STATEMENT OF PRIORITY

[0001] This application claims priority to U.S. Application No. 14/636898 which was filed March 3, 2015, the contents of which are hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present invention relates to a new family of aluminosilicate zeolites. This family of zeolites are pentasil zeolites similar to MFI type zeolites, and is characterized by unique x-ray diffraction patterns and compositions and have catalytic properties for carrying out various hydrocarbon conversion processes.

BACKGROUND

[0003] Zeolites are crystalline aluminosilicate compositions which are microporous and which are formed from corner sharing A10 ₂ and Si0 ₂ tetrahedra. Numerous zeolites, both naturally occurring and synthetically prepared, are used in various industrial processes. Synthetic zeolites are prepared via hydrothermal synthesis employing suitable sources of Si, Al and structure directing agents such as alkali metals, alkaline earth metals, amines, or organoammonium cations. The structure directing agents reside in the pores of the zeolite and are largely responsible for the particular structure that is ultimately formed. These species balance the framework charge associated with aluminum and can also serve as space fillers. Zeolites are characterized by having pore openings of uniform dimensions, having a significant ion exchange capacity, and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without significantly displacing any atoms which make up the permanent zeolite crystal structure. Zeolites can be used as catalysts for hydrocarbon conversion reactions, which can take place on outside surfaces as well as on internal surfaces within the pore.

[0004] One particular zeolitic material, classified as ZSM-5, is disclosed in Beck, et al., U.S. Patent No. 6, 180,550, issued on Jan. 30, 2001. The zeolite comprises a synthetic porous crystalline material having a composition involving the molar relationship Χ ₂ 0 ₃ :(η)Υ0 ₂ , wherein X is a trivalent element, such as aluminum, boron, iron and/or gallium, preferably aluminum; Y is a tetravalent element such as silicon and/or germanium, preferably silicon; and n is less than 25, and Wherein the slope of the nitrogen sorption isotherm of the material at a partial pressure of nitrogen of 0.4 to 0.7 and a temperature of 77° K is greater than 30.

[0005] While there are many types of zeolites, new zeolites provide for improved reaction conditions in the conversion of lower value hydrocarbon streams to higher value hydrocarbon products.

SUMMARY

The present invention comprises a pentasil-layered zeolite having a microporous crystalline structure comprising a framework of A10 ₂ and Si0 ₂ tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of M _m ⁿ⁺ R _r ^p+ AlSiyO _z where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, "m" is the mole ratio of M to Al and varies from 0 to 3, R is at least one organo cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations, quaternary phosphonium cations, and methonium cations, "r" is the mole ratio of R to Al and has a value of 0.1 to 30, "n" is the weight average valence of M and has a value of 1 to 2, "p" is the weighted average valence of R and has a value of 1 to 2, "y" is the mole ratio of Si to Al and varies from greater than 32 to 200 and "z" is the mole ratio of O to Al and has a value determined by the equation z=(m n+r p+3+4 y)/2. An embodiment of the invention is one, any or all of prior

embodiments in this paragraph up through the first embodiment in this paragraph further characterized by the x-ray diffraction pattern having at least the d spacing and intensities set forth in the following Table A

Table A

23.10-23.18 3.83-3.84 vs

23.86-24.05 3.69-3.72 m

29.90-30.05 2.97-2.98 w

45.02-45.17 2.00-2.01 w

[0006] An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the zeolite has a microporous crystalline structure comprising a framework of A10 ₂ and Si0 ₂ tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of M _m ⁿ⁺ R _r ^p+ Ali _-x E _x Si _y O _z where "m" is the mole ratio of M to (Al+E) and varies from 0 to 3, "r" is the mole ratio of R to (Al+E) and has a value between 0.1 and 30, E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, "x" is the mole fraction of E and has a value from 0 to 1.0, "y" is the mole ratio of Si to (Al+E) and varies from greater than 32 to 200 and "z" is the mole ratio of O to (Al+E) and has a value determined by the equation z=(m n+r p+3+4 y)/2. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the zeolite has a mesopore surface area between 140 m ² /g and 400 m ² /g. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein M is selected from the group consisting of lithium, sodium, potassium, and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein M is a mixture of an alkali metal and an alkaline earth metal. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein R is selected from the group consisting of where R is selected from the group consisting of tetrabutyl ammonium hydroxide, tetrabutylphosphonium hydroxide, hexamethonium dihydroxide and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein R is a halide or hydroxide compound of an

organoammonium cation. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein R is a mixture of tetrabutylammonium cation and a quaternary ammonium cation. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the silica/alumina (Si/Al ₂ ) ratio is between 32 and 400.

[0007] An embodiment of the invention is a process for the production of a pentasil- layered zeolite catalyst, comprising forming a reaction mixture comprising reactive compounds M, R, Al and Si; and reacting the mixture at reaction conditions, wherein the reaction conditions include a temperature between 80°C and 150°C, and a reaction time between 10 hours and 5 days, to form a microporous crystalline structure comprising a framework of A10 ₂ and Si0 ₂ tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of M _m ⁿ⁺ R _r ^p+ AlSi _y O _z ; wherein the reactive compounds include M, a cation selected from the group consisting of alkali and alkaline earth metals; R, an organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations; and wherein "m" is the mole ratio of M to Al and varies from 0 to 3, "r" is the mole ratio of R to Al and has a value of between 0.1 and 30, "n" is the weight average valence of M and has a value of 1 to 2, "p" is the weighted average valence of R and has a value of 1 to 2, "y" is the mole ratio of Si to Al and varies from greater than 32 to 200 and "z" is the mole ratio of O to Al and has a value determined by the equation z=(m n+r p+3+4 y)/2. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through this embodiment in this paragraph further comprising the addition of reactive source E, wherein E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, to form a microporous crystalline structure comprising a framework of A10 ₂ and Si0 ₂ tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of M _m ⁿ⁺ R _r ^p+ Ali _-x E _x Si _y O _z ; wherein m" is the mole ratio of M to (Al+E) and varies from 0 to 1, "r" is the mole ratio of R to (Al+E) and has a value between 0.1 and 30, "n" is the weight average valence of M and has a value of 1 to 2, "p" is the weighted average valence of R and has a value of 1 to 2, "x" is the mole fraction of E and has a value from 0 to 1.0, "y" is the mole ratio of Si to (Al+E) and varies from greater than 32 to 200 and "z" is the mole ratio of O to (Al+E) and has a value determined by the equation z=(m n+r p+3+4 y)/2. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through this embodiment in this paragraph where R is selected from the group consisting of tetrabutyl ammonium hydroxide, tetrabutylphosphonium hydroxide and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through this embodiment in this paragraph wherein R is a halide or hydroxide compound of an organoammonium cation. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through this embodiment in this paragraph where R is a mixture of tetrabutylammonium hydroxide and a quaternary ammonium cation. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through this embodiment in this paragraph where M is selected from the group consisting of sodium, potassium, and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through this embodiment in this paragraph where the reaction mixture is reacted at a temperature between 100°C and 125°C. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through this embodiment in this paragraph where the reaction mixture is reacted at a temperature between 110°C and 150°C.

[0008] Another, or second embodiment of the process of making the zeolite, is a process for the production of a pentasil MFI/MEL-layered zeolite catalyst having a 2-D structure, comprising forming a reaction mixture containing reactive sources of M, R, Al, and Si; and reacting the reaction mixture at reaction conditions of 80°C to 150°C for a period of time of between 10 hours and 5 days the reaction mixture having the a composition expressed in terms of mole ratios of the oxides of aM _2/n ObRi _2/n OcR _{2 2/n} Al ₂ 03eSi0 ₂ hH ₂ 0; wherein the reactive compounds include M, a cation selected from the group consisting of alkali, alkaline earth metals and mixtures thereof; R, an organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations and mixtures thereof; Al in the form of A1 ₂ 0 ₃ ; and Si in the form of Si0 ₂ ; and wherein "a" has a value of 0.1 to 3, "b" has a value of 1 to 30, "c" has a value of 0 to 1, "e" has a value of 64 to 400 and "h" has a value of 50 to 1000. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising forming the reaction mixture with reactive source E, wherein E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof; and reacting the reaction mixture at reaction conditions of 85°C to 225°C for a period of time of 1 day to 15 days the reaction mixture having the a composition expressed in terms of mole ratios of the oxides of aM _2/n ObRi _2/n OcR _{2 2/n} l-dAl ₂ 0 ₃ dE ₂ 0 ₃ eSi0 ₂ hH ₂ 0; wherein "a" has a value of 0.1 to 3, "b" has a value of 1 to 30, "c" has a value of 0 to 1, "d" has a value of 0 to 1, "e" has a value of 64 to 400 and "h" has a value of 50 to 1000.

[0009] Other objects, advantages and applications of the present invention will become apparent to those skilled in the art from the following detailed description.

DETAILED DESCRIPTION

[OOIO] A new family of zeolitic materials has been successfully prepared. The topology of this zeolite is unique as determined by its x-ray diffraction spectrum. The structure is related to MFI/MEL class of zeolite framework types.

[OOl 1] There are many allotropes for zeolites having similar chemical formulae. The different allotropes can have very different physical and chemical properties, and can lead to many different uses. The easiest example is to look at the allotropes of carbon, a single type of atom but with many different structures, that leads to materials having, in some cases, diametrically opposed properties. Likewise for the allotropes of many zeolites, the discovery of new allotropes can be unexpected and their properties can also be unexpected and subsequently can lead to new uses from those properties.

[0012] For industrial catalytic application there is a need for zeolite of high external surface areas. Applicants have successfully prepared this new family of pentasil zeolites similar to MFI/MEL type zeolites. The materials are prepared via the use of a single commercially available structure directing agent, such as tetrabutylammonium hydroxide, using the Charge Density Mismatch Approach to zeolite synthesis (U.S. Pat. No. 7,578,993). The organoammonium compounds used to make this pentasil zeolite are non-cyclic or contain cyclic substituents and are generally quite simple. Examples of organoammonium compounds used to make this pentasil zeolite include tetrabutylammonium (TBA) and tetrabutylphosphonium (TBP) cation

[0013] The present invention is a new pentasil layer zeolite and forms a porous structure that has a mesopore surface area between 140 m ² /g and 400 m ² /g. The zeolite has a microporous crystalline structure comprising a framework of A10 ₂ and Si0 ₂ tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:

M _m ⁿ⁺ R _r ^p+ AlSi _y O _z . [0014] In the formula, M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, "m" is the mole ratio of M to Al and varies from 0 to 3, R is at least one organo cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations, quaternary phosphonium cations, and methonium cations, "r" is the mole ratio of R to Al and has a value of 0.1 to 30, "n" is the weight average valence of M and has a value of 1 to 2, "p" is the weighted average valence of R and has a value of 1 to 2, "y" is the mole ratio of Si to Al and varies from greater than 32 to 200 and "z" is the mole ratio of O to Al and has a value determined by the equation:

z = (m n + rp + 3 + 4 y)/2.

[0015] The zeolite is further characterized in that it has the x-ray diffraction pattern having at least the d spacing and intensities set forth in Table A:

Table A

[0016] The zeolite can be seen as characterized by the very strong peak in the x-ray diffraction pattern at 2Θ from 23.10-23.18.

[0017] In one embodiment, the zeolite can be formed with a metal E. The zeolite forms a microporous crystalline structure and has the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:

M _m ⁿ⁺ R _r ^p+ Al _1-x E _x Si _y O _z where "m" is the mole ratio of M to (Al+E) and varies from 0 to 3, "r" is the mole ratio of R to (Al+E) and has a value of 0.1 to 30, E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, "x" is the mole fraction of E and has a value from 0 to 1.0, "y" is the mole ratio of Si to (Al+E) and varies from greater than 32 to 200 and "z" is the mole ratio of O to (Al+E) and has a value determined by the equation:

z = (m n + rp + 3 + 4 y)/2. [0018] The metal M can be a mixture of alkali metals and alkaline earth metals, with a preferred metal or metal combination comprising one or more of lithium, sodium and potassium. The organo cation can comprise an organoammonium ion such as

tetrabutyl ammonium cation, or an organophosphonium ion such as tetrabutylphosphonium cation, or a methonium ion such as hexamethonium cation. These can be selected for the reaction mixture to form the zeolite from tetrabutyl ammonium hydroxide,

tetrabutylphosphonium hydroxide, and hexamethonium dihydroxide. The R can be selected from a mixture of quaternary organoammonium cations. The R can be a halide or a hydroxide of the organoammonium cation. A preferred R comprises a mixture of tetrabutyl ammonium cation and a quaternary ammonium cation.

[0019] The pentasil zeolite formed will have a silica to alumina ratio (Si/Al ₂ ) ratio is between 32 and 400.

[0020] The pentasil-zeolite is formed by creating a reaction mixture comprising reactive compounds having M, R, Al and Si. The reaction mixture is reacted under reaction conditions that include a temperature between 80°C and 150°C, and a reaction time between 10 hours and 5 days. This forms a microporous crystalline structure comprising a framework of A10 ₂ and S1O ₂ tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:

M _m ⁿ⁺ R _r ^p+ AlSi _y O _z .

[0021] The process can further include adding the additional reactive source E, wherein E is an element selected from one or more of the metals: gallium, iron, boron and indium to form the structure with the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:

M _m ⁿ⁺ R _r ^p+ Al _1-x E _x Si _y O _z .

[0022] The reaction temperature is preferred to be between 100°C and 125°C, or with a preferred reaction temperature between 110°C and 150°C.

[0023] In one embodiment, the process to produce the zeolite includes forming a reaction mixture with the reactive sources of M, R, Al, and Si. The mixture is reaction at a temperature between 80°C to 150°C for a period of time of between 10 hours and 5 days and the reaction mixture has a composition expressed in terms of mole ratios of the oxides of: aM _2/n O:bRi _2/n O:cR _{2 2/n} : Al ₂ 0 ₃ :eSi0 ₂ :hH ₂ 0.

[0024] The reactive sources include M, a cation selected from alkali or alkaline earth elements; R an organoammonium cation; Al in the form of A1 ₂ 0 ₃ ; and Si in the form of Si0 ₂ . In the mixture, the value of "a" is between 0.1 and 3, the value of "b" is between 1 and 30, the value of "c" is between 0 and 1, the value of "e" is between 64 and 400, and the value of "h" is between 50 and 1000.

[0025] The process can further include adding the additional reactive species E, wherein E is one or more elements from gallium, iron, boron and indium. The reaction conditions include a temperature between 85°C and 225°C for a period from 1 day to 15 days. The reaction mixture has a composition expressed in terms of mole ratios of the oxides of:

aM _2/n O:bRi _2/n O:cR _{2 2/n} : l-dAl ₂ 0 ₃ :dE ₂ 0 ₃ :eSi0 ₂ :hH ₂ 0; wherein "a" has a value of 0.1 to 3, "b" has a value of 1 to 30, "c" has a value of 0 to 1, "d" has a value of 0 to 1, "e" has a value of 64 to 400 and "h" has a value of 50 to 1000.

EXAMPLE 1 [0026] An aluminosilicate reaction solution was prepared by first mixing 13.15 g of aluminum tri-sec-butoxide (95 ⁺ %), 777.62 g tetrabutylammonium hydroxide (55 mass-% solution), and 700 g of ice water mixture while stirring vigorously. After thorough mixing, 1167.98 g tetraethyl orthosilicate was added. The reaction mixture was homogenized for an additional hour with a high speed mechanical stirrer. A composite aqueous solution containing 2.75 g of NaOH dissolved in 137.7 g distilled water was added, drop-wise, to the aluminosilicate solution. After the addition was completed, the resulting reaction mixture was homogenized for 1 hour, transferred to a 2000 ml Parr stainless steel autoclave which was heated to 115°C and maintained at that temperature for 59 hrs. The solid product was recovered by centrifugation, washed with de-ionized water, and dried at 80°C.

[0027] The product was identified as a pentasil zeolite by powder x-ray diffraction.

Representative diffraction lines observed for the product are shown in Table 1. The product composition was determined by elemental analysis to consist of the following mole ratios: Si/Al = 59.8, Na/Al = 0.82. A portion of the material was calcined by ramping to 560°C for 5 hours followed by an 8 hour dwell in air. The BET surface area was 697 m ² /g, the micropore area was 474 m ² /g, the mesopore area was 223 m ² /g, the micropore volume was 0.253cc/g, and mesopore volume was 0.953 cc/g. Scanning Electron Microscopy (SEM) revealed clusters of nano spheres of less than 20 nm. Chemical analysis was as follows: 0.74% Al, 46.0% Si, and 0.52% Na, Na/Al=0.82, Si/Al ₂ =l 19.

TABLE 1

EXAMPLE 2

[0028] An aluminosilicate reaction solution was prepared by first mixing 13.87 g of aluminum tri-sec-butoxide (95 ⁺ %), 386.39 g tetrabutylammonium hydroxide (55 mass-% solution), and 300 g of ice water mixture while stirring vigorously. After thorough mixing, 580.35 g tetraethyl orthosilicate was added. The reaction mixture was homogenized for an additional hour with a high speed mechanical stirrer. A composite aqueous solution containing 2.73 g of NaOH dissolved in 116.67 g distilled water was added, drop-wise, to the aluminosilicate solution. After the addition was completed, the resulting reaction mixture was homogenized for 1 hour, transferred to a 2000 ml Parr stainless steel autoclave which was heated to 115°C and maintained at that temperature for 57 hrs. The solid product was recovered by centrifugation, washed with de-ionized water, and dried at 80°C.

[0029] The product was identified as a pentasil zeolite by powder x-ray diffraction.

Representative diffraction lines observed for the product are shown in Table 2. The product composition was determined by elemental analysis to consist of the following mole ratios: Si/Al = 24.9, Na/Al = 0.92. A portion of the material was calcined by ramping to 560°C for 5 hours followed by a 8 hour dwell in air. The BET surface area was 517 m ² /g, the micropore area was 258 m ² /g, the mesopore area was 259 m ² /g, the micropore volume was 0.135 cc/g, and mesopore volume was 0.94 cc/g. Scanning Electron Microscopy (SEM) revealed clusters of nano spheres of less than 20 nm. Chemical analysis was as follows: 1.73% Al, 44.9% Si, and 1.37% Na, Na/Al=0.93, Si/Al ₂ =49.8.

TABLE 2

EXAMPLE 3

[0030] An aluminosilicate reaction solution was prepared by first mixing 13.73 g of aluminum tri-sec-butoxide (95 ⁺ %), 559.89 g tetrabutylphosphonium hydroxide (40 mass- % solution), and 200 g of ice water mixture while stirring vigorously. After thorough mixing, 574.76 g tetraethyl orthosilicate was added. The reaction mixture was homogenized for an additional hour with a high speed mechanical stirrer. A composite aqueous solution containing 2.70 g of NaOH dissolved in 48.92 g distilled water, was added, drop-wise, to the aluminosilicate solution. After the addition was completed, the resulting reaction mixture was homogenized for 1 hour, transferred to a 2000 ml Parr stainless steel autoclave which was heated to 115°C and maintained at that temperature for 120 hrs. The solid product was recovered by centrifugation, washed with de-ionized water, and dried at 80°C.

[0031] The product was identified as a pentasil zeolite by powder x-ray diffraction.

Representative diffraction lines observed for the product are shown in Table 3. The product composition was determined by elemental analysis to consist of the following mole ratios: Si/Al = 33.78, Na/Al = 0.67. A portion of the material was calcined by ramping to 560°C for 5 hours followed by a 8 hour dwell in air. The BET surface area was 526 m ² /g, the micropore area was 220 m ² /g, the mesopore area was 306 m ² /g, the micropore volume was 0.115 cc/g, and mesopore volume was 0.99 cc/g. Scanning Electron Microscopy (SEM) revealed clusters of nano spheres of less than 20 nm. Chemical analysis was as follows: 1.22% Al, 42.8% Si, and 0.70% Na, Na/Al=0.67, Si/Al ₂ =67.5. TABLE 3

EXAMPLE 4

[0032] An aluminosilicate reaction solution was prepared by first mixing 2.17 g of aluminum tri-sec-butoxide (95 ⁺ %), 362.46 g tetrabutylammonium hydroxide (55 mass-% solution), and 300 g of water ice while stirring vigorously. After thorough mixing, 544.42 g tetraethyl orthosilicate was added. The reaction mixture was homogenized for an additional hour with a high speed mechanical stirrer. A composite aqueous solution containing 0.85 g of NaOH dissolved in 90.10 g distilled water was added, drop-wise, to the aluminosilicate solution. After the addition was completed, the resulting reaction mixture was homogenized for 1 hour, transferred to a 2000 ml Parr stainless steel autoclave which was heated to 115°C and maintained at that temperature for 48 hrs. The solid product was recovered by centrifugation, washed with de-ionized water, and dried at 80°C.

[0033] The product was identified as a pentasil zeolite by powder x-ray diffraction. Representative diffraction lines observed for the product are shown in Table 4. The product composition was determined by elemental analysis to consist of the following mole ratios: Si/Al = 202, Na/Al = 1.33. A portion of the material was calcined by ramping to 560°C for 5 hours followed by an 8 hour dwell in air. The BET surface area was 567 m ² /g, the micropore area was 206 m ² /g, the mesopore area was 361 m ² /g, the micropore volume was 0.1 lcc/g, and mesopore volume was 0.92 cc/g. Scanning Electron Microscopy (SEM) revealed clusters of nano spheres of less than 20 nm. Chemical analysis was as follows: 0.22% Al, 46.2% Si, and 0.22% Na, Na/Al=1.33, Si/Al ₂ =404. TABLE 4

[0034] While the invention has been described with what are presently considered the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.