CN104870368B - Hydrocarbon conversion process using UZM-43, an EUO-NES-NON zeolite - Google Patents

Abstract

A new family of crystalline aluminosilicate zeolites, designated UZM-43, has been synthesized. These zeolites are similar to the previously known ERS-10, SSZ-47 and RUB-35 zeolites, but are characterized by unique x-ray diffraction patterns and compositions and have catalytic properties for carrying out various hydrocarbon conversion processes. Catalysts made from these zeolites are used in hydrocarbon conversion reactions.

Description

Hydrocarbon conversion process using UZM-43, an EUO-NES-NON zeolite

Priority claims from earlier national applications

This application claims priority to US Application No. 13/718,003, filed December 18, 2012.

Background of the invention

The present invention relates to zeolite UZM-43, a process for its preparation and its use as catalyst in hydrocarbon conversion processes. The zeolite is represented by the following empirical formula:

where M represents sodium or a combination of sodium and potassium exchangeable cations, "m" is the M:(Al+E) molar ratio and is 0.05-5, R1 is a singly charged propyltrimethylammonium cation, and "r1" is R : (Al+E) molar ratio and have a value of 0.25-8.0, R2 is an amine, "r2" is R: (Al+E) molar ratio and has a value of 0.0-5, E is selected from gallium, iron, boron Elements of the group consisting of and mixtures thereof, "x" is the mole fraction of E and has a value of 0-1.0, "y" is the Si:(Al+E) molar ratio and is greater than 5 to 40, and "z" is O: (Al+E) molar ratio and has a value determined by the following equation: z=(m+r1+r2+3+4·y)/2. Zeolite UZM-43 has an intergrowth of the framework EUO-NES-NON. It can be present in the catalyst as unmodified zeolite UZM-43 or UZM-43 modified zeolite. Catalysts comprising UZM-43 can take one of several forms including, for example, spherical oil droplet catalysts or extruded catalysts.

Zeolites are microporous and crystalline aluminosilicate compositions formed by corner sharing _AlO2 and _SiO2 tetrahedra. Naturally occurring and synthetically prepared large numbers of zeolites are used in various industrial processes. Synthetic zeolites are prepared by hydrothermal synthesis using suitable sources of Si, Al and structure directing agents such as alkali metals, alkaline earth metals, amines or organoammonium cations. The structure directing agent resides in the pores of the zeolite and is primarily responsible for the specific structure that is ultimately formed. These species balance the framework charges associated with aluminum and can also act as steric fillers. Zeolites are characterized by an adsorbed phase with uniformly sized open pores, significant ion exchange capacity, and the ability to reversibly desorb and disperse throughout the internal voids of the crystal without significantly displacing any of the atoms that make up the permanent zeolite crystal structure. Zeolites can be used as catalysts for hydrocarbon conversion reactions that occur on the outer surfaces as well as on the inner surfaces within the pores.

The three framework types EUO, NON and NES are closely related and can be composed of the same two-layer building blocks LBU A and LBU B extending along the a' and b' axis directions shown below. LBU A consists of TO _tetrahedra connected in two dimensions to produce silicate sheets with 12-ring openings. LBU B consists of linear chains of TO ₄ tetrahedra. To generate the 3D backbone structures of EUO, NON, and NES, the two types of layers were stacked in a characteristic order along the c′-axis direction.

The above diagram shows layered structural units of the EUO-NES-NON family as seen perpendicular to (001). (a) Layer A consists of [TO4] tetrahedra interconnected to form 12 rings and (b) Layer B consists of rods of [TO4] tetrahedra running parallel to a'.

The diagram above shows a representation of the framework structure and the stacking order of (a) NON, (b) EUO and (c) NES as seen perpendicular to (100).

For NON, only LBU A layer is stacked a). The stacking order is AA'AA', where every other A layer is shifted by 1/2a' and designated as A'. Although each layer contains 12 rings, an alternating displacement of 1/2a' units is obtained and the resulting NON framework is a dense phase. It is not actually a zeolite, but a clathrasil, since it contains cages accessible by pores no larger than 6 rings (designated nns by J.V.Smith1).

The EUO framework type can be b) formed by inserting a B layer between the AA' bilayers, resulting in a stacking order AA'BAA'B. The resulting backbone contains one-dimensional 10-ring channels with side pockets into the truncated nns cage.

NES backbone types can be c) formed by alternating A and B layers to give the stacking order AB'A'BAB'A'B, where A' and B' are displaced by 1/2a'. The resulting framework contains two-dimensional 10-ring channels perpendicular to the b' axis.

Several related molecular sieves are disclosed, but there are clear distinctions between those and the present invention. In US 6,123,914, the intergrowth of EU-1 and EUO-NES type molecular sieves is disclosed for the removal of amorphous B and aluminum from the channels by using mild treatment with sodium hydroxide. The present invention relates to silica/alumina materials that do not contain boron.

US 7,459,073 discloses the use of a rigid template (N-cyclopentyl-1,4-diazabicyclo[2.2.2]octane cation (N-cyclopenyl-1,4-diabicyclo[2.2.2 ] octane cation)) prepared molecular sieve SSZ-47B, which is more expensive to produce and produces a zeolite with more EUO characteristics than other materials.

US 5,910,299 discloses ERS-10 zeolites prepared using a template such as 6-azspiro-[5,5]-undecane hydroxide. It is claimed to have a Si/ _Al2 ratio from 50 to pure silica. The present invention is prepared at a lower Si/ _Al2 ratio than ERS-10.

New materials containing EUO-NES-NON framework intergrowth for use in hydrocarbon processes were prepared.

Summary of the invention

As stated, the present invention relates to a new aluminosilicate zeolite called UZM-43 comprising EUO-NES-NON framework intergrowth. Accordingly, one embodiment of the present invention is a microporous crystalline zeolite having a _{three -} dimensional framework of at least AlO and SiO tetrahedral units and an empirical composition, as-synthesized and on anhydrous basis, represented by the following empirical formula:

where M represents sodium or a combination of sodium and potassium exchangeable cations, "m" is the M:(Al+E) molar ratio and is 0.05-5, R1 is a singly charged propyltrimethylammonium cation, and "r1" is R : (Al+E) molar ratio and have a value of 0.25-8.0, R2 is an amine, "r2" is R: (Al+E) molar ratio and has a value of 0.0-5, E is selected from gallium, iron, boron Elements of the group consisting of and mixtures thereof, "x" is the mole fraction of E and has a value of 0-1.0, "y" is the Si:(Al+E) molar ratio and is greater than 5 to 40, "z" is O : (Al+E) molar ratio and has a value determined by the following equation:

z=(m+r1+r2+3+4 y)/2

and characterized in that it has an x-ray diffraction pattern having at least the d-spacing and intensity described in Table A.

Table A

After calcination, the x-ray diffraction pattern shown in Table B was observed.

Form B

Another aspect of the invention is a method of preparing the material by using propyltrimethylammonium cation (SACHEM) or propyltrimethylammonium cation and an amine. The prior art SSZ-47 material is obtained by using N,N-dimethyl-3-azabicyclo[4.2.1]nonane cation or N,N-dimethyl-3-azabicyclo[3.2.1]octane Alkane cations are prepared, which are much more expensive and result in materials with more EUO character than those prepared by the present invention. ERS-10 was prepared with another expensive template, 6-azaspiro-[5,5]-undecane hydroxide and produced a zeolitic material with a higher Si/ _Al2 ratio than UZM-43.

Yet another embodiment of the present invention is a hydrocarbon conversion process using the above-mentioned zeolite. The process includes contacting a hydrocarbon with a zeolite under conversion conditions to obtain a converted hydrocarbon product. Hydrocarbon conversion processes include paraffin cracking, aromatics conversion such as xylene isomerization, toluene disproportionation, ring opening and cracking to remove benzene azeotropes and alkylation of aromatics with paraffins.

Brief description of the drawings

Figure 1 shows the layered structural units of the EUO-NES-NON family as shown perpendicular to (001).

Figure 2 shows a representation of the framework structure and the stacking order of (a) NON, (b) EUO and (c) NES as shown perpendicular to (100).

Detailed description of the invention

Applicants prepared a topology fitting EUO-NES-NON framework and similar to that described in the Atlas of Zeolite Framework Types maintained by the International Zeolite Association Structure Commission at http://topaz.ethz.ch/IZA-SC/StdAtlas.htm Aluminosilicate zeolites of the RUB-35, SSZ-47 and ERS-10 types. These new zeolites are called UZM-43. As shown in detail, UZM-43 differs from known zeolites by a number of features.

As shown in detail in the Examples, the UZM-43 material is thermally stable at temperatures of at least 600°C, and in another embodiment at least 800°C. As also shown in the Examples, the UZM-43 material can have a micropore volume greater than 60% as a percentage of the total pore volume.

UZM materials are prepared from reaction mixtures with compositions expressed in terms of molar ratios of oxides:

aM ₂ O:bR _2/p O:1-cAl ₂ O ₃ :cE ₂ O ₃ :dSiO ₂ :eH ₂ O

where "a" has a value from 0.05-5.0, "b" has a value from 1.5-40, "c" has a value from 0-1.0, "d" has a value from 4-40, and "e" has a value from 25-4000 . The source of M is selected from the group consisting of halide salts, nitrates, acetates, hydroxides, sulfates and mixtures thereof.

The source of E is selected from the group consisting of alkaline borates, boric acid, precipitated gallium hydroxide hydroxide, gallium sulfate, ferric sulfate, ferric chloride, and mixtures thereof. The source of aluminum is selected from the group consisting of aluminum isopropoxide, aluminum sec-butoxide, precipitated alumina, Al(OH) ₃ , aluminum metal and aluminum salts. The silicon source is selected from the group consisting of tetraethylorthosilicate, fumed silica, colloidal silica and precipitated silica. The reaction mixture is reacted at a temperature of 150-185° C. for a period of 1 day to 3 weeks. Preferably, the reaction mixture is reacted at a temperature of 165-175° C. for a period of 1 day to 3 weeks. R1 is a singly charged propyltrimethylammonium cation, "r1" is the R:(Al+E) molar ratio and has a value of 0.25-8.0, and R2 is an amine, r2 is morpholine. The method may further comprise adding UZM-43 seeds to the reaction mixture.

Example 1

The aluminosilicate reaction gel was prepared by first mixing 48.92g liquid sodium aluminate (LSA) (46.55% solution), 225.23g propyltrimethylammonium hydroxide (20% SACHEM), 36.11g morpholine (Aldrich) and 865.38 g of water, while stirring vigorously. After thorough mixing, 224.36g of Ultrasil VN SP 89% was added. After the addition was complete, the resulting mixture was homogenized for 1 hour and transferred to a 2-L Parr stainless steel stirred autoclave. The mixture was crystallized at 175°C for 160 hours with stirring at 250 RPM. The solid product was recovered by centrifugation, washed with deionized water and dried at 95°C. The product was identified as UZM-43 by XRD. Representative diffraction lines observed for this product are shown in Table 1. The composition of the product was determined by elemental analysis to consist of the following molar ratios: Si/Al=13.76, Na/Al=0.23. A portion of the material was calcined by raising the temperature to 600° C. for 2 hours, followed by 6 hours in air. The BET surface area is 176 m ² /g and the micropore volume is 0.07 cc/g. Scanning electron microscopy (SEM) showed crystals with a round (grape-like) shape smaller than 100 nm. The chemical analysis is as follows: 3.06% Al, 42.9% Si, 0.99% Na, N/Al=0.78, Na/Al=0.38, Si/Al ₂ =27. The diffraction lines observed for UZM-43 are shown in Table 1 below.

Table 1

Representative diffraction lines observed for calcined UZM-43 are shown in Table 2.

Table 2

Example 2

The aluminosilicate reaction gel was prepared by first mixing 48.92g liquid sodium aluminate (LSA) (46.55% solution), 225.23g propyltrimethylammonium hydroxide (20% SACHEM), 36.11g morpholine (Aldrich) and 865.38 g of water, while stirring vigorously. After thorough mixing, 224.36g of Ultrasil VN SP 89% was added. After the addition was complete, the resulting mixture was homogenized for 1 hour and transferred to a 2-L Parr stainless steel stirred autoclave. The mixture was crystallized at 175°C for 160 hours with stirring at 350 RPM. The solid product was recovered by centrifugation, washed with deionized water and dried at 95°C. The product was identified as UZM-43 by XRD. Representative diffraction lines observed for this product are shown in Table 3. The composition of the product was determined by elemental analysis to consist of the following molar ratios: Si/Al=13.5, Na/Al=0.38 and N/Al=0.78. A portion of the material was calcined by raising the temperature to 600° C. for 2 hours, followed by 6 hours in air. The BET surface area is 192 m ² /g and the micropore volume is 0.07 cc/g. Scanning electron microscopy (SEM) showed crystals with a circular shape smaller than 100 nm.

table 3

Example 3

An aluminosilicate reaction gel was prepared by first mixing 36.61 g liquid sodium aluminate (LSA) (46.55% solution), 24.3 g sodium hydroxide (50% solution) and 749.05 g water while stirring vigorously. After thorough mixing, 421.53 g of Propyltrimethylammonium bromide (25% SACHEM) was added followed by 167.99 g of Ultrasil VN SP 89%. After the addition was complete, the resulting reaction mixture was homogenized for 1 hour and transferred to a 2-L Parr stainless steel stirred autoclave. The mixture was crystallized at 175°C for 132 hours with stirring at 350 RPM. The solid product was recovered by centrifugation, washed with deionized water and dried at 95°C. The product was identified as UZM-43 by XRD. Representative diffraction lines observed for this product are shown in Table 4. The composition of the product was determined by elemental analysis to consist of the following molar ratios: Si/Al=13.05, Na/Al=0.34. A portion of the material was calcined by raising the temperature to 600° C. for 2 hours, followed by 6 hours in air. The BET surface area is 292 m ² /g and the micropore volume is 0.101 cc/g. Scanning electron microscopy (SEM) showed crystals with a circular shape smaller than 100 nm.

Table 4

Representative diffraction lines observed for calcined UZM-43 are shown in Table 5.

table 5

UZM-43 synthesized according to Examples 1 and 2 was formulated as a catalyst comprising 70% UZM-43 and 30% alumina. In catalyst preparation, Catapal B alumina was first peptized with nitric acid using 0.17 g _HNO3 per gram of Catapal B alumina. The peptized alumina was then added to the mortar while mixing until a mass with a texture suitable for extrusion was formed. The mass was then extruded to form a 1/16" diameter cylinder, which was dried overnight at 100°C and then fractionated into a length:diameter ratio of 3. The dry extrudate was flowed in an oven at 600°C Air calcination for ₅ hours to remove the template. _{The calcined} support was then exchanged at 75°C using a ₁₀ wt. The extrudate was dried at 120°C for 4 hours and then activated at 550°C.

For each sample listed in Table 1, the observed diffraction patterns were compared with the DIFFaX simulated patterns to obtain estimates of the αN and αS transition probabilities, which represent EUO, NES, and NON clustering tendencies. The percentages of EUO, NES and NON are calculated from the transition probabilities. The best fits to the simulations are summarized in Table 6.

Table 6

DIFFaX simulation results of test graph

Samples 1 and 2: The synthesized samples 1 and 2 have very similar diffraction patterns and can be matched to the same DIFFaX simulation. They all showed only a slight tendency to cluster in NES-like regions and an even slighter tendency to cluster in EUO- and NON-like regions, resulting in structures with slightly more EUOs and NONs than NES-like.

Sample 3: The synthesized Sample 3 has a slightly different diffractogram than the first two. This plot can be fitted with the simulated plot, showing that the sample contains slightly more NON features and less EUO features than the first two samples.

Regarding the diffraction of the prior art samples, the following observations were made.

ERS-10. Of the literature samples, ERS-10 has the most similar diffraction pattern to the present invention, but there are significant differences. The plot can be fitted with simulations, indicating a similar composition, but with slightly more EUO content and a higher Si/ _Al2 ratio than UZM-43.

The diffractograms of SSZ-47 are different from those of samples 1, 2 and 3 and are consistent with structures containing more NON features.

RUB-35 has the most different diffractograms from those illustrating the samples of the present invention. Its map is consistent with a structure with high EUO features. The wrong model in RUB-35 was developed thinking it was not clustering. Their best fit was to a structure characterized by 78% EUO type and 22% NON type. The model reported here yielded similar results (82% EUO, 12% NON, 8% NES) and indicated the presence of some NES-type features.

specific implementation plan

Along with a description of specific embodiments below, it should be understood that this description is intended to illustrate and not to limit the scope of the preceding description and appended claims.

One embodiment of the present invention relates to a hydrocarbon conversion process comprising contacting a hydrocarbon stream with a catalyst under hydrocarbon conversion conditions to obtain a conversion product, wherein the catalyst comprises a modified UZM-43 microporous crystalline zeolite, wherein the modified UZM-43 A three-dimensional framework with at least _AlO2 and _SiO2 tetrahedral units and an empirical composition expressed in anhydrous terms by the following empirical formula:

M _m +R1 _r1 R2 _r2 Al _1-x E _x Si _y O _z

where M represents sodium or a combination of sodium and potassium exchangeable cations, "m" is the M:(Al+E) molar ratio and is 0.05-5, R1 is a singly charged propyltrimethylammonium cation, and "r1" is R : (Al+E) molar ratio and have a value of 0.25-8.0, R2 is an amine, "r2" is R: (Al+E) molar ratio and has a value of 0.0-5, E is selected from gallium, iron, boron Elements of the group consisting of and mixtures thereof, "x" is the mole fraction of E and has a value of 0-1.0, "y" is the Si:(Al+E) molar ratio and is greater than 5 to 40, "z" is O : (Al+E) molar ratio and has a value determined by the equation z=(m+r1+r2+3+4 y)/2, and is characterized in that it has at least the d-spacing and intensity described in Table A The x-ray diffraction pattern of:

Table A

And is thermally stable at a temperature of at least 600°C and has a BET surface area of less than 420 m ² /g. An embodiment of the invention is one, any or all of the first embodiment in this paragraph through the previous embodiments in this paragraph, wherein the hydrocarbon conversion process is selected from the group consisting of alkylation, dealkylation, transalkylation of aromatics, Group consisting of isomerization of aromatics, alkylation of olefins with isoparaffins, dimerization of olefins, oligomerization of olefins, catalytic cracking and dewaxing. An embodiment of the present invention is one, any or all of the first embodiment in this paragraph through the previous embodiments in this paragraph, wherein the modified UZM-43 microporous crystalline zeolite has a composition comprising 33-34% by weight EUO, 24- EUO-NES-NON framework structure with 31 wt% NES and 34-43 wt% NON. An embodiment of the invention is one, any or all of the first embodiment in this paragraph through the previous embodiments in this paragraph, wherein the catalyst further comprises alumina.

Without further description, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Accordingly, the foregoing preferred specific embodiments are to be understood as illustrative only, and not limiting in any way to the remainder of the disclosure.

In the foregoing, unless otherwise indicated, all temperatures are described in °C and all parts and percentages are by weight.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

Claims (8)

1. A hydrocarbon conversion process comprising contacting a hydrocarbon stream with a catalyst under hydrocarbon conversion conditions to obtain a conversion product, wherein the catalyst comprises a modified UZM-43 microporous crystalline zeolite, wherein the modified UZM _- 43 has at least AlO and SiO ₂ The three-dimensional framework of the tetrahedral unit and the empirical composition represented by the following empirical formula in terms of anhydrous: M _m +R1 _r1 R2 _r2 Al _1-x E _x Si _y O _z where M represents sodium or a combination of sodium and potassium exchangeable cations, "m" is the M:(Al+E) molar ratio and is 0.05-5, R1 is a singly charged propyltrimethylammonium cation, and "r1" is R : (Al+E) molar ratio and have a value of 0.25-8.0, R2 is an amine, "r2" is R: (Al+E) molar ratio and has a value of 0.0-5, E is selected from gallium, iron, boron The elements of the group consisting of and mixtures thereof, "x" is the mole fraction of E and has a value of 0-1.0, "y" is the molar ratio of Si:(Al+E) and is greater than 5 and less than or equal to 40, "z" is O:(Al+E) molar ratio and has a value determined by the following equation: z=(m+r1+r2+3+4 y)/2 and characterized in that it has an x-ray diffraction pattern having at least the d-spacing and intensity described in Table A: Table A And is thermally stable at a temperature of at least 600°C, and has a BET surface area of less than 420 m ² /g. 2. The process according to claim 1, wherein the hydrocarbon conversion process is selected from the group consisting of alkylation, dealkylation, transalkylation of aromatics, isomerization of aromatics, olefin dimerization, olefin oligomerization, catalytic cracking and dewaxing group. 3. The method of claim 2, wherein alkylating comprises alkylating the olefin with an isoparaffin. 4. The process according to claim 1, wherein the hydrocarbon conversion process is aromatics conversion selected from the group consisting of xylene isomerization, toluene disproportionation, ring opening and cracking to remove benzene azeotropes and alkylation of aromatics with paraffins . 5. The method of claim 2, wherein the hydrocarbon conversion process is an alkylation process. 6. The method according to claim 2, wherein said hydrocarbon conversion process is a catalytic cracking process. 7. The method according to claim 1, wherein the modified UZM-43 microporous crystalline zeolite has an EUO-NES-NON framework comprising 33-34 wt% EUO, 24-31 wt% NES and 34-43 wt% NON structure. 8. The method of claim 1, wherein the catalyst further comprises alumina.