WO2017158415A1

WO2017158415A1 - Tetraethyl ammonium hydroxide templated meapso molecular sieve catalysts for conversion of alkyl chlorides to olefins

Info

Publication number: WO2017158415A1
Application number: PCT/IB2016/057900
Authority: WO
Inventors: Dustin FICKEL; Neeta Kulkarni
Original assignee: Sabic Global Technologies B.V.
Priority date: 2016-03-16
Filing date: 2016-12-21
Publication date: 2017-09-21

Abstract

Disclosed are methods and systems of catalyzing the reaction of alkyl halides to light olefins using a TEAOH templated MeAPSO-34 molecular sieve catalyst. These methods and systems have been shown to have maximum combined selectivity of ethylene and propylene of at least 70% or 90% to 98%.

Description

TETRAETHYL AMMONIUM HYDROXIDE TEMPLATED MeAPSO MOLECULAR SIEVE CATALYSTS FOR CONVERSION OF ALKYL CHLORIDES TO OLEFINS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Patent Application No. 62/309, 130 filed March 16, 2016, and U.S. Provisional Patent Application No. 62/366,894 filed July 26, 2016. The entire contents of each of the above-referenced disclosures are specifically incorporated herein by reference without disclaimer.

BACKGROUND OF THE INVENTION

A. Field of the Invention [0002] The invention generally concerns the use of tetraethyl ammonium hydroxide templated metal incorporated silicoaluminophosphate (MeAPSO) molecular sieve catalysts to catalyze the reaction of alkyl halides to light olefins.

B. Description of Related Art

[0003] Light olefins such as ethylene and propylene are used by the petrochemical industry to produce a variety of key chemicals that are then used to make numerous downstream products. By way of example, both of these olefins are used to make a multitude of plastic products that are incorporated into many articles of manufacture. FIGS. 1 A and IB provide examples of products generated from ethylene (FIG. 1 A) and propylene (FIG. IB).

[0004] Methane activation to higher hydrocarbons, especially to light olefins, has been the subject of great interest over many decades. Recently, the conversion of methane to light olefins via a two-step process that includes conversion of methane to methyl halide {e.g., methyl chloride) followed by conversion of the methyl halide to light olefins has attracted great attention. Micro pore zeolite {e.g., ZSM-5) or zeolite type catalysts {e.g., SAPO-34) have been commonly employed for methyl chloride (or other methyl halide) conversion reactions. However, the selectivity to a desired olefin {e.g., propylene), rapid catalyst deactivation due to carbon deposition (coking), and the synthesis cost of the catalyst remain the major challenges for scale-up and commercial success of the reaction.

[0005] SAPO catalysts have an open microporous structure with regularly sized channels, pores or "cages." These materials are sometimes referred to as "molecular sieves" in that they have the ability to sort molecules or ions based primarily on the size of the molecules or ions. SAPO materials are both microporous and crystalline, and have a three-dimensional crystal framework of P0₄ ⁺, A10₄ ^" and Si0₄ tetrahedra. SAPO-34 and MeSAPO-34 catalysts have been prepared by a range of methods. Various synthetic methods using templates have been employed to prepare SAPO molecular sieves and metal incorporated SAPO molecular sieves. By way of example, Razavian et al. in "Recent Advances in Silicoaluminophosphate Nanocatalysts Synthesis Techniques and Their Effects on Particle Size Distribution, Reviews on Advancement of Material Science, 2011, Vol. 29, pp. 83-99 describes various templating agents to make SAPO-34 catalysts. MeAPSO molecular sieves with a RHO framework for a gas absorption process are described in U.S. Patent Application Publication No. 20150147269 to Tian et al. Other references that use amines as the templating agent to make MeAPSO molecular sieves include Chinese Patent No. 100448537 to Wei et al. and U.S. Patent Application Publication No. 20100310440 to Bull et al. The templating agent used in each of these references was morpholine or mixtures that include morpholine.

[0006] MnAPSO made using triethylamine as a templating agent has been used in chloromethane to olefin reactions {See, for example, Wei et al., in "Study of Mn incorporation into SAPO framework: Synthesis characterization and catalysis in chloromethane conversion to light olefins", Microporous and Mesoporous Materials 2006, Vol. 90, pp. 188-197). The produced crystals in Wei et al. were larger than SAPO-34 crystals prepared under the same conditions. This catalyst suffered from loss of activity after sixty minutes of time on stream.

SUMMARY OF THE INVENTION

[0007] A discovery has been made that addresses the problems {e.g., low catalytic activity and fast deactivation) associated with using SAPO-34 catalysts in alkyl halide to olefin reactions. The discovery is premised on a metal incorporated SAPA-34 (MeAPSO-34, where Me is the total metal) catalyst prepared using tetraethylammonium hydroxide (TEAOH) as the templating agent, which results in a catalyst having a small particle size {e.g., 200 nm to 1000 nm or 200 nm to 500 nm, or less than 1000 nm) when compared with MeAPSO-34 made using other amine templating agents or mixtures of templating agents. Surprisingly, using TEAOH resulted in catalyst particles of comparatively smaller size than the prior art (see, e.g., FIGS. 3-5). Further, these smaller sized catalysts of the present invention had commercially relevant activity and conversion and selectivity properties when used in the alkyl halide to light olefin reaction process. Therefore, the catalysts of the present invention offer a more efficient and scalable product for the alkyl halide to light olefin (e.g., C₂ to C₄ olefins) reaction process. [0008] In one aspect of the present invention, there is disclosed a method for converting an alkyl halide to an olefin, the method includes contacting a tetraethylammonium hydroxide (TEAOH) templated metal silicoaluminophosphate-34 (MeAPSO-34) catalyst with a feed including an alkyl halide (e.g., methyl halide or methyl chloride) under reaction conditions sufficient to produce an olefin hydrocarbon product that includes olefins. The metal in the MeAPSO-34 is incorporated into the SAPO-34 framework. The metal can be manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof, preferably manganese, tin, manganese and iron, manganese and germanium, manganese and tin, or tin and iron. The TEOH templated MeAPSO-34 catalyst can be the reaction product of heat treatment of a synthesis mixture having a molar composition of: aAl:6Si:cP:i¾0:eTEAOH:/ e_xO_y where 0 < α≤1, 0 < 6≤1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 <f< 1, x is 1 to 2, and_y is 1 to 3. In one instance, a is 1, b is 0.4, c is 1, d is 60, e is 2 and / is 0.05 or 0.1. Heat treatment can include (a) heating the synthesis mixture to obtain a crystalline material; and (b) calcining the crystalline material. In some aspects, the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt.% alcohol, or preferably is alcohol free. The olefins can include C₂-C₄ olefins and the maximum combined selectivity of ethylene and propylene can be at least 70%, preferably at least 80%), or more preferably 90%> to 98%>, the maximum combined space time yield of ethylene and propylene can be at least 1/hr or 1/hr to 3/hr; and the maximum conversion of alkyl halide can be at least 80%> or 85%> to 100%>. Maximum selectivity of ethylene can be 40%) to 55%) and the maximum selectivity of propylene can be 30%> to 45%>. The produced olefin hydrocarbon product can be collected, stored, transported, or combinations thereof. Reaction conditions for the conversion of an alkyl halide to olefins can include an average temperature from 300 °C to 500 °C, an average pressure of 0.5 MPa or less, and a weighted hourly space velocity (WHSV) of 0.5 to 10 h^"1.

[0009] In certain aspects of the method, the reaction for converting an alkyl halide to an olefin occurs in a fluid catalytic cracking (FCC) process or reactor or fluidized circulating bed process or reactor. The method can further include collecting or storing the produced olefin hydrocarbon product and using the produced olefin hydrocarbon product to produce a petrochemical or a polymer. The method can also include regenerating the used/deactivated catalyst in a continuous process such as a FCC-type process or reactor or a circulating catalyst bed process or reactor. [0010] In some embodiments, a catalyst capable of catalyzing an alkyl halide to olefin reaction is described. The catalyst can have the general formula of _eTEAOH(Me Si_aAl_¾P_c)0₂, where: Me is manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof and Me is incorporated into the framework of the catalyst; e is the molar amount of tetraethylammonium hydroxide (TEOH) per mole of (Me Si_aAl¾P_c)0₂; and a, b, and c are the molar fractions of metal, silicon, aluminum, and phosphorous respectively, where 0 < e < 4, 0 </< l, 0 < α <1, 0 < ό < 1, 0 < c < l, and the sum off, a, b, and c is equal to 1. The catalyst can be in particulate form and have an average particle size of 200 to 1000 nm or 200 nm to 500 nm. Surprisingly, it was found that the TEAOH templated catalyst had a particle size less than the particle size of a triethyl amine templated MeAPSO-34 catalyst or SAPO-34 catalyst. In one embodiment, the catalyst can have a formula of (Sn_/Si_aAl_¾P_c)0₂, where a, b, and c are the molar fractions of tin, silicon, aluminum, and phosphorous respectively, where 0 </< l, 0 < a <l, 0 < 0 < l, 0 < c < l, and the sum off, a, b, and c is equal to 1.

[0011] Methods of making the catalyst of the present invention are also described. A method can include (a) heating a synthesis mixture having has a molar composition of: aAl:6Si:cP:<¾0:eTEAOH:/ e_xO_y where 0 < a < 1, 0 < b < 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 </< l, is l to 2 and y is 1 to 3 to obtain a crystalline material; and (b) calcining the crystalline material (e.g., heating the crystalline material in air at a temperature of 450 °C to 600 °C). Heating the synthesis mixture can include hydrothermally crystallizing the synthesis mixture at 180 °C to 210 °C for 18 to 48 hours under autogenous pressure; and drying the mixture at 90 °C to 110 °C.

[0012] In another embodiment of the present invention there is disclosed a system for producing olefins. The system can include an inlet for a feed including the alkyl halide, a reaction zone that is configured to be in fluid communication with the inlet, and an outlet configured to be in fluid communication with the reaction zone to remove an olefin hydrocarbon product from the reaction zone. The reaction zone can include the feed and the TEAOH templated MeAPSO-34 catalyst described above and in the specification. During use, the reaction zone can further include a FCC-type reactor or a circulating catalyst bed reactor, and a collection device that is capable of collecting the olefin hydrocarbon product.

[0013] In the context of the present invention 20 embodiments are described. Embodiment 1 describes a method for converting an alkyl halide to an olefin. The method can include contacting a tetraethylammonium hydroxide (TEAOH) templated metal silicoaluminophosphate-34 (MeAPSO-34) catalyst with a feed comprising an alkyl halide under reaction conditions sufficient to produce an olefin hydrocarbon product comprising olefins, wherein the metal (Me) is incorporated into the SAPO-34 framework. Embodiment 2 is the method of embodiment 1, wherein the incorporated metal (Me) is manganese (Mn), magnesium (Mg), cobalt (Co), nickel (Ni), iron (Fe), copper (Cu), zinc (Zn), tin (Sn), germanium (Ge), titanium (Ti), rhenium (Re), or any combination thereof, preferably manganese, tin, manganese and iron, manganese and germanium, manganese and tin, or tin and iron. Embodiment 3 is the method of any one of embodiments 1 to 2, wherein the olefins are C₂ to C₄ olefins. Embodiment 4 is the method of embodiment 3, wherein the maximum combined selectivity of ethylene and propylene is at least 70%, preferably at least 80%, or more preferably 90% to 98%, the maximum combined space time yield of ethylene and propylene is at least 1/hr or 1/hr to 3/hr, and the maximum conversion of alkyl halide is at least 80% or 85% to 100%. Embodiment 5 is the method of embodiment 4, wherein the maximum selectivity of ethylene is 40% to 55%, and the maximum selectivity of propylene is 30% to 45%. Embodiment 6 is the method of any one of embodiments 1 to 5, wherein the reaction conditions include a temperature from 300 °C to 500 °C, a pressure of 0.5 MPa or less, and a weighted hourly space velocity (WHSV) of 0.5 to 10 h^"1. Embodiment 7 is the method of any one of embodiments 1 to 5, wherein the TEAOH templated MeAPSO-34 catalyst is the reaction product of heat treatment of a synthesis mixture having a molar composition of: aAl₂0₃:6Si0₂:cP₂0₅:^₂0:eTEAOH:/ e_xO_y; where 0 < α≤ 1, 0 < 6≤ 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 < f < 1, x is 1 to 2, and y is 1 to 3. Embodiment 8 is the method of embodiment 7, wherein a is 1, b is 0.4, c is I, d is 60, e is 2 and /is 0.05 or 0.1. Embodiment 9 is the method of embodiment 7, wherein the heat treatment comprises: (a) heating the synthesis mixture to obtain a crystalline material; and (b) calcining the crystalline material. Embodiment 10 is the method of any one of embodiments 1 to 9, wherein the alkyl halide is a methyl halide, preferably methyl chloride. Embodiment 1 1 is the method of any one of embodiments 1 to 10, wherein the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt. % alcohol, or preferably is alcohol free. Embodiment 12 is the method of any one of embodiments 1 to 11, wherein the reaction occurs in a fixed feed reactor, a fluid catalytic cracking (FCC) reactor or fluidized circulating bed reactor. Embodiment 13 is the method of any one of embodiments 1 to 12, further comprising collecting or storing the produced olefin hydrocarbon product. [0014] Embodiment 14 is a catalyst capable of catalyzing an alkyl halide to an olefin reaction, the catalyst having a general formula of _eTEAOH(Me/Si_aAl_¾P_c)0₂, where Me is manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof and Me is incorporated into the framework of the catalyst, e is the molar amount of tetraethylammonium hydroxide (TEAOH) per mole of (Me Si_aAl¾P_c)0₂ and a, b, and c are the molar fractions of metal, silicon, aluminum, and phosphorous respectively and 0 < e < 4, 0 <f< 1, 0 < a < 1, 0 < b < 1, 0 < c < 1, and f+a+b+c = 1, wherein the catalyst is capable of catalyzing an alkyl halide to olefin reaction. Embodiment 15 is the catalyst of embodiment 14, having an average particle size of 200 nm to 1000 nm or 200 nm to 500 nm. Embodiment 16 is the catalyst of any one of embodiments 14 to 15, wherein the particle size of the catalyst is less than the particle size of a triethyl amine templated catalyst and/or a mixed templated catalyst.

[0015] Embodiment 17 is a system for producing olefins, the system comprising: an inlet for a feed comprising an alkyl halide; a reaction zone that is configured to be in fluid communication with the inlet, wherein the reaction zone comprises the feed and the catalyst of any one of embodiments 14 to 16; and an outlet configured to be in fluid communication with the reaction zone to remove an olefin hydrocarbon product from the reaction zone. Embodiment 18 is the system of embodiment 17, wherein the reaction zone includes a fluid catalytic cracking (FCC)-type reactor or a circulating catalyst bed reactor. Embodiment 19 is the system of any one of embodiments 17 to 18, further comprising a collection device that is capable of collecting the olefin hydrocarbon product. Embodiment 20 is a method of making the catalyst of any one of embodiments 14 to 16, the method comprising: (a) heating a synthesis mixture to obtain a crystalline material; and (b) calcining the crystalline material, wherein the synthesis mixture has a molar composition of aAl₂03:*Si02:cP₂05:<iH20:eTEAOH^Me_xO_y where 0 < a < 1, 0 < b < 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 <f< 1, x is 1 to 2, and^ is 1 to 3.

[0016] The following includes definitions of various terms and phrases used throughout this specification. [0017] The term "catalyst" means a substance which alters the rate of a chemical reaction. "Catalytic" means having the properties of a catalyst.

[0018] The term "conversion" means the mole fraction (i.e., percent) of a reactant converted to a product or products. [0019] The term "selectivity" refers to the percent of converted reactant that went to a specified product, for example C2-C4 olefin selectivity is the % of alkyl halide that formed C2-C4 olefins.

[0020] The term "about" or "approximately" are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0021] The term "substantially" and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0022] The terms "wt.%", "vol.%", or "mol.%" refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.

[0023] The terms "inhibiting" or "reducing" or "preventing" or "avoiding" or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0024] The term "effective," as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0025] The use of the words "a" or "an" when used in conjunction with any of the terms "comprising," "including," "containing," or "having" in the claims or the specification may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."

[0026] The words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0027] The catalysts of the present invention can "comprise," "consist essentially of," or "consist of particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase "consisting essentially of," in one non- limiting aspect, a basic and novel characteristic of the catalysts of the present invention are their size {e.g., 200 nm to 1000 nm or 200 nm to 500 nm, or less than 1000 nm) as well as their ability to selectivity produce light olefins, and in particular, ethylene and propylene, from alkyl halides {e.g., methyl chloride).

[0028] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIGS 1A and IB depict illustrations of various chemicals and products that can be produced from ethylene (FIG. 1 A) and propylene (FIG. IB).

[0030] FIG. 2 depicts a system for producing olefins from alkyl halides using the catalyst of the present invention.

[0031] FIGS. 3A and 3B are SEM images of crystals of TEAOH templated MnAPSO-34 catalyst of the present invention at various magnifications. [0032] FIG. 4 is an SEM image of crystals of TEAOH templated FeAPSO-34 catalyst of the present invention.

[0033] FIG. 5 is an SEM image of crystals of TEA templated MnAPSO-34 catalyst of the prior art. [0034] FIG. 6 shows graphs of percent CH₃C1 conversion of the TEAOH templated catalysts of present invention and the comparative catalyst (SAPO-34).

[0035] FIG. 7 shows graphs of percent CH₃CI conversion of the TEAOH templated catalysts 2 and 3 (MnAPSO-34) of present invention and the comparative catalyst (SAPO- 34).

[0036] FIG. 8 shows graphs of CH₃CI conversion, ethylene selectivity, propylene selectivity and methane selectivity of the catalyst 2 (MnAPSO-34) of present invention and the comparative catalyst (SAPO-34).

[0037] FIG. 9 shows graphs of CH₃CI conversion, ethylene selectivity, and propylene selectivity of the catalyst 8 (SnAPSO-34) of present invention and the comparative catalyst (SAPO-34).

[0038] FIG. 10 shows graphs of CH₃CI conversion, ethylene selectivity, and propylene selectivity of the catalyst 10 (TiAPSO-34) of present invention and the comparative catalyst (SAPO-34). [0039] FIG. 11 shows graphs of CH₃CI conversion, ethylene selectivity, and propylene selectivity of the catalyst 1 1 (ReAPSO-34) of present invention and the comparative catalyst (SAPO-34).

DETAILED DESCRIPTION OF THE INVENTION

[0040] While currently available SAPO-34 catalysts, and some TEA templated MeAPSO-34 catalysts, show high activity for alkyl halide conversion with selectivity to light olefins (e.g., ethylene and propylene), they deactivate quickly. A discovery has been made that provides a solution to the deactivation of the catalyst. The discovery is premised on forming a microporous catalyst having a small crystal size and desirable surface Bransted acidity using tetraethylammonium hydroxide as the templating agent. The catalyst is capable of converting alkyl halides to olefins with less deactivation than SAPO-34 catalysts made with the same templating agent. Further, the catalysts used in the methods and systems of the current invention have been shown to have maximum combined selectivity of ethylene and propylene of at least 70% or ranging from 90% to 98%. [0041] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

A. Methods of Making TEAOH Templated MeAPSO-34 Catalysts

[0042] The MeAPSO-34 catalysts of the present invention are prepared as TEAOH templated SAPO-34 catalysts using TEAOH in the hydrothermal crystallization process of making the catalyst. The metal atom is incorporated into the SAPO-34 framework. The addition of a structure-directing or template agent/ion effects the pre-organization provided by the coordination sphere and can results in significant modification of physical/chemical/electronic properties of the template complex formed. It was surprisingly found that the addition of TEAOH as the structure-directing or template agents resulted in a profound effect on the resultant crystal morphology (size, shape, dispersion, surface area, distribution) and surface Bransted acidity of the MeAPSO-34 catalyst formed. This is illustrated in non-limiting examples in FIGS. 1-4 as well as comparative FIG. 5.

[0043] Non-limiting examples of making MeAPSO catalysts of the present invention are provided in the Examples section. Generally, MeAPSO catalysts are prepared using a gel containing aluminum (Al), phosphorus (P), silicon (Si) compounds, and metal precursors with structure-directing agents under crystallization conditions. A general non-limiting method of making the MeAPSO catalysts includes preparing an aqueous mixture of aluminum z^'so-propoxide with phosphoric acid and, optionally hydrochloric acid. Colloidal silica can be added to the aluminum/phosphorous mixture with agitation followed by the metal precursor, and then addition of tetraethylammonium hydroxide (TEAOH). The metal precursor can be salts (e.g., acetate or nitrate salts) of the desired metal. Non-limiting examples of metal salts include acetate or nitrate salts of manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, and rhenium metals. In some embodiments, salt solutions of two or more metals can be used. For example, manganese and iron salt solution(s), manganese and germanium salt solution(s), manganese and tin salt solution(s), or tin and iron salt solution(s) can be used. The synthesis mixture can have molar composition of: αΑ1₂0₃ : b Si0₂ : cP₂0₅ :dH₂0 : eTE AOH: Me_xO_y where 0 < a < 1, 0 < b < 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 <f< 1, x is 1 to 2, and y is 1 to 3. Non-limiting nano-crystal MeAPSO-34 catalysts can include a molar ratio where a is 1, b is

0.4, c is l, 50-70, e is 2 and /is 0.05; a is 1, b is 0.4, c is 1, <i is 50-70, e is 2 and /is 0.1; a is 1, b is 0.4, c is 1, d is 50-70, e is 3 and /is 0.05; a is 1, b is 0.4, c is 1, d is 50-70, e is 3 and is 0.1; a is 1, b is 0.4, c is 1, <f is 50-70, e is 4 and /is 0.05; a is 1, 6 is 0.4, c is 1, <f is 50-70, e is 4 and /is 0.1; a is 1, b is 0.35, c is 1, d is 50-70, e is 2 and /is 0.05; a is 1, b is 0.35, c is

1, d is 50-70, e is 2 and /is 0.1; a is 1, Ms 0.35, c is 1, d is 50-70, e is 3 and /is 0.05; a is 1, b is 0.35, c is 1, d is 50-70, e is 3 and /is 0.1; a is 1, is 0.35, c is I, d is 50-70, e is 4 and /is 0.05; a is 1, is 0.35, c is 1, <iis 50-70, e is 4 and /is 0.1; a is 1, Ms 0.45, c is 1, <i is 50-70, e is 2 and /is 0.05; a is 1, £ is 0.45, c is 1, d s 50-70, e is 2 and /is 0.1; a is 1, £ is 0.45, c is 1, d is 50-70, e is 3 and /is 0.05; a is 1, b is 0.45, c is 1, d is 50-70, e is 3 and /is 0.1 ; a is 1, b is 0.50, c is 1, i/ is 50-70, e is 2 and /is 0.05; a is 1, is 0.5, c is 1, d \s 50-70, e is 2 and /is 0.1; a is 1, £ is 0.4, c is 1, d is 60, e is 2 and /is 0.05; a is 1, b is 0.4, c is 1, d is 60, e is 2 and /is 0.1.

[0044] The synthesis mixture can then be heat treated to form a crystalline material. Crystal growth can be performed in a pressure vessel, such as an autoclave using autogenous pressure, by a temperature-difference method, temperature-reduction method, or a metastable-phase technique. In a particular embodiment, the crystal growth can be performed in an autoclave. The heat treatment can be performed at 150 °C to 250 °C, preferably 175 °C to 225 °C, or more preferably at 180 °C to 210 °C for a desired amount of time {e.g., 18 to 48 hours, or 24 hours) in an heated high pressure reactor {e.g., autoclave) with or without agitation. Average crystallization temperatures can range from 180 °C to 210 °C, and all temperatures there between including 181 °C , 182 °C , 183 °C , 184 °C , 185 °C, 186 °C, 187 °C, 188 °C, 189 °C, 190 °C, 191 °C, 192 °C, 193 °C, 194 °C, 195 °C, 196 °C, 197 °C, 198 °C, or 199 °C, 200 °C, 201 °C, 202 °C, 203 °C, 204 °C, 205 °C, 206 °C, 207 °C, 208 °C, or 209 °C. Heating can be performed for 12 hours to 36 hours and all periods of time there between including 12 hours, 15 hours, 20 hours, 25 hours, 30 hours, or 35 hours. After heating, the crystalline material can be separated and washed with water, and dried at about 90 °C and then calcined to remove any remaining templating agent. The calcining step can be performed in air at 400 °C to 700 °C, preferably 450 °C to 650 °C, or more preferably from 500 °C to 600 °C, for a sufficient period of time {e.g., 3 to 10 hours). Without wishing to be bound by theory, it is believed that MeAPSO-34 catalysts prepared using a TEAOH as a structure-directing agent provides effects on the chemical composition, morphology, and surface acidity that benefit the methods and systems for converting alkyl halides to olefins as currently disclosed.

B. Structural Characteristics of the TEAOH Templated MeAPSO-34 Catalysts

[0045] The MeAPSO-34 crystal produced using the methods above and in the Examples above can have any type of morphology. Non-limiting examples of morphologies include a wire, a particle, a sphere, a rod, a tetrapod, a hyper-branched structure, a tube, a cube, a plate, or mixtures thereof. The crystalline MeAPSO-34 catalysts can have an average particle size of 200 nm to 1000 nm or 200 nm to 500 nm. The average particle size of 200 nm to 1000 nm includes all average particle sizes between 200 nm to 1000 nm, for instance 200 nm, 225 nm, 250 nm, 275 nm, 300 nm, 325 nm, 350 nm, 375 nm, 400 nm, 425 nm, 450 nm, 475 nm, 500 nm, 525 nm, 550 nm, 575 nm, 600 nm, 625 nm, 650 nm, 675 nm, 700 nm, 725 nm, 750 nm, 775 nm, 800 nm, 825 nm, 850 nm, 875 nm, 900 nm, 925 nm, 950 nm, 975 nm, 1000 nm, and all values and ranges in between. Particle size can be determined using Scanning Electron Microscopy (SEM) or Transmission Electron Spectroscopy (TEM). C. Olefin Production

1. Methods and Systems

[0046] The TEAOH templated MeAPSO catalysts of the present invention help to catalyze the conversion of alkyl halides to C₂-C₄ olefins such as ethylene, propylene and butene (butylene). Butene can include 1-butene, (Z -but-2-ene, (J¾)-but-2-ene, 2- methylpropene, and combinations thereof. The following non-limiting two-step process is an example of conversion of methane to methyl chloride and conversion of methyl chloride to ethylene, propylene and butene. Equation (II) illustrates the reactions that are believed to occur in the context of the present invention:

CH₄ + X₂ ► CH₃X + HX (I) MeAPSO-34

9CH₃X C₂H₄ + C₃H₆ + C₄H₈ + 9HX (II)

Besides the C₂-C₄ olefins the reaction may produce byproducts such as methane, C₅ olefins, C₂-C₅ alkanes and aromatic compounds such as benzene, toluene and xylene.

[0047] Conditions sufficient for olefin production (e.g., ethylene, propylene and butylene as shown in Equation (II)) include temperature, time, alkyl halide concentration, space velocity, and pressure. The temperature range for olefin production may range from about 300 °C to 500 °C, preferably ranging 350 °C to 450 °C. A weight hourly space velocity (WHSV) of alkyl halide higher than 0.5 h^"1 can be used, preferably between 1.0 and 10 h^"1, more preferably between 2.0 and 3.5 h^"1. The conversion of alkyl halide is carried out at a pressure less than 145 psig (1 MPa) and preferably less than 73 psig (0.5 MPa), or at atmospheric pressure. The conditions for olefin production may be varied based on the type of the reactor.

[0048] The methods and system disclosed herein also include the ability to regenerate used/deactivated catalyst in a continuous process such as in a fluid catalytic cracking (FCC)- type process or reactor or a circulating catalyst bed process or reactor. The method and system can further include collecting or storing the produced olefin hydrocarbon product along with using the produced olefin hydrocarbon product to produce a petrochemical or a polymer.

[0049] Referring to FIG. 2, a system 100 is illustrated, which can be used to convert alkyl halides to olefin hydrocarbon products with the TEAOH templated MeAPSO catalysts of the present invention. The system 100 can include an alkyl halide source 102, a reactor 104, and a collection device 106. The alkyl halide source 102 can be configured to be in fluid communication with the reactor 104 via an inlet 108 on the reactor. As explained above, the alkyl halide source can be configured such that it regulates the amount of alkyl halide feed entering the reactor 104. The reactor 104 can include a reaction zone 110 having the TEAOH templated MeAPSO-34 catalyst 112 of the present invention. The amounts of the alkyl halide feed and the catalyst 112 used can be modified as desired to achieve a given amount of product produced by the system 100. Non-limiting examples of reactors that can be used include fixed-bed reactors, fluidized bed reactors, bubbling bed reactors, slurry reactors, rotating kiln reactors, or any combinations thereof when two or more reactors are used. In preferred aspects, reactor 104 is a fluid catalytic cracking (FCC)-type reactor or a circulating catalyst bed reactor that permits the regeneration of used/deactivated catalyst in a continuous process. The reactor 104 can include an outlet 114 for products produced in the reaction zone 110. The products produced can include ethylene, propylene and butylene. The collection device 106 can be in fluid communication with the reactor 104 via the outlet 114. Both the inlet 108 and the outlet 114 can be open and closed as desired. The collection device 106 can be configured to store, further process, or transfer desired reaction products {e.g., C2-C4 olefins) for other uses. By way of example only, FIG. 1 provides non-limiting uses of ethylene and propylene produced from the catalysts and processes of the present invention. Still further, the system 100 can also include a heating source 1 18. The heating source 1 18 can be configured to heat the reaction zone 18 to a temperature sufficient (e.g., 300 to 500 °C or 325 to 375 °C) to convert the alkyl halides in the alkyl halide feed to olefin hydrocarbon products. Non-limiting examples of a heating source 1 18 can be a temperature controlled furnace, tube-in-shell heat exchangers, heaters, and the like. Additionally, any unreacted alkyl halide can be recycled and included in the alkyl halide feed to further maximize the overall conversion of alkyl halide to olefin products. Further, certain products or byproducts such as butylene, C₅+ olefins and C₂+ alkanes can be separated and used in other processes to produce commercially valuable chemicals (e.g., propylene). This increases the efficiency and commercial value of the alkyl halide conversion process of the present invention.

2. Catalyst Activity/Selectivity

[0050] Catalytic activity as measured by alkyl halide conversion can be expressed as the % moles of the alkyl halide converted with respect to the moles of alkyl halide fed. In particular aspects, the combined selectivity of ethylene and propylene is at least 70%, preferably at least 80%>, more preferably at least 90%, or most preferably 90% to 98% under certain reaction conditions, wherein the maximum combined space time yield (STY) of ethylene and propylene is at least 1/hr or 1/hr to 3/hr, and/or wherein the maximum conversion of alkyl halide is at least 65% or 70% to 80%. In certain instances, the selectivity of ethylene is about 40% or higher and the selectivity of propylene is about 30% or higher, wherein the maximum selectivity of ethylene is 50% to 60% and the maximum selectivity of propylene is 35% to 45%.

[0051] As an example, chloromethane (CH₃C1) is used here to define conversion and maximum selectivity of products by the following equations (III)-(VII):

(CH₃C1)° - (CH₃CI)

% CH₃CI Conversion x 100, (III)

(CH₃C1)° where, (CH3CI)⁰ and (CH₃C1) are moles of methyl chloride in the feed and reaction product, respectively. [0052] Maximum selectivity is defined as C-mole% and are defined for ethylene, propylene, and so on as follows:

2(C₂H₄)

% Ethylene Selectivity = x 100, (IV)

(CH₃C1)° - (CH₃CI) where the numerator is the carbon adjusted mole of ethylene and the denominator is the moles of carbon converted.

[0053] Maximum selectivity for propylene may be expressed as:

3(C₃H₆)

% Propylene Selectivity = x 100, (V)

(CH₃C1)° - (CH₃CI) where the numerator is the carbon adjusted mole of propylene and the denominator is the moles of carbon converted.

[0054] Maximum selectivity for butylene may be expressed as: 4(C₄H₈)

% Butylene Selectivity = x 100, (VI)

(CH₃C1)° - (CH₃CI)

where the numerator is the carbon adjusted mole of butylene and the denominator is the moles of carbon converted. [0055] Selectivity for aromatic compounds may be expressed as:

6(C₆H₆) + 7(C₇H₈) + 8(C₈H₁₀)

% Aromatics Selectivity = x 100 (VII)

(CH₃C1)° - (CH₃CI) where the numerator is the carbon adjusted mole of aromatic compounds and the denominator is the moles of carbon converted.

D. Materials

1. MeAPSO Materials

[0056] MeAPSO catalysts are made from silicon (Si), aluminum (Al), and phosphorous (P) in various molar ratios. Non-limiting examples of silicon sources include colloidal silica, fumed silica, tetramethyl orthosilicate, tetraethyl orthosilicate, or tetraisopropyl orthosilicate. Non-limiting examples of aluminum sources include aluminum methoxide, aluminum ethoxide, aluminum isopropoxide, or aluminums tert-butoxide. Non-limiting examples of phosphorus sources include phosphoric acid. These compounds can be obtained from various commercial sources, of which Sigma Aldrich® (U.S. A) is a non-limiting example. Templating agents can be used to direct crystal growth, pore size and the like. The templating agent, tetraethyl ammonium hydroxide (TEAOH) is available from commercial sources, for example, Sigma Aldrich® (U.S. A) or SACHEM, Inc., (USA) under the tradename ZeoGen™.

[0057] The metal or metal oxide denoted "Me" in the MeASPO materials can include metals or metal oxides from Columns 2, 4, 7 to 12, and 14 of the Periodic Table or combinations thereof. Non-limiting examples of metals include manganese (Mn), magnesium (Mg), copper (Cu), cobalt (Co), iron (Fe), nickel (Ni), germanium (Ge), tin (Sn), titanium (Ti), rhenium (Re), or zinc (Zn). The metals or metal oxides or metal precursors can be purchased from commercial manufactures such as Sigma-Aldrich®. 2. Alkyl Halide Feed

[0058] The alkyl halide feed includes one or more alkyl halides. The alkyl halide feed may contain alkyl monohalides, alkyl dihalides, alkyl trihalides, preferably alkyl monohalide with less than 10 mol.% of other halides relative to the total halides. The alkyl halide feed may also contain nitrogen, helium, steam, and so on as inert compounds. The alkyl halide in the feed may have the following structure: C_nH(2_n+2)-m m, where n and m are integers, n ranges from 1 to 5, preferably 1 to 3, even more preferably 1, m ranges 1 to 3, preferably 1, X is Br, F, I, or CI. In particular aspects, the feed may include about 10, 15, 20, 40, 50 mol.% or more of the alkyl halide. In particular embodiments, the feed contains up to 10 mol.% or more of a methyl halide. In preferred aspects, the methyl halide is methyl chloride, methyl bromide, methyl fluoride, or methyl iodide, or any combination thereof. The feed stream can also include alcohol. In a particular embodiment, the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt.% alcohol, or preferably is alcohol free, and in one instance that alcohol is methanol.

[0059] The production of alkyl halide, particularly of methyl chloride (CH₃C1) is commercially produced by thermal chlorination of methane at 400 °C to 450 °C and at a raised pressure. Catalytic oxychlorination of methane to methyl chloride is also known. In addition, methyl chloride is industrially made by reaction of methanol and HC1 at 180 °C to 200 °C using a catalyst. Alternatively, methyl halides are commercially available from a wide range of sources (e.g., Praxair, Danbury, CT; Sigma-Aldrich Co. LLC, St. Louis, Mo.; BOC Sciences USA, Shirley, NY). In preferred aspects, methyl chloride and methyl bromide can be used alone or in combination.

EXAMPLES

[0060] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results. The materials used in the following examples are described in Table 1, and were used as-described unless specifically stated otherwise.

Table 1

EXAMPLE 1

(Preparation of Comparative SAPO-34 Catalyst)

[0061] Comparative Catalyst 1 was synthesized using the following molar ratios lAl₂O3:0.4SiO₂: lP₂O₅:60H₂O:2TEAOH. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH was then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL DI water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The SAPO-34 had a Si/Al ratio of 0.18 and a Al/P ratio of 1.34. The material was confirmed to be SAPO-34 by X-ray diffraction (XRD).

EXAMPLE 2

(Preparation of TEAOH Templated MnAPSO-34 Catalysts) [0062] Catalysts 2 and 3 were synthesized using the following molar ratios 1 Al₂O₃:0.4SiO₂: 1Ρ₂Ο₅:60Η₂Ο:2ΤΕΑΟΗ:0.05ΜηΟ and lAl₂O₃:0.4SiO₂: lP₂O₅:60H₂O:2TEAOH:0.1MnO, respectively. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH was added to the mixture and then manganese acetate was added. The final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. Catalyst 2 had a Si/Al ratio of 0.16, a Al/P ratio of 1.19 and contained 1.31 wt.% of Mn based on the total weight of the catalyst. Catalyst 3 had a Si/Al ratio of 0.16, a Al/P ratio of 1.10 and contained 2.34 wt.% of Mn based on the total weight of the catalyst. The material was confirmed to be of the CHA structure by XRD.

EXAMPLE 3

(Preparation of TEAOH Templated FeAPSO-34 Catalyst)

[0063] Catalyst 4 was synthesized using the following molar ratios lAl₂O₃:0.4SiO₂: lP₂O₅:60H₂O:2TEAOH:0.05Fe₂O₃. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and iron nitrate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Pan- autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.

EXAMPLE 4

(Preparation of TEAOH Templated CoAPSO-34 Catalyst) [0064] Catalyst 5 was synthesized using the following molar ratios lAl₂O3:0.4SiO₂: lP₂O₅:60H₂O:2TEAOH:0.05CoO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and cobalt acetate tetrahydrate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.

EXAMPLE 5

(Preparation of TEAOH Templated CuAPSO-34 Catalyst)

[0065] Catalyst 6 was synthesized using the following molar ratios lAl₂O₃:0.4SiO₂: lP₂O₅:60H₂O:2TEAOH:0.05CuO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and copper acetate monohydrate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.

EXAMPLE 6

(Preparation of TEAOH Templated MgAPSO-34 Catalyst)

[0066] Catalyst 7 was synthesized using the following molar ratios lAl₂O3:0.4SiO₂: lP₂O₅:60H₂O:2TEAOH:0.05MgO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and magnesium acetate tetrahydrate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.

EXAMPLE 7

(Preparation of TEAOH Templated SnAPSO-34 Catalyst) [0067] Catalyst 8 was synthesized using the following molar ratios lAl₂O₃:0.4SiO₂: lP₂O₅:60H₂O:2TEAOH:0.05SnO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and tin oxide were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 200 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD. EXAMPLE 8

(Preparation of TEAOH Templated TiAPSO-34 Catalyst)

[0068] Catalyst 9 was synthesized using the following molar ratios lAl₂O3:0.4SiO₂: lP₂O₅:60H₂O:2TEAOH:0.05TiO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and titanium ethoxide were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190-200 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD. EXAMPLE 9

(Preparation of TEAOH Templated ReAPSO-34 Catalyst)

[0069] Catalyst 10 was synthesized using the following molar ratios lAl₂O₃:0.4SiO₂: lP₂O₅:60H₂O:2TEAOH:0.05ReO. Aluminum isopropoxide was added slowly (over course of 30 mins) to a dilute solution of phosphoric acid under vigorous stirring. The slurry was allowed to stir for an additional 1 hour. Colloidal silica was added drop-wise (over course of 15 mins) to the above slurry and the resulting mixture was stirred for 30 minutes. TEAOH and ammonium perrhenate were then added and the final mixture was stirred for 30 minutes. The slurry was added to a Teflon liner and placed in a 300 mL Parr autoclave. The sample was crystallized hydrothermally at 190-200 °C for 24 hours. After crystallization the product was washed with 400 mL deionized water and separated by centrifugation. The solution was decanted and the washing was repeated 3 times. The final product was dried at 90 °C overnight and then calcined at 550 °C for 8 hours. The material was confirmed to be of the CHA structure by XRD.

EXAMPLE 10

(MeSAPO-34 Catalyst Characterization)

[0070] Scanning Electron Microscopy (SEM) analysis. SEM analysis was performed on the comparative Example 1 and inventive sample from Examples 2 and 3 using a JSM- 7800F-PRIME scanning electron microscope operating at 5kV. FIG. 3A is a SEM image of the catalyst of Example 2 at magnification of 2 kx, viewing field of 12.8 micrometers. FIG. 3B is a SEM image of the catalyst of Example 2 at magnification of 19.999 kx, viewing field of 12.8 micrometers. FIG. 3B is a SEM image of the catalyst of Example 2 at magnification of 20.001 kx, viewing field of 12.8 micrometers. From the SEM, it was determined that regular cubed shaped nanoparticles of MnAPSO-34 having average dimension of 500 nm were formed. FIG. 4 is a SEM image of the crystals of Example 3 at a scale of 4 μπι. From the SEM, it was determined that regular cubed shaped nanoparticles of FeAPSO-34 having average dimension of 500 nm were formed. FIG. 5 is a SEM image of crystals from a TEA templated MnAPSO-34 catalyst of the prior art at 2 kx magnification taken at 20 kV (See, Wei et al), which has a particles of approximately 4-5 microns (4000 to 5000 nm).

EXAMPLE 11

(Methyl chloride Conversion Reactions)

[0071] The TEAOH templated MeAPSO-34 catalysts shown in Table 2 and the comparative SAPO-34 catalyst were tested for methyl chloride conversion by using a fixed- bed tubular reactor at about 450 °C for a period of 6 h. The MeAPSO-34 catalysts were made using the same procedure as in Examples 2 and 3 using the various materials in Table 1.

Table 2

The catalyst powder was pressed and then crushed and sized between 20 and 40 mesh screens. In each test, a fresh load of sized (20-40 mesh) catalyst (1.0 g) was loaded in a stainless steel tubular (1/2-inch outer diameter) reactor. The catalyst was dried at 200 °C under N₂ flow (100 cm³/min) for an hour and then temperature was raised to 450 °C at which time N₂ was replaced by methyl chloride feed (100 cm³/min) containing 20 mol% CH₃C1 in N₂. The weight hourly space velocity (WHSV) of CH₃C1 was about 0.8 h^"1 to 3.0 h^"1 and reactor inlet pressure was about 0 MPa. The percent CH₃C1 conversion, C₂ percent selectivity, C₃ percent selectivity of the catalyst of present invention and the comparative catalyst are listed in Table 3 at 3 h^"1, 450 °C, and 0 psig. Selectivities were based on methyl chloride and are carbon-based. FIG. 6 shows graphs of percent CH₃C1 conversion of catalysts 1, 2, and 4-7 listed in Table 2 of present invention and the comparative catalyst (SAPO-34). FIG. 7 shows graphs of percent CH₃C1 conversion of the catalysts 2 and 3 (MnAPSO-34) of present invention and the comparative catalyst (SAPO-34). FIG. 8 shows graphical representations of the data in Table 3 for MnAPSO-34. The graphs show CH₃C1 conversion, ethylene selectivity, propylene selectivity and methane selectivity of the catalyst 2 (MnAPSO-34) of present invention and the comparative catalyst (SAPO-34). FIGS. 9-11 show graphical representations of the data for catalysts 8-10 in Table 3 respectively. The graphs show the CH₃C1 conversion, ethylene selectivity, and propylene selectivity of separately catalyst 8 (SnAPSO-34), catalyst 9 (TiAPSO-34), and catalyst 10 (ReAPSO-34) of present invention and the comparative catalyst (SAPO-34). The higher ethylene selectivity of the TEAOH templated MeAPSO-34 catalysts was attributed to higher acidity of the catalyst due to the presence of the Lewis acid metal. From the data, it was determined that the TEAOH templated MeAPSO-34 catalysts had better conversion, STY, C₂-C₃ selectivity, C₃ selectivity and activity as compared to the TEAOH templated SAPO-34 (see, for example Wei et al). Without wishing to be bound by theory, it is believed that the smaller particle size of the catalyst attributed to the higher activity and overall selectivity of the MeAPSO-34 catalysts of the present invention as compared to TEAOH templated SAPO-34 catalysts.

Table 3

* Space time yield = Tonnes Ethylene&Propylene/Tonne Catalyst/hr. STY is calculated based on carbon-based selectivities.

Claims

1. A method for converting an alkyl halide to an olefin, the method comprising contacting a tetraethylammonium hydroxide (TEAOH) templated metal silicoaluminophosphate-34 (MeAPSO-34) catalyst with a feed comprising an alkyl halide under reaction conditions sufficient to produce an olefin hydrocarbon product comprising olefins, wherein the metal (Me) is incorporated into the SAPO-34 framework.

2. The method of claim 1, wherein the incorporated metal (Me) is manganese (Mn), magnesium (Mg), cobalt (Co), nickel (Ni), iron (Fe), copper (Cu), zinc (Zn), tin (Sn), germanium (Ge), titanium (Ti), rhenium (Re), or any combination thereof, preferably manganese, tin, manganese and iron, manganese and germanium, manganese and tin, or tin and iron.

3. The method of claim 1, wherein the olefins are C₂ to C₄ olefins.

4. The method of claim 3, wherein: the maximum combined selectivity of ethylene and propylene is at least 70%, preferably at least 80%, or more preferably 90% to 98%, the maximum combined space time yield of ethylene and propylene is at least 1/hr or 1/hr to 3/hr; and the maximum conversion of alkyl halide is at least 80% or 85% to 100%.

5. The method of claim 4, wherein the maximum selectivity of ethylene is 40% to 55%, and the maximum selectivity of propylene is 30% to 45%.

6. The method of any one of claims 1 to 5, wherein the reaction conditions include a temperature from 300 °C to 500 °C, a pressure of 0.5 MPa or less, and a weighted hourly space velocity (WHSV) of 0.5 to 10 h^"1.

7. The method of any one of claims 1 to 5, wherein the TEAOH templated MeAPSO-34 catalyst is the reaction product of heat treatment of a synthesis mixture having a molar composition of: aAl₂0₃:6Si0₂:cP₂0₅:^₂0:eTEAOH:/ e_xO_y where 0 < a < 1, 0 < b <1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 <f< 1, x is 1 to 2, and y is 1 to 3.

8. The method of claim 7, wherein a is 1, b is 0.4, c is I , d is 60, e is 2 and /is 0.05 or 0.1.

9. The method of claim 7, wherein the heat treatment comprises:

(a) heating the synthesis mixture to obtain a crystalline material; and

(b) calcining the crystalline material.

10. The method of claim 1 , wherein the alkyl halide is a methyl halide, preferably methyl chloride.

1 1. The method of claim 1, wherein the feed stream includes less than 5 wt.% alcohol, preferably less than 1 wt. % alcohol, or preferably is alcohol free.

12. The method of claim 1, wherein the reaction occurs in a fixed feed reactor, a fluid catalytic cracking (FCC) reactor or fluidized circulating bed reactor.

13. The method of claim 1, further comprising collecting or storing the produced olefin hydrocarbon product.

14. A catalyst capable of catalyzing an alkyl halide to an olefin reaction, the catalyst having a general formula of: eTEAOH(M_e/Si_aAl₅P_c)0₂,

where:

Me is manganese, magnesium, cobalt, nickel, iron, copper, zinc, tin, germanium, titanium, rhenium, or any combination thereof and Me is incorporated into the framework of the catalyst;

e is the molar amount of tetraethylammonium hydroxide (TEAOH) per mole of (Me Si_aAl¾P_c)0₂ and a, b, and c are the molar fractions of metal, silicon, aluminum, and phosphorous respectively;

0 < e < 4, 0 <f< 1, 0 < a < 1, 0 < b < 1, 0 < c < 1, and f+a+b+c = 1, wherein the catalyst is capable of catalyzing an alkyl halide to olefin reaction.

15. The catalyst of claim 14, having an average particle size of 200 nm to 1000 nm or 200 nm to 500 nm.

16. The catalyst of claim 14, wherein the particle size of the catalyst is less than the particle size of a triethyl amine templated catalyst and/or a mixed templated catalyst.

17. A system for producing olefins, the system comprising: an inlet for a feed comprising an alkyl halide; a reaction zone that is configured to be in fluid communication with the inlet, wherein the reaction zone comprises the feed and the catalyst of claim 14; and an outlet configured to be in fluid communication with the reaction zone to remove an olefin hydrocarbon product from the reaction zone.

18. The system of claim 17, wherein the reaction zone includes a fluid catalytic cracking (FCC)-type reactor or a circulating catalyst bed reactor.

19. The system of claim 17, further comprising a collection device that is capable of collecting the olefin hydrocarbon product.

20. A method of making the catalyst of claim 14, the method comprising:

(a) heating a synthesis mixture to obtain a crystalline material; and

(b) calcining the crystalline material,

wherein the synthesis mixture has a molar composition of: aAl₂0₃:6Si0₂:cP₂0₅:^₂0:eTEAOH:/ e_xO_y where 0 < a <1, 0 < b < 1, 0 < c < 1, d is 30 to 80, 0 < e < 4; 0 < f<\, x is 1 to 2, and .y is 1 to 3.