.9 Pr ₂ NH: SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 22H ₂ O Placed in a Teflon bottle in a pressure vessel and heated at 200 ° C. for 5 days at spontaneous pressure without stirring. Remove the supernatant, remove the product, wash with water,
Dried at 121 ° C. for 8 hours and calcined in air at 566 ° C. for 8 hours. The average grain size was smaller than 0.5μ.

Of 85% H ₃ PO ₄ of Example 3. 231.2g, it was added to distilled of H ₂ O 238g in a Teflon beaker in an ice bath. 408.4 g of Al (OC ₃
Slowly added with stirring H _{7) 3,} were mixed with a Polytron until then becomes uniform. 60g Cabosil M-5
Was added with mixing and mixed until uniform. next
91.2 g of di-n-propylamine were added with mixing. The pH of the mixture was then adjusted to 6.5 using concentrated HCl. The mixture had the following composition, expressed as a molar ratio of oxides: 0.9Pr ₂ NH: SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 15H ₂ O The mixture was made of stainless steel with Teflon inserts Placed in a pressure vessel and heated at 200 ° C. for 8 days at a spontaneous pressure without agitation. The supernatant was removed, the product was filtered off, washed with water, dried at 121 ° C. overnight and calcined in air at 593 ° C. for 8 hours. The average grain size was smaller than 0.5μ.

Of 85% H ₃ PO ₄ of Example 4. 472.4g, it was added to distilled of H ₂ O 1208g in a Teflon beaker in an ice bath. 816.8g Al (OC
₃ H _{7) 3} was added slowly with stirring and mixed with a Polytron until then becomes uniform. 120g Cabosil M-
5 was added with mixing and then mixed for another 15 minutes. 18
2.4 g of di-n-propylamine are added with mixing,
Mix for another 15 minutes. It was then added with further mixing of 85% H ₃ PO ₄ in 9.6 g. The mixture had a pH of 6.5 and had the following composition, expressed as a molar ratio of oxides: 0.9Pr ₂ NH: SiO ₂ : Al ₂ O ₃ : 1.04P ₂ O ₅ : 36H ₂ O mixture, Placed in a Teflon bottle in a stainless steel pressurized vessel and heated at 200 ° C. for 5 days at a spontaneous pressure without agitation. Remove the supernatant, remove the product, wash with water,
Dried overnight at 121 ° C., then calcined in air at 566 ° C. for 8 hours. The average grain size was smaller than 0.5μ.

Of 85% H ₃ PO ₄ of Example 5. 472.4g, it was added to distilled of H ₂ O 1208g in a Teflon beaker in an ice bath. 816.8g Al (OC
₃ H _{7) 3} was added slowly with stirring and mixed with a Polytron until then becomes uniform. 120g Cabosil M-
5 was added with mixing and mixed for an additional 15 minutes. Then 18
2.4 g of di-n-propylamine was added and mixed for 15 minutes. It was then added with further mixing of 85% H ₃ PO ₄ of 30g.
The mixture had a pH of 6.5 and had the following composition, expressed as a molar ratio of oxides: 0.9Pr ₂ NH: 1.0SiO ₂ : Al ₂ O ₃ : 1.09P ₂ O ₅ : 36H ₂ O And placed in a Teflon bottle in a stainless steel pressurized vessel and heated at 200 ° C. for 5 days at a spontaneous pressure without stirring. Remove the supernatant, remove the product, wash with water,
Dried at 121 ° C. overnight, then calcined in air at 566 ° C. for 8 hours. The average grain size was smaller than 0.5μ.

X-ray diffraction images of each of the synthesized and as-calcined Examples 1-5 are shown in Tables I and II, respectively.
As described in US Pat. No. 4,440,871, SAPO-11
It was characteristic.

The molecular sieve of Examples 1 to 5 was impregnated with 1 wt% Pt by _{Pt (NH 3) 4 (NO} 3) pore filling method using the _second solution. Dry the molecular sieves at 121 ° C overnight and in air at 204 ° C
For 4 hours and at 454 ° C. for 4 hours. Then they were tested in the following as performed a C ₈ activity test: 24 × 42 mesh catalyst 0.5g was placed in a 3 / 16in internal diameter stainless steel reactor, the remaining space acid washing neutralizing 24 mesh Filled with alundum. The reactor was placed in a high pressure continuous flow pilot plant clam shell furnace equipped with a Hewlett Packard 5880 gas chromatograph using a sampling valve and a capillary column. 1000 psig catalyst, 2.8 W
HSV, and at 16H ₂ / HC, were tested using the feed consisting of a 50/50 by weight mixture of 2,2,4-trimethylpentane and n- octane. The reactor temperature was adjusted to 40% nC ₈ conversion.

C ₈ activity test gives information about the activity of the catalyst.

The ESCA analysis of the molecular sieves of Examples 1-5 before impregnation with platinum is given in Table III.

The results of activity tests on molecular sieves after impregnation with platinum and calcination are also given in Table III.

Examples 6 and 7 and Comparative Examples 8 and 9 The reaction mixtures are expressed as oxides, 0.9Pr ₂ NH: 0.6SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : bH ₂ O (where b is a variable) Samples of Examples 6, 7, and relatively 8 were prepared having a molar composition of The body SiO ₂ / Al ₂ O ₃ ratio of the product was 0.20 ± 0.02. Comparative Example 9 below corresponds to Example 17 of U.S. Patent No. 4,440,877.

Of 85% H ₃ PO ₄ of Example 6. 115.6 g, was added to distilled water 59g in a Teflon beaker in an ice bath. 204.2g Al (OC
₃ H _{7) 3} was added slowly with stirring and mixed until the next uniform. It was then added with mixing those put Kyabuoshiru M-5 of 19g of distilled of H ₂ O 42 g. 45.6g
Of di-n-propylamine was added and mixed with a Polytron. The mixture had a pH of 6.0 and the H ₂ O / Al ₂ O ₃ molar ratio was 13. The mixture was placed in a Teflon bottle in a stainless steel pressurized vessel and heated at 200 ° C. for 5 days at a spontaneous pressure without agitation. The supernatant was removed, the product was washed, washed with water, dried at 121 ° C. overnight and calcined in air at 538 ° C. for 8 hours. The average grain size was smaller than 0.5μ.

Example 7. SM-3 was prepared as in Example 6,
Was added sufficient distilled water to H ₃ PO ₄ to H ₂ O / Al ₂ O ₃ molar ratio of the mixture take up 33. The pH of the reaction mixture was 6.1. The average grain size was about 0.5μ.

Comparative Example 8. A molecular sieve was prepared as in Example 6, but with a H ₂ O / Al ₂ O ₃ molar ratio of the mixture up to 62 and sufficient distilled water to fall outside the scope of the invention. It was added to H ₃ PO _4. The pH of the reaction mixture (7.5) was lowered to 6.5 by adding concentrated HCl. The average grain size was in the range of 0.5μ.

Comparative Example 9. SAPO-11 silicoaluminophosphate was prepared according to the procedure of Example 17 of U.S. Patent No. 4,440,871 using twice the amount of the material shown there. The pH of the reaction mixture was 10.7. The average grain size was less than about 1 micron. X-ray diffraction images for each of the synthesized, as-calcined Examples 6, 7 and Comparative Examples 8, 9 are shown in Tables I and II, respectively, and are described in U.S. Patent No. 4,440,871. It was characteristic of SAPO-11.

The molecular sieves of Examples 6 and 7, Comparative Examples 8 and 9, and Examples 1 to
As in case 5, platinum was impregnated and calcined.

The ESCA analysis values of the molecular sieves of Examples 6, 7 and Comparative Examples 8, 9 before impregnation with platinum are shown in Table IV. Examples 6 and 7 and Comparative Examples 8 and 9 after impregnation with platinum and calcination.
The activity test data for the molecular sieves are also shown in Table IV.

The molecular sieves of Examples 6 and 7, which fall within the scope of the present invention with respect to the body and surface P ₂ O ₅ / Al ₂ O ₃ molar ratio and SiO ₂ / Al ₂ O ₃ molar ratio, fall outside the scope of the present invention. 9 shows improved activity compared to Examples 8 and 9.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification symbol FI C10G 49/08 C10G 49/08 (58) Investigated field (Int.Cl. ⁷ , DB name) C01B 33/20-33/46 C01B 37/00-39/54 B01J 21/00-38/74

Claims (16)

(57) [Claims] 1. A powder having a characteristic X-ray powder diffraction image including at least the d interval shown in Table I, wherein the surface P ₂ O ₅ of silicoaluminophosphate to alumina molar ratio is 0.80 or less, and the P ₂ O of the body of the silicoaluminophosphate is ₅ pairs and the alumina mole ratio is 0.96 or more, SiO ₂ to alumina mole ratio of the surface of the silicoaluminophosphate salt, body large crystalline silicoaluminophosphate salt molecule sieve than the ratio. 2. A crystalline silicoaluminophosphate molecular sieve having a composition represented by the following formula in terms of a molar ratio of oxides on an anhydrous basis: mR: Al ₂ O ₃ : nP ₂ O ₅ : qSiO _{2 wherein} "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the number of moles of "R" present, 0.02 per mole of aluminum.
Has a value such that ２2 moles of R are present; n is 0.96-1.1.
Wherein q has a value of 0.1 to 4, and the silicoaluminophosphate has a characteristic X-ray powder diffraction image including at least the d interval shown in Table I, and P ₂ O _Five
The molar ratio of alumina to alumina is 0.80 or less, and the P ₂ O ₅ to alumina molar ratio of the body of the silicoaluminophosphate is 0.96 or more,
The molar ratio of SiO ₂ to alumina on the surface of the silicoaluminophosphate is greater than the molar ratio of SiO ₂ to alumina on the body of the silicoaluminophosphate]. 3. The silicoaluminophosphate according to claim 2, wherein the organic template is selected from the group consisting of di-n-propylamine, diisopropylamine, and mixtures thereof. 4. A silicoaluminophosphate obtained from the heat treatment of the silicoaluminophosphate according to claim 1. 5. The silicoaluminophosphate according to claim 4, which has a characteristic X-ray powder diffraction image shown in Table II. 6. A rare earth metal, a Group IIA metal, a Group VI or a Group II metal.
The silicoaluminophosphate according to claim 1, 2 or 4, comprising a Group VIII metal. 7. A rare earth metal, a Group IIA metal, a Group VI or a Group
The silicoaluminophosphate according to claim 1, 2 or 4, wherein the group VIII metal is occluded in the silicoaluminophosphate. 8. An aqueous reaction mixture comprising: (a) a reactive source of SiO ₂ , aluminum isopropoxide, phosphoric acid, and an organic template agent, wherein said reaction mixture is expressed as a molar ratio of oxides and has the following composition: 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 agent; “a” constitutes an effective amount of R Have a value large enough to
"B" is aluminum oxide per mole 10-40 moles of H ₂
O having a value such that O is present), wherein the reaction mixture combines the alumina and phosphorus sources in the substantial absence of the silicon source, and then combines the resulting mixture with the silicon source. (B) bringing the pH of the reaction mixture to between 6.0 and 8.5, and (c) reacting the mixture with the organic template agent to form a complete reaction mixture. Bringing the mixture to a temperature in the range 170 ° C to 240 ° C,
Heating until silicoaluminophosphate crystals are formed,
The method for producing a crystalline silicoaluminophosphate according to claim 1, wherein (d) recovering the crystal. 9. The method of claim 8, wherein the organic templating agent is selected from the group consisting of di-n-propylamine, diisopropylamine, or a mixture thereof. 10. The method according to claim 8, wherein the crystal size of the recovered crystals is smaller than 1 μm. 11. A hydrocarbon conversion process comprising contacting a hydrocarbonaceous feed with the crystalline silicoaluminophosphate molecular sieve of claim 1 under hydrocarbon conversion conditions. 12. At least 90% of the hydrocarbonaceous feed is 60%.
12. The process of claim 11 for the selective production of middle distillate hydrocarbons by hydrocracking and isomerizing a hydrocarbonaceous feed having a boiling point greater than 0 ° F (315.6 ° C), comprising: a) contacting the hydrocarbonaceous feed under hydrocracking conditions with a catalyst comprising the crystalline silicoaluminophosphate molecular sieve of claim 1 and at least one hydrogenation component; and (b) hydrocarbonaceous effluent. More than 40% by volume of the effluent is higher than 300 ° F (148.9 ° C) and 725 ° F (385
Recovering a hydrocarbonaceous effluent boiling below 0 ° C. and having a pour point below 0 ° F. (−17.8 ° C.). 13. The method according to claim 12, wherein the catalyst further comprises an inorganic oxide matrix. 14. The process of claim 12, wherein a catalyst is disposed downstream of the reaction zone, wherein the hydrocarbon feed is contacted with the active hydrodenitrification catalyst at hydrotreating conditions in the reaction zone. 15. The process of claim 11 wherein the hydrocarbon oil feed boiling at a temperature above 350 ° F. (176.7 ° C.) and comprising linear and slightly branched chain hydrocarbons is catalytically dewaxed. Contacting the hydrocarbon oil feed with a crystalline silicoaluminophosphate molecular sieve of claim 1 and a catalyst comprising at least one Group VIII metal. 16. The method of claim 11 for producing a lubricating oil, comprising: (a) hydrocracking a hydrocarbonaceous feedstock in a hydrocracking zone to obtain an effluent comprising hydrocracked oil. And (b) catalytically dewaxing the hydrocracked oil directly in the dewaxing zone with a catalyst comprising the crystalline silicoaluminophosphate molecular sieve of claim 1 and a Group VIII metal.