Molecular Sieve CIT-17, Its Synthesis and Use
20240173708 ยท 2024-05-30
Inventors
Cpc classification
C01B37/08
CHEMISTRY; METALLURGY
B01J29/85
PERFORMING OPERATIONS; TRANSPORTING
C01P2002/72
CHEMISTRY; METALLURGY
B01J37/0018
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J29/85
PERFORMING OPERATIONS; TRANSPORTING
C01B37/08
CHEMISTRY; METALLURGY
B01J37/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present disclosure is directed to novel silicoaluminophosphate (SAPO)-based material with an SAT framework structure (topology type) (SAPO-SAT) that is substantially free of a non-SAPO-SAT phase, as well as the synthesis and use of that SAPO-SAT.
Claims
1. A silicoaluminophosphate-based molecular sieve having an SAT framework structure (SAPO-SAT), wherein the SAPO-SAT is substantially free of a non-SAPO-SAT phase.
2. The SAPO-SAT of claim 1, wherein the SAPO-SAT is substantially free of SAPO-AFX.
3. The SAPO-SAT of claim 1, wherein the Si/T-atom ratio is from about 0.068 to about
0. 094 as determined by EDS elemental analysis, wherein T=Si+Al+P.
4. The SAPO-SAT of claim 3, wherein the Si/T-atom ratio is 0.083 as determined by EDS elemental analysis, wherein T=Si+Al+P.
5. The SAPO-SAT of claim 1, wherein the SATO-SAT has a pore volume of about 0.15 cm.sup.3/g.
6. The SAPO-SAT of claim 1, wherein the SATO-SAT has an XRD substantially the same as that shown in
7. A process for making the SAPO-SAT molecular sieve of claim 1, the process comprising: a. preparing a synthesis gel by a process comprising: i. mixing a phosphorus source and water, and stirring the resulting mixture for 10 minutes; ii. adding an aluminum source, and allowing the resulting gel to homogenize for 3-4 hours; iii. adding a silica source to the mixture; iv. adding an organic structure determining agent (OSDA); b. aging the resulting synthesis gel at room temperature for 20-24 hours; c. heating the aged synthesis gel to about 160-200? C. for about 3 days; d. washing the resulting powder with distilled water and acetone; e. drying the powder in a convection oven at about 80? C.
8. The process of claim 7, the process comprising: a. preparing a synthesis gel by a process comprising: i. mixing phosphoric acid (H.sub.3PO.sub.4) (85%) and water, and stirring the resulting mixture for 10 minutes; ii. adding aluminum hydroxide, and allowing the resulting gel to homogenize for 3-4 hours; iii. adding fumed silica to the mixture; iv. adding an organic structure determining agent (OSDA); b. aging the resulting synthesis gel at room temperature for 20-24 hours; c. heating the aged synthesis gel to about 160-200? C. for about 3 days; d. washing the resulting powder with distilled water and acetone; e. drying the powder in a convection oven at about 80? C.
9. The process of claim 7, further comprising thermally treating the powder that is the product of step e. under flowing air in a furnace by: a. heating to about 150? C. and holding for about 3 h; and then b. heating to about 580? C. and holding for about 12 h, or until complete combustion of any remaining OSDA has been accomplished.
10. The process of claim 7, wherein the OSDA is DiQ-C.sub.4, DiQ-C.sub.5, or DiDABCO-C.sub.4.
11. The process of claim 7, wherein the synthesis gel has a molar composition of: 0.06-0.15 SiO.sub.2; 0.44-0.5 Al.sub.2O.sub.3; 0.44-0.5 P.sub.2O.sub.5; 0.17-0.33 R(OH).sub.2 wherein R is DiQ-C.sub.4, DiQ-C.sub.5, or DiDABCO-C.sub.4; and 40-75 H.sub.2O
12. The process of claim 7, wherein the synthesis gel has a molar composition of: 0.1 SiO.sub.2; 0.44-0.5 Al.sub.2O.sub.3; 0.44-0.5 P.sub.2O.sub.5; 0.2-0.33 R(OH).sub.2 wherein R=DiDABCO-C.sub.4; and 40-75 H.sub.2O.
13. The process of claim 7, wherein the synthesis gel has a molar composition of: 0.06-0.1 SiO.sub.2; 0.5 Al.sub.2O.sub.3; 0.45-0.5 P.sub.2O.sub.5; 0.17-0.33 R(OH).sub.2 wherein R=DiQ-C.sub.4; and 40-75 H.sub.2O.
14. The process of claim 7, wherein the synthesis gel has a molar composition of: 0.06-0.15 SiO.sub.2; 0.5 Al.sub.2O.sub.3; 0.45-0.49 P.sub.2O.sub.5; 0.23-0.27 R(OH).sub.2 wherein R=DiQ-C.sub.5; and 40 H.sub.2O.
15. A process for the production of propylene from a methanol-containing feed, the process comprising: passing the methanol-containing feed to a reactor, wherein the reactor comprises a catalyst comprising a SAPO-SAT molecular sieve, wherein the SAPO-SAT molecular sieve is substantially free of a non-SAPO-SAT phase, and wherein the reactor is operated at reaction conditions sufficient to generate an effluent stream comprising propylene and having a propylene to ethylene ratio between about 1.6 and about 4.2.
16. A process for the production of propylene from a methanol-containing feed, the process comprising: passing the methanol-containing feed to a reactor, wherein the reactor comprises a catalyst comprising a MeAPO-SAT molecular sieve, wherein the MeAPO-SAT molecular sieve is substantially free of a non-MeAPO-SAT phase, wherein Me is cobalt or magnesium, and wherein the reactor is operated at reaction conditions sufficient to generate an effluent stream comprising propylene and having a propylene to ethylene ratio between about 1.6 and about 4.2.
17. The process of claim 15, wherein the reactor is a fluidized bed, fixed bed, or swing fixed bed reactor.
18. The process of claim 15, wherein the process is operated at ambient pressure.
19. The process of claim 15, wherein the methanol-containing feed flow rate provides a weight hourly space velocity (WHSV) of about 0.65 h.sup.?1 to about 2.61 h.sup.?1.
20. The process of claim 15, wherein the reactor is operated at a temperature of about 350? C.-about 600? C.
21. The process of claim 15, wherein greater than 97% of the methanol in the methanol-containing feed is converted.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
[0040] In the present disclosure the singular forms a, an, and the include the plural reference, and reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to a material is a reference to at least one of such materials and equivalents thereof known to those skilled in the art, and so forth.
[0041] When a value is expressed as an approximation by use of the descriptor about, it will be understood that the particular value forms another embodiment. In general, use of the term about indicates approximations that can vary depending on the desired properties sought to be obtained by the disclosed subject matter and is to be interpreted in the specific context in which it is used, based on its function. The person skilled in the art will be able to interpret this as a matter of routine. In some embodiments, the term about as modifying a number indicates the recited number ?10% of the recited number. Where present, all ranges are inclusive and combinable. That is, references to values stated in ranges include every value within that range.
[0042] It is to be appreciated that certain features of the invention which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. That is, unless obviously incompatible or specifically excluded, each individual embodiment is deemed to be combinable with any other embodiment(s) and such a combination is considered to be another embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step may also be considered an independent embodiment in itself, combinable with others.
[0043] The transitional terms comprising, consisting essentially of, and consisting are intended to connote their generally in accepted meanings in the patent vernacular; that is, (i) comprising, which is synonymous with including, containing, or characterized by, is inclusive or open-ended and does not exclude additional, unrecited elements or method steps; (ii) consisting of excludes any element, step, or ingredient not specified in the claim; and (iii) consisting essentially of limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention. Embodiments described in terms of the phrase comprising (or its equivalents), also provide, as embodiments, those which are independently described in terms of consisting of and consisting essentially of.
[0044] When a list is presented, unless stated otherwise, it is to be understood that each individual element of that list, and every combination of that list, is a separate embodiment. For example, a list of embodiments presented as A, B, or C is to be interpreted as including the embodiments, A, B, C, A or B, A or C, B or C, or A, B, or C, as separate embodiments.
[0045] Throughout this specification, words are to be afforded their normal meaning, as would be understood by those skilled in the relevant art. However, so as to avoid misunderstanding, the meanings of certain terms will be specifically defined or clarified.
[0046] The terms method(s) and process(es) are considered interchangeable within this disclosure.
[0047] The present invention may be understood more readily by reference to the following description taken in connection with the accompanying Figures and Examples, all of which form a part of this disclosure. It is to be understood that this invention is not limited to the specific products, methods, conditions or parameters described or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of any claimed invention. Similarly, unless specifically otherwise stated, any description as to a possible mechanism or mode of action or reason for improvement is meant to be illustrative only, and the invention herein is not to be constrained by the correctness or incorrectness of any such suggested mechanism or mode of action or reason for improvement. Throughout this text, it is recognized that the descriptions refer to compositions and methods of making and using said compositions. That is, where the disclosure describes or claims a feature or embodiment associated with a composition or a method of making or using a composition, it is appreciated that such a description or claim is intended to extend these features or embodiment to embodiments in each of these contexts (i.e., compositions, methods of making, and methods of using).
[0048] A material disclosed herein may be referred to as being characterized by graphical data as shown in a Figure. Such data include, for example, powder X-ray diffractograms (XRD), thermogravimetric analysis (TGA) profiles, NMR spectra and the like. As is well-known in the art, the graphical data potentially provides additional technical information to further define the respective solid state form which can not necessarily be described by reference to numerical values or peak positions alone. Thus, the term substantially as shown in when referring to graphical data in a Figure herein means a pattern that is not necessarily identical to those depicted herein, but that falls within the limits of experimental error or deviations, when considered by one of ordinary skill in the art. The skilled person would readily be able to compare the graphical data in the Figures herein with graphical data generated for an unknown material and confirm whether the two sets of graphical data are characterizing the same material or two different materials.
Compositions
[0049] The present invention is directed to new compositions of matter, including those comprising CIT-17, and methods of making and using these compositions.
[0050] In some aspects, the disclosure is directed to a silicoaluminophosphate-based molecular sieve having an SAT framework structure (SAPO-SAT), wherein the SAPO-SAT is substantially free of a non-SAPO-SAT phase. The SAPO-SAT that is substantially free of a non-SAPO-SAT phase may be referred to herein as CIT-17.
[0051] The framework structure of CIT-17 belongs to a family of molecular sieve solids that are built up by stacking six-membered rings (6 MRs) at different positions in the xy plane of a hexagonal unit cell and then connected via 4 MRs. The stacking sequence of the 6 MRs for SAT is ABBCBCCACAAB. A single column of this structure consists of double six-membered rings (D6 Rs), CAN cages, and elongated cages (SAT-cages) that are interconnected via elliptical 8 MRs.
[0052] In these aspects, the term substantially free of a non-SAPO-SAT phase means that the CIT-17 does not include a detectable amount of a non-SAPO-SAT phase. Methods of detecting a non-SAPO-SAT phase in a sample of CIT-17 are known to those of skill in the art, and include, for example XRD.
[0053] In some embodiments, the CIT-17 of the disclosure has an x-ray powder diffraction pattern substantially the same as shown in
[0054] In other embodiments, the CIT-17 of the disclosure has an x-ray powder diffraction pattern exhibiting peaks at at least five of the peaks shown in
[0055] In other embodiments, the CIT-17 of the disclosure has an x-ray powder diffraction pattern substantially as shown in
[0056] In other embodiments, the CIT-17 of the disclosure has an x-ray powder diffraction pattern substantially as shown in
[0057] In other embodiments, the CIT-17 of the disclosure exhibits a powder X-ray diffraction (XRD) pattern exhibiting at least five of the characteristic peaks at 8.4?0.2, 13.66?0.2, 16.06?0.2, 16.5 ?0.2, 19.62?0.2, 21.12?0.2, 21.94?0.2, 23.76?0.2, 25.6?0.2, 27.5?0.2, 29.46?0.2, and 32.02?0.2 degrees 2-?. In separate embodiments, the composition exhibits six, seven, eight, nine, or ten of the characteristic peaks at 8.4?0.2, 13.66?0.2, 16.06?0.2, 16.58?0.2, 19.62?0.2, 21.12?0.2, 21.94?0.2, 23.76?0.2, 25.6?0.2, 27.5?0.2, 29.46?0.2, and 32.02?0.2 degrees 2-?.
[0058] In other embodiments, the SATO-SAT of the disclosure is characterized by a TGA profile substantially as shown in
[0059] In other embodiments, the thermally treated SATO-SAT of the disclosure is characterized by an .sup.27Al MAS NMR substantially as shown in
[0060] In other embodiments, the thermally treated SATO-SAT of the disclosure is characterized by a .sup.29Si MAS NMR substantially as shown in
[0061] In other embodiments, the thermally treated SATO-SAT of the disclosure is characterized by a .sup.31P MAS NMR substantially as shown in
[0062] In other embodiments, the thermally treated SATO-SAT of the disclosure is characterized by a .sup.1H MAS NMR substantially as shown in
[0063] In other embodiments, the thermally treated SATO-SAT of the disclosure is characterized by N.sub.2-adsorption-desorption isotherms substantially as shown in
[0064] As noted, the CIT-17 of the disclosure is substantially free of a non-SAPO-SAT phase. In some embodiments, the CIT-17 is substantially free of SAPO-AFX.
[0065] Depending on the processing of the crystalline compositions, the CIT-17 compositions may contain the organic structure determining agent (OSDA) used in their preparation, or may be substantially free or devoid of any such OSDA. The specific OSDAs used to prepare CIT-17 are also described elsewhere herein.
[0066] The presence of these OSDAs may be identified using, for example, .sup.13C NMR or any of the methods defined in the Examples. It is a particular feature of the present invention that the cationic OSDAs retain their original structures, including their stereochemical conformations during the synthetic processes, these structures being compromised during the subsequent calcinations or oxidative treatments.
[0067] In some embodiments, the CIT-17 is characterized by the Si/T-atom ratio wherein T=Si+Al+P . The Si/T-atom ratio may be determined by methods known in the art, including, for example, EDS elemental analysis. In some embodiments of the CIT-17 of the disclosure, the Si/T-atom ratio is from about 0.068 to about 0.094, such as for example, about 0.068, about 0.069, about 0.070, about 0.071, about 0.072, about 0.073, about 0.074, about 0.075, about 0.076, about 0.077, about 0.078, about 0.079, about 0.080, about 0.081, about 0.082, about 0.083, about 0.084, about 0.085, about 0.086, about 0.087, about 0.088, about 0.089, about 0.090, about 0.091, about 0.092, about 0.093, or about 0.094.
[0068] In other embodiments of the CIT-17 of the disclosure, the Si/T-atom ratio is from 0.068 to 0.094, such as for example, 0.068, 0.069, 0.070, 0.071, 0.072, 0.073, 0.074, 0.075, 0.076, 0.077, 0.078, 0.079, 0.080, 0.081, 0.082, 0.083, 0.084, 0.085, 0.086, 0.087, 0.088, 0.089, 0.090, 0.091, 0.092, 0.093, or 0.094. The Si/T-atom ratio may be determined by methods known in the art, including, for example, EDS elemental analysis. wherein T=Si+Al+P.
[0069] In other embodiments of the CIT-17 of the disclosure, the Si/T-atom ratio is from 0.068 to 0.094, such as for example, 0.068, 0.069, 0.070, 0.071, 0.072, 0.073, 0.074, 0.075, 0.076, 0.077, 0.078, 0.079, 0.080, 0.081, 0.082, 0.083, 0.084, 0.085, 0.086, 0.087, 0.088, 0.089, 0.090, 0.091, 0.092, 0.093, or 0.094. The Si/T-atom ratio may be determined by methods known in the art, including, for example, EDS elemental analysis. wherein T=Si+Al+P.
[0070] In other embodiments of the CIT-17 of the disclosure, the Si/T-atom ratio is 0.083 as determined by EDS elemental analysis.
[0071] In some aspects of the disclosure, the CIT-17 is characterized by its pore volume. In some embodiments, the CIT-17 has a pore volume of about 0.1 cm.sup.3/g to about 0.2 cm.sup.3/g, such as, for example, about 0.1 cm.sup.3/g, about 0.11 cm.sup.3/g, about 0.12 cm.sup.3/g, about 0.13 cm.sup.3/g, about 0.14 cm.sup.3/g, about 0.15 cm.sup.3/g, about 0.16 cm.sup.3/g, about 0.17 cm.sup.3/g, about 0.18 cm.sup.3/g, about 0.19 cm.sup.3/g, or about 0.2 cm.sup.3/g.
[0072] In some embodiments, the CIT-17 has a pore volume of 0.1 cm.sup.3/g, 0.11 cm.sup.3/g, 0.12 cm.sup.3/g, 0.13 cm.sup.3/g, 0.14 cm.sup.3/g, 0.15 cm.sup.3/g, 0.16 cm.sup.3/g, 0.17 cm.sup.3/g, 0.18 cm.sup.3/g, 0.19 cm.sup.3/g, or 0.2 cm.sup.3/g.
[0073] In some embodiments, the CIT-17 has a pore volume of about 0.15 cm.sup.3/g. In other embodiments, the CIT-17 has a pore volume of 0.15 cm.sup.3/g.
[0074] In some aspects, the disclosure also provides Me-aluminophosphate-based molecular sieves having an SAT framework structure (MeAPO-SAT), wherein Me is a metal, and wherein the MeAPO-SAT is substantially free of a non-MeAPO-SAT phase.
[0075] In some embodiments of the MeAPO-SAT that is substantially free of a non-MeAPO-SAT phase, the Me is a rare earth, Group 1, Group 2, or transition metals, such as, for example Ca, Cd, Co, Cu, Fe, Mg, Mn, Ni, Pt, Pd, Re, Sn, Ti, V, W, Zn and their mixtures.
[0076] In some embodiments of the MeAPO-SAT that is substantially free of a non-MeAPO-SAT phase, the Me is magnesium (Mg) or cobalt (Co).
[0077] In some embodiments of the MeAPO-SAT that is substantially free of a non-MeAPO-SAT phase, the Me is magnesium (Mg).
[0078] In some embodiments of the MeAPO-SAT that is substantially free of a non-MeAPO-SAT phase, the Me is cobalt (Co).
Methods of Making the Compositions of the Disclosure
[0079] In some aspects, the disclosure provides methods of making CIT-17.
[0080] In general, the methods of making CIT-17 comprise: [0081] a. preparing a synthesis gel by mixing a phosphorus source, water, an aluminum source, a silica source and an organic structure determining agent (OSDA); [0082] b. aging the resulting synthesis gel; [0083] c. heating the aged synthesis gel; [0084] d. washing the resulting powder; and [0085] e. drying the powder.
[0086] In some embodiments, the methods of making CIT-17 comprise: [0087] a. preparing a synthesis gel by a process comprising: [0088] i. mixing a phosphorus source and water; [0089] ii. adding an aluminum source, and allowing the resulting gel to homogenize; [0090] iii. adding a silica source to the mixture; and [0091] iv. adding an organic structure determining agent (OSDA); and [0092] b. aging the resulting synthesis gel at room temperature; [0093] c. heating the aged synthesis gel; [0094] d. washing the resulting powder; and [0095] e. drying the powder.
[0096] In some embodiments, the methods of making CIT-17 comprise: [0097] a. preparing a synthesis gel by a process comprising: [0098] i. mixing a phosphorus source and water, and stirring the resulting mixture for 10 minutes; [0099] ii. adding an aluminum source, and allowing the resulting gel to homogenize for 3-4 hours; [0100] iii. adding a silica source to the mixture; [0101] iv. adding an organic structure determining agent (OSDA); [0102] b. aging the resulting synthesis gel at room temperature for 20-24 hours; [0103] c. heating the aged synthesis gel to about 160-200? C.; [0104] d. washing the resulting powder with distilled water and acetone; [0105] e. drying the powder in a convection oven at about 80? C.
[0106] In some embodiments, the aged synthesis gel in step c. is heated to about 160-200? C., such as, for example, about 160? C., about 165? C., about 170? C., about 175? C., about 180? C., about 185? C., about 190? C., about 195? C., or about 200? C.
[0107] In some embodiments, the methods of making CIT-17 comprise: [0108] a. preparing a synthesis gel by a process comprising: [0109] i. mixing a phosphorus source and water, and stirring the resulting mixture for 10 minutes; [0110] ii. adding an aluminum source, and allowing the resulting gel to homogenize for 3-4 hours; [0111] iii. adding a silica source to the mixture; [0112] iv. adding an organic structure determining agent (OSDA); [0113] b. aging the resulting synthesis gel at room temperature for 20-24 hours; [0114] c. heating the aged synthesis gel to about 190? C. in an oven for about 3 days; [0115] d. washing the resulting powder with distilled water and acetone; [0116] e. drying the powder in a convection oven at about 80? C.
[0117] In some embodiments, the oven used in step c. is a static oven. In other embodiments, the oven used in step c. is a rotating oven.
[0118] In some embodiments, the methods of making CIT-17 comprise: [0119] a. preparing a synthesis gel by a process comprising: [0120] i. mixing a phosphorus source and water, and stirring the resulting mixture for 10 minutes; [0121] ii. adding an aluminum source, and allowing the resulting gel to homogenize for 3-4 hours; [0122] iii. adding a silica source to the mixture; [0123] iv. adding an organic structure determining agent (OSDA); [0124] b. aging the resulting synthesis gel at room temperature for 20-24 hours; [0125] c. heating the aged synthesis gel to about 190? C. in a rotating oven (55-60 rpm) at autogenous pressure for about 3 days; [0126] d. washing the resulting powder with distilled water and acetone; [0127] e. drying the powder in a convection oven at about 80? C.
[0128] In some embodiments, the phosphorus source used for making the CIT-17 of the disclosure is phosphoric acid. In other embodiments, the phosphorus source used for making the CIT-17 of the disclosure is P.sub.2O.sub.5.
[0129] In some embodiments, the aluminum source used for making the CIT-17 of the disclosure is alurninates, alumina, and aluminum compounds such as Al.sub.2(SO.sub.4);, Al(OH).sub.3, kaolin clays, and other zeolites. In some embodiments, the aluminum source used for making the CIT-17 of the disclosure is aluminum hydroxide.
[0130] The silica (silicon oxide) source used in the methods of the disclosure may comprise a silicate, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicate, a silica hydroxide or combination thereof. In some embodiments, the silica source used for making the CIT-17 of the disclosure is fumed silica.
[0131] In embodiments, the OSDA is DiQ-C.sub.4, DiQ-C.sub.5, or DiDABCO-C.sub.4.
[0132] In some embodiments, the OSDA is DiQ-C.sub.4. As used herein, DiQ-C.sub.4 refers to a dianion salt of 1,1-(butane-1,4-diyl)bis(quinuclidin-1-ium):
##STR00001##
[0133] In some embodiments, DiQ-C.sub.4 is used as the dibromide salt. In other embodiments, DiQ-C.sub.4 is used as the dihydroxide salt. In yet other embodiments, DiQ-C.sub.4 is used as a mixture of the hydroxide and bromide salts.
[0134] In other embodiments, the OSDA is DiQ-C.sub.5. As used herein, DiQ-C.sub.5 refers to a dianion salt of 1,1-(pentane-1,5-diyl)bis(quinuclidin-1-ium):
##STR00002##
[0135] In some embodiments, DiQ-C.sub.5 is used as the dibromide salt. In other embodiments, DiQ-C.sub.5 is used as the dihydroxide salt. In yet other embodiments, DiQ-C.sub.5 is used as a mixture of the hydroxide and bromide salts.
[0136] In other embodiments, the OSDA is DiDABCO-C.sub.4. As used herein, DiDABCO-C.sub.4 refers to a dianion salt of 1,1-(butane-1,4-diyl)bis(1,4-diazabicyclo[2.2.2]octan-1-ium):
##STR00003##
[0137] In some embodiments, DiDABCO-C.sub.4 is used as the dibromide salt. In other embodiments, DiDABCO-C.sub.4 is used as the dihydroxide salt. In yet other embodiments, DiDABCO-C.sub.4 is used as a mixture of the hydroxide and bromide salts.
[0138] In some embodiments, the methods of making the CIT-17 of the disclosure comprise: [0139] a. preparing a synthesis gel by a process comprising: [0140] i. mixing phosphoric acid (H.sub.3PO.sub.4) (85%) and water, and stirring the resulting mixture for about 5-20 minutes; [0141] ii. adding aluminum hydroxide, and allowing the resulting gel to homogenize for about 2-6 hours; [0142] iii. adding fumed silica to the mixture; [0143] iv. adding an organic structure determining agent (OSDA); [0144] b. aging the resulting synthesis gel at about 15-35? C. for about 15-30 hours; [0145] c. heating the aged synthesis gel to about 160-200? C. in an oven at autogenous pressure for about 1-5 days; [0146] d. washing the resulting powder with distilled water and acetone; [0147] e. drying the powder in a convection oven at about 60-100? C.
[0148] In some embodiments, the methods of making the CIT-17 of the disclosure comprise: [0149] a. preparing a synthesis gel by a process comprising: [0150] i. mixing phosphoric acid (H.sub.3PO.sub.4) (85%) and water, and stirring the resulting mixture for about 10 minutes; [0151] ii. adding aluminum hydroxide, and allowing the resulting gel to homogenize for 3-4 hours; [0152] iii. adding fumed silica to the mixture; [0153] iv. adding an organic structure determining agent (OSDA); [0154] b. aging the resulting synthesis gel at room temperature for 20-24 hours; [0155] c. heating the aged synthesis gel to about 190? C. in a rotating oven (55-60 rpm) at autogenous pressure for about 3 days; [0156] d. washing the resulting powder with distilled water and acetone; [0157] e. drying the powder in a convection oven at about 80? C.
[0158] In some aspects of the methods of making the CIT-17 of the disclosure, the method further comprising thermally treating, or calcining, the powder that is the product of step e.
[0159] In some aspects of the methods of making the CIT-17 of the disclosure, the method further comprising thermally treating the powder that is the product of step e. under flowing air in a furnace by: [0160] a. heating to about 120-180? C. and holding for about 1-5 h; and then [0161] b. heating to about 550-600? C. and holding for about 8-18 h, or until complete combustion of any remaining OSDA has been accomplished.
[0162] In some embodiments of the methods of making the CIT-17 of the disclosure, the method further comprising thermally treating the powder that is the product of step e. under flowing air in a furnace by: [0163] a. heating to about 150? C. and holding for about 3 h; and then [0164] b. heating to about 580? C. and holding for about 12 h, or until complete combustion of any remaining OSDA has been accomplished.
[0165] In some aspects, the disclosure provides synthesis gels that are useful for producing the SAPO-SAT molecular sieve that is substantially free of a non-SAPO-SAT phase.
[0166] In some aspects of the methods of making CIT-17, the molar ratio of the components of the synthesis gel are critical in producing the SAPO-SAT molecular sieve that is substantially free of a non-SAPO-SAT phase. In some embodiments, the molar ratio of the OSDA in the synthesis gel is critical in producing the SAPO-SAT molecular sieve that is substantially free of a non-SAPO-SAT phase.
[0167] In some embodiments, the molar ratios in the synthesis gel are as follows: [0168] 0.06-0.15 SiO.sub.2, such as, for example, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, or 0.15; [0169] 0.44-0.5 Al.sub.2O.sub.3, such as, for example, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, or 0.5; [0170] 0.44-0.5 P.sub.2O.sub.5, such as, for example, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, or 0.5; [0171] 0.17-0.33 R(OH).sub.2, such as, for example, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, or 0.33, wherein R is DiQ-C.sub.4, DiQ-C.sub.5, or DiDABCO-C.sub.4; and [0172] 40-75 H.sub.2O, such as, for example, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75.
[0173] In other embodiments, the molar ratios in the synthesis gel are as follows: [0174] 0.1 SiO.sub.2; [0175] 0.44-0.5 Al.sub.2O.sub.3, such as, for example, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, or 0.5; [0176] 0.44-0.5 P.sub.2O.sub.5, such as, for example, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, or 0.5; 0.2-0.33 R(OH).sub.2, such as, for example, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, or 0.33, wherein R=DiDABCO-C.sub.4, and [0177] 40-75 H.sub.2O, such as, for example, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75.
[0178] In other embodiments, the molar ratios in the synthesis gel are as follows: [0179] 0.06-0.1 SiO.sub.2, such as, for example, 0.06, 0.07, 0.08, 0.09, or 0.1; 0.5 Al.sub.2O.sub.3; [0180] 0.45-0.5 P.sub.2O.sub.5, such as, for example, 0.45, 0.46, 0.47, 0.48, 0.49, or 0.5; [0181] 0.17-0.33 R(OH).sub.2 such as, for example, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, or 0.33, wherein R=DiQ-C.sub.4; and [0182] 40-75 H.sub.2O, such as, for example, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75.
[0183] In other embodiments, the molar ratios in the synthesis gel are as follows: [0184] 0.06-0.15 SiO.sub.2, such as, for example, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, or 0.15; [0185] 0.5 Al.sub.2O.sub.3; [0186] 0.45-0.49 P.sub.2O.sub.5, such as, for example, 0.45, 0.46, 0.47, 0.48, or 0.49; [0187] 0.23-0.27 R(OH).sub.2, such as, for example, 0.23, 0.24, 0.25, 0.26, or 0.27, wherein R=DiQ-C.sub.5; and [0188] 40 H.sub.2O.
[0189] In yet other embodiments, the molar ratios in the synthesis gel are one of those set forth in Table 1 herein.
[0190] In some aspects, the disclosure provides methods of making MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase, wherein the methods comprise: [0191] a. preparing a synthesis gel by a process comprising: [0192] i. mixing a phosphorus source and water; [0193] ii. adding an aluminum source, and allowing the resulting gel to homogenize; [0194] iii. adding a magnesium source or a cobalt source to the mixture; [0195] iv. adding an organic structure determining agent (OSDA); [0196] b. aging the resulting synthesis gel; [0197] c. heating the aged synthesis gel; [0198] d. washing the resulting powder; and [0199] e. drying the powder.
[0200] In some embodiments, the methods of making MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase comprise: [0201] a. preparing a synthesis gel by a process comprising: [0202] i. mixing a phosphorus source and water, and stirring the resulting mixture for 10 minutes; [0203] ii. adding an aluminum source, and allowing the resulting gel to homogenize for 3-4 hours; [0204] iii. adding a magnesium source or a cobalt source to the mixture; [0205] iv. adding an organic structure determining agent (OSDA); [0206] b. aging the resulting synthesis gel at room temperature for 20-24 hours; [0207] c. heating the aged synthesis gel to about 190? C. in a rotating oven (55-60 rpm) at autogenous pressure for about 3 days; [0208] d. washing the resulting powder with distilled water and acetone; [0209] e. drying the powder in a convection oven at about 80? C.
[0210] In other embodiments, the methods of making MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase comprise: [0211] a. preparing a synthesis gel by a process comprising: [0212] i. mixing phosphoric acid (H.sub.3PO.sub.4) (85%) and water, and stirring the resulting mixture for 10 minutes; [0213] ii. adding aluminum hydroxide, and allowing the resulting gel to homogenize for 3-4 hours; [0214] iii. adding cobalt (II) acetate tetrahydrate or magnesium acetate tetrahydrate to the mixture; [0215] iv. adding an organic structure determining agent (OSDA); [0216] b. aging the resulting synthesis gel at room temperature for 20-24 hours; [0217] c. heating the aged synthesis gel to about 190? C. in a rotating oven (55-60 rpm) at autogenous pressure for about 3 days; [0218] d. washing the resulting powder with distilled water and acetone; [0219] e. drying the powder in a convection oven at about 80? C.
[0220] In some aspects of the methods of making the MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase of the disclosure, the method further comprising thermally treating the powder that is the product of step e. under flowing air in a furnace by: [0221] a. heating to about 120-180? C. and holding for about 1-5 h; and then [0222] b. heating to about 550-600? C. and holding for about 8-18 h, or until complete combustion of any remaining OSDA has been accomplished.
[0223] In some embodiments of the methods of making the MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase of the disclosure, the method further comprising thermally treating the powder that is the product of step e. under flowing air in a furnace by: [0224] a. heating to about 150? C. and holding for about 3 h; and then [0225] b. heating to about 580? C. and holding for about 12 h, or until complete combustion of any remaining OSDA has been accomplished.
[0226] In some embodiments of the methods of making the MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase of the disclosure, the OSDA is DiQ-C.sub.4, DiQ-C.sub.5, or DiDABCO-C.sub.4.
[0227] In some embodiments of the methods of making the MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase of the disclosure, the OSDA is DiQ-C.sub.4.
[0228] In some embodiments of the methods of making the MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase of the disclosure, the OSDA is DiQ-C.sub.5.
[0229] In some embodiments of the methods of making the MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase of the disclosure, the OSDA is DiDABCO-C.sub.4.
[0230] In some aspects of the disclosed methods of making MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase the synthesis gel has a molar composition of: [0231] 0.02-0.08 cobalt (II) acetate tetrahydrate, such as, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, or 0.08; [0232] 0.45-0.5 Al.sub.2O.sub.3, such as, for example, 0.45, 0.46, 0.47, 0.48, 0.49, or 0.5; 0.45-0.55 P.sub.2O.sub.5, such as, for example, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, or 0.55; [0233] 0.27-0.4 R(OH).sub.2, such as, for example, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, or 0.4, wherein R is DiQ-C.sub.4, DiQ-C.sub.5, or DiDABCO-C.sub.4; and [0234] 40-75 H.sub.2O, such as, for example, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75.
[0235] In some aspects of the disclosed methods of making MeAPO-SAT molecular sieves that are substantially free of non-MeAPO-SAT phase the synthesis gel has a molar composition of: [0236] 0.1 magnesium acetate tetrahydrate; [0237] 0.45 Al.sub.2O.sub.3; [0238] 0.5 P.sub.2O.sub.5; [0239] 0.4 R(OH).sub.2 wherein wherein R is DiQ-C.sub.4, DiQ-C.sub.5, or DiDABCO-C.sub.4; and [0240] 40 H.sub.2O.
Oxygenate ConversionMethanol-To-Olefin (MTO) Reaction
[0241] In some aspects, the disclosure provides processes for catalytic conversion of a feedstock comprising one or more oxygenates comprising alcohols and ethers to a hydrocarbon product containing light olefins, i.e., C.sub.2, C.sub.3 and/or C.sub.4 olefins. In these aspects, the feedstock is contacted with a SAPO-SAT molecular sieve of the disclosure at effective process conditions to produce light olefins. The term oxygenate as used herein refers to oxygen-containing compounds such as alcohols, ethers, and carbonyl compounds (e.g., aldehydes, ketones, carboxylic acids). The oxygenate can contain from 1 to 10 carbon atoms, e.g., from 1 to 4 carbon atoms.
[0242] In some embodiments, the process is conducted in the presence of one or more diluents which can be present in the oxygenate feed in an amount of from 1 to 99 mole %, based on the total number of moles of all feed and diluent components. Diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, paraffins, hydrocarbons (such as methane and the like), aromatic compounds, or mixtures thereof
[0243] In some embodiments, the process is conducted in the vapor phase such that the oxygenate feedstock is contacted in a vapor phase in a reaction zone with SAPO-SAT molecular sieve of the disclosure at process conditions effective to produce hydrocarbons, i.e., an effective temperature, pressure, WHSV and, optionally, an effective amount of diluent. The process is conducted for a period of time sufficient to produce the desired light olefins. In general, the residence time employed to produce the desired product can vary from seconds to a number of hours. It will be readily appreciated that the residence time will be determined to a significant extent by the reaction temperature, the molecular sieve catalyst, the WHSV, the phase (liquid or vapor) and process design characteristics.
[0244] In some aspects, the process is conducted at a wide range of pressures, including but not limited to autogenous pressures and pressures in the range from 0.1 kPa to 10 MPa. In some embodiments, the pressure can be in the range from 7 kPa to 5 MPa, e.g., from 50 kPa to 1 MPa. The foregoing pressures are exclusive of diluents, if any are present, and refer to the partial pressure of the feedstock as it relates to oxygenate compounds and/or mixtures thereof.
[0245] In some embodiments, the temperature which can be employed in the oxygenate conversion process can vary over a wide range. In general, the process can be conducted at an effective temperature of from 250? C. to 600? C.
[0246] In some aspects, the SAPO-SAT molecular sieve of the disclosure can be incorporated into solid particles in which the catalyst is present in an amount effective to promote the desired conversion of oxygenates to light olefins. In one aspect, the solid particles comprise a catalytically effective amount of the catalyst and at least one matrix material such as binder materials, filler materials and mixtures thereof to provide a desired property or properties, e.g., desired catalyst dilution, mechanical strength and the like to the solid particles.
[0247] In some aspects, the disclosure provides processes for the production of propylene from a methanol-containing feed, wherein the process comprises passing the methanol-containing feed to a reactor, wherein the reactor comprises a catalyst comprising a SAPO-SAT molecular sieve, wherein the SAPO-SAT molecular sieve is substantially free of a non-SAPO-SAT phase, and wherein the reactor is operated at reaction conditions sufficient to generate an effluent stream comprising propylene and having a propylene to ethylene ratio between about 1.6 and about 4.2.
[0248] In other aspects, the disclosure provides processes for the production of propylene from a methanol-containing feed, the process comprising: passing the methanol-containing feed to a reactor, wherein the reactor comprises a catalyst comprising a MeAPO-SAT molecular sieve, wherein the MeAPO-SAT molecular sieve is substantially free of a non-MeAPO-SAT phase, wherein Me is cobalt or magnesium, and wherein the reactor is operated at reaction conditions sufficient to generate an effluent stream comprising propylene and having a propylene to ethylene ratio between about 1.6 and about 4.2.
[0249] In some embodiments of the MTO processes of the disclosure, the reactor is a fluidized bed, fixed bed, or swing fixed bed reactor.
[0250] In some embodiments of the MTO processes of the disclosure, the reactor is a fluidized bed reactor.
[0251] In other embodiments of the MTO processes of the disclosure, the reactor is a fixed bed reactor.
[0252] In yet other embodiments of the MTO processes of the disclosure, the reactor is swing fixed bed reactor.
[0253] In some embodiments of the MTO processes of the disclosure, the catalyst comprises a SAPO-SAT molecular sieve of the disclosure, that is, a SAPO-SAT molecular sieve that is substantially free of a non-SAPO-SAT phase.
[0254] In other embodiments of the MTO processes of the disclosure, the catalyst comprises a MeAPO-SAT molecular sieve of the disclosure, that is, a MeAPO-SAT molecular sieve that is substantially free of a non-MeAPO-SAT phase.
[0255] In some aspects, the MTO processes of the disclosure utilize a methanol-containing feed which is fed to the reactor. The methanol containing feed is a feed stream that comprises methanol. In some embodiments, the methanol-containing feed is methanol.
[0256] In some aspects of the MTO processes of the disclosure, the reactor is operated at reaction conditions sufficient to generate an effluent stream comprising propylene and having a propylene to ethylene ratio between about 1.6 and about 4.2, such as, for example, a propylene to ethylene ratio of about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9, about 3.0, about 3.1, about 3.2, about 3.3. about 3.4, about 3.5, about 3.6, about 3.7, about 3.8, about 3.9, about 4.0, about 4.1, or about 4.2.
[0257] In some embodiments of the MTO processes of the disclosure, the reactor is operated at reaction conditions sufficient to generate an effluent stream comprising propylene and having a propylene to ethylene ratio between about 1.6 and about 4.2, such as, for example, a propylene to ethylene ratio of 1.6, 1.7, 1.8, 1.9, 2.0, 7.1 2.2, 2.3. 2.4. 2.5, 2.6, 2.7. 2.8, 2.9, 3.0, 3.1 3.2 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, or 4.2.
[0258] In some aspects of the MTO processes of the disclosure, the reactor is operated at ambient pressure.
[0259] In some aspects of the MTO processes of the disclosure, the reactor is operated at elevated pressure.
[0260] In some aspects of the MTO processes of the disclosure, the methanol-containing feed flow rate provides a weight hourly space velocity (WHSV) of about 0.6511 h.sup.?1 to about 2.61 h.sup.?1, such as, for example, about 0.65 h.sup.?1, about 0.7 h.sup.?1, about 0.75 h.sup.?1, about 0.8 h.sup.?1, about 0.8511 h.sup.?1, about 0.9 h.sup.?1, about 0.95 h.sup.?1, about 1.0 h.sup.?1, about 1.05 h.sup.?1, about 1.1 h.sup.?1, about 1.15 h.sup.?1, about 1.2 h.sup.?1, about 1.25 h.sup.?1, about 1.3 h.sup.?1, about 1.35 h.sup.?1, about 1.4 h.sup.?1, about 1.45 h.sup.?1, about 1.5 h.sup.?1, about 1.55 h.sup.?1, about 1.6 h.sup.?1, about 1.65 h.sup.?1, about 1.7 h.sup.?1, about 1.75 h.sup.?1, about 1.8 h.sup.?1, about 1.85 h.sup.?1, about 1.9 j.sup.?1, about 1.95 h.sup.?1, about 2.0 h.sup.?1, about 2.05 h.sup.?1, about 2.1 h.sup.?1, about 2.15 h.sup.?1, about 2.2 h.sup.?1, about 2.25 h.sup.?1, about 2.3 h.sup.?1, about 2.35 h.sup.?1, about 2.4 h.sup.?1, about 2.45 h.sup.?1 about 2.5 h.sup.?1, about 2.55 h.sup.?1, or about 2.6 h.sup.?1.
[0261] In some aspects of the MTO processes of the disclosure, the methanol-containing feed flow rate provides a weight hourly space velocity (WHSV) of about 0.65 h.sup.?1 to about 2.6 h.sup.?1, such as, for example, 0.65 h.sup.?0.711 h.sup.?, 0.75 h.sup.?1, 0.8 h.sup.?1, 0.85 h.sup.?1, 0.9 h.sup.?1, 0.95 h.sup.?1, 1.0 h.sup.?1, 1.05 h.sup.?1, 1.1 h.sup.?1, 1.15 h.sup.?1, 1.2 h.sup.?1, 1.25 h.sup.?1, 1.3 h.sup.?1, 1.35 h.sup.?1, 1.4 h.sup.?1, 1.45 h.sup.?1, 1.5 h.sup.?1, 1.55 h.sup.?1, 1.6 h.sup.?1, 1.65 h.sup.?1, 1.7 h.sup.?1, 1.75 h.sup.?1, 1.8 h.sup.?1, 1.85 h.sup.?1, 1.9 h.sup.?1, 1.95 h.sup.?1, 2.0 h.sup.?1, 2.05 h.sup.?1, 2.111 h.sup.?1, 2.15 h.sup.?, 2.2 h.sup.?1, 2.25 h.sup.?1, 2.3 h.sup.?1, 2.35 h.sup.?1, 2.4 h.sup.?1, 2.45 h.sup.?1, 2.5 h.sup.?1, 2.55 h.sup.?1, or 2.611 h.sup.?1.
[0262] In some aspects of the MTO processes of the disclosure, the reactor is operated at a temperature of about 350? C.-about 600? C., such as, for example, about 350? C., about 355? C., about 360? C., about 365? C., about 370? C., about 375? C., about 380? C., about 385? C., about 390? C., about 395? C., about 400? C., about 405? C., about 410? C., about 415? C., about 420? C., about 425? C., about 430? C., about 435? C., about 440? C., about 445? C., about 450? C., about 455? C., about 460? C., about 465? C., about 470? C., about 475? C., about 480? C., about 485? C., about 490? C., about 495? C., about 500? C., about 505? C., about 510? C., about 515? C., about 520? C., about 525? C., about 530? C., about 535? C., about 540? C., about 545? C., about 550? C., about 555? C., about 560? C., about 565? C., about 570? C., about 575? C., about 580? C., about 585? C., about 590? C., about 595? C., or about 600? C.
[0263] In some aspects of the MTO processes of the disclosure, the reactor is operated at a temperature of 350? C.-600? C., such as, for example, 350? C., 355? C., 360? C., 365? C., 370? C., 375? C., 380? C., 385? C., 390? C., 395? C., 400? C., 405? C., 410? C., 415? C., 420 ? C., 425? C., 430? C., 435? C., 440? C., 445? C., 450? C., 455? C., 460? C., 465? C., 470? C., 475? C., 480? C., 485? C., 490? C., 495? C., 500? C., 505? C., 510? C., 515? C., 520? C., 525? C., 530? C., 535 ? C., 540? C., 545? C., 550? C., 555? C., 560? C., 565? C., 570? C., 575? C., 580? C., 585? C., 590? C., 595? C., or 600? C.
[0264] In some aspects of the MTO processes of the disclosure, the reactor is operated at a temperature of about 350? C.-about 400? C., such as, for example, about 350? C., about 355? C., about 360? C., about 365? C., about 370? C., about 375? C., about 380? C., about 385? C., about 390? C., about 395? C., or about 400? C.
[0265] In some aspects of the MTO processes of the disclosure, the reactor is operated at a temperature of 350? C.-400? C., such as, for example, 350? C., 355? C., 360? C., 365? C., 370? C., 375? C., 380? C., 385? C., 390? C., 395? C., or 400? C.
[0266] In some aspects of the MTO processes of the disclosure, greater than 97% of the methanol in the methanol-containing feed is converted, such as for example, greater than 97%, greater than 97.1%, greater than 97.2%, greater than 97.3%, greater than 97.4%, greater than 97.5%, greater than 97.6%, greater than 97.7%, greater than 97.8%, greater than 97.9%, greater than 98%, greater than 98.1%, greater than 98.2%, greater than 98.3%, greater than 98.4%, greater than 98.5%, greater than 98.6%, greater than 98.7%, greater than 98.8%, greater than 98.9%, greater than 99%, greater than 99.1%, greater than 99.2%, greater than 99.3%, greater than 99.4%, greater than 99.5%, greater than 99.6%, greater than 99.7%, greater than 99.8%, or greater than 99.9%.
[0267] In some embodiments of the MTO processes of the disclosure, the catalyst is first pretreated by heating to an elevated temperature, and holding at that temperature for a period of time under flowing air.
[0268] In some embodiments of the MTO processes of the disclosure, the catalyst is first pretreated by heating to about 150? C. at 1? C./min, holding for about 3 h, and then heated further to about 580? C. at 1? C./min and holding for about 12 h under flowing air (breathing-grade D).
[0269] In some embodiments of the MTO processes of the disclosure, after the catalyst deactivates (as shown by either its conversion drops below 85% or DME selectivity surpasses 50%), the methanol-containing feed is shut shut off and the catalyst is cooled before being re-activated (air) by heating to an elevated temperature, and holding at that temperature for a period of time under flowing air.
[0270] In other embodiments of the MTO processes of the disclosure, after the catalyst deactivates (as shown by either its conversion drops below 85% or DME selectivity surpasses 50%), the methanol-containing feed is shut shut off and the catalyst is cooled before being re-activated (air) by heating to about 150? C. at 1? C./min, holding for about 3 h, and then heated further to about 580? C. at 1? C./min and holding for about 12 h under flowing air (breathing-grade D).
[0271] In other embodiments of the MTO processes of the disclosure, after the catalyst deactivates (as shown by either its conversion drops below 85% or DME selectivity surpasses 50%), the methanol-containing feed is shut shut off and the catalyst is cooled to approximately 100? C. before being re-activated (air) by heating to an elevated temperature, and holding at that temperature for a period of time under flowing air.
[0272] In other embodiments of the MTO processes of the disclosure, after the catalyst deactivates (as shown by either its conversion drops below 85% or DME selectivity surpasses 50%), the methanol-containing feed is shut shut off and the catalyst is cooled to approximately 100? C. before being re-activated (air) by heating to about 150? C. at 1? C./min, holding for about 3 h, and then heated further to about 580? C. at 1? C./min and holding for about 12 h under flowing air (breathing-grade D).
Other Uses
[0273] The SAPO-SAT molecular sieves of the disclosure also are useful in other applications, including as an adsorbent for gas separations; as a catalyst for making small amines; to reduce oxides of nitrogen in a gas streams, such as automobile exhaust; as a cold start hydrocarbon trap in combustion engine pollution control systems; and for trapping C.sub.3 fragments.
Gas Separation
[0274] The SAPO-SAT molecular sieves of the disclosure can be used to separate gases. For example, they can be used to separate carbon dioxide from natural gas. Typically, the molecular sieve is used as a component in a membrane that is used to separate the gases. Examples of such membranes are disclosed in U.S. Pat. No. 6,508,860.
Synthesis of Amines
[0275] The SAPO-SAT molecular sieves of the disclosure can be used in a catalyst to prepare methylamine or dimethylamine. Dimethylamine is generally prepared in industrial quantities by continuous reaction of methanol (and/or dimethyl ether) and ammonia in the presence of a silica-alumina catalyst. The reactants are typically combined in the vapor phase, at temperatures of from 300? C. to 500? C., and at elevated pressures. Such a process is disclosed in U.S. Pat. No. 4,737,592.
Reduction of Oxides of Nitrogen (NOx)
[0276] The SAPO-SAT molecular sieves of the disclosure can be used for the catalytic reduction of the oxides of nitrogen in a gas stream. Typically, the gas stream also contains oxygen, often a stoichiometric excess thereof. Also, the molecular sieve can contain a metal or metal ions within or on it which are capable of catalyzing the reduction of the nitrogen oxides. Examples of such metals or metal ions include lanthanum, chromium, manganese, iron, cobalt, rhodium, nickel, palladium, platinum, copper, zinc, and mixtures thereof. See, e.g., U.S. Pat. No. 4,297,328.
Treatment of Engine Exhaust (Cold Start Emissions)
[0277] The SAPO-SAT molecular sieves of the disclosure can also be used in adsorbent beds to adsorb the hydrocarbons during the cold start portion of the engine. Although the process typically will be used with hydrocarbon fuels, the present disclosure can also be used to treat exhaust streams from alcohol-fueled engines. The adsorbent bed is typically placed immediately before the catalyst. Thus, the exhaust stream is first flowed through the adsorbent bed and then through the catalyst. The adsorbent bed preferentially adsorbs hydrocarbons over water under the conditions present in the exhaust stream. After a certain amount of time, the adsorbent bed has reached a temperature (typically about 150? C.) at which the bed is no longer able to remove hydrocarbons from the exhaust stream. That is, hydrocarbons are actually desorbed from the adsorbent bed instead of being adsorbed. This regenerates the adsorbent bed so that it can adsorb hydrocarbons during a subsequent cold start. The use of adsorbent beds to minimize hydrocarbon emissions during a cold start engine operation is known in the art. See, for example, U.S. Pat. Nos. 2,942,932; 3,699,683; and 5,078,979.
[0278] In some embodiments, the engine exhaust gas stream which is to be treated is flowed over a molecular sieve bed comprising SAPO-SAT molecular sieves of the disclosure as a first exhaust stream. The first exhaust stream which is discharged from the molecular sieve bed is now flowed over a catalyst to convert the pollutants contained in the first exhaust stream to innocuous components and provide a treated exhaust stream which is discharged into the atmosphere. It is understood that prior to discharge into the atmosphere, the treated exhaust stream can be flowed through a muffler or other sound reduction apparatus well known in the art.
[0279] When the molecular sieve bed reaches a sufficient temperature, typically from 150? C. to 200? C., the pollutants which are adsorbed in the bed begin to desorb and are carried by the first exhaust stream over the catalyst. At this point the catalyst has reached its operating temperature and is therefore capable of fully converting the pollutants to innocuous components. Exemplary uses of molecular sieves in this manner are given in U.S. Pat. No. 9,700,878.
[0280] The disclosure is also directed to the following aspects:
[0281] Aspect 1. A silicoaluminophosphate-based molecular sieve having an SAT framework structure (SAPO-SAT), wherein the SAPO-SAT is substantially free of a non-SAPO-SAT phase.
[0282] Aspect 2. The SAPO-SAT of aspect 1, wherein the SAPO-SAT is substantially free of SAPO-AFX.
[0283] Aspect 3. The SAPO-SAT of aspect 1 or aspect 2, wherein the Si/T-atom ratio is from about 0.068 to about 0.094 as determined by EDS elemental analysis, wherein T=Si+Al+P.
[0284] Aspect 4. The SAPO-SAT of aspect 3, wherein the Si/T-atom ratio is 0.083 as determined by EDS elemental analysis, wherein T=Si+Al+P.
[0285] Aspect 5. The SAPO-SAT of any one of aspects 1 to 4, wherein the SATO-SAT has a pore volume of about 0.15 cm.sup.3/g.
[0286] Aspect 6. The SAPO-SAT of any one of aspects 1 to 5, wherein the SATO-SAT has an XRD substantially the same as that shown in
[0287] Aspect 7. A process for making the SAPO-SAT molecular sieve of any one of aspects 1-6, the process comprising: [0288] a. preparing a synthesis gel by a process comprising: [0289] i. mixing a phosphorus source and water, and stirring the resulting mixture for 10 minutes; [0290] ii. adding an aluminum source, and allowing the resulting gel to homogenize for 3-4 hours; [0291] iii. adding a silica source to the mixture; [0292] iv. adding an organic structure determining agent (OSDA); [0293] b. aging the resulting synthesis gel at room temperature for 20-24 hours; [0294] c. heating the aged synthesis gel to about 160-200? C. for about 3 days; [0295] d. washing the resulting powder with distilled water and acetone; [0296] e. drying the powder in a convection oven at about 80? C.
[0297] Aspect 8. The process of aspect 7, the process comprising: [0298] a. preparing a synthesis gel by a process comprising: [0299] i. mixing phosphoric acid (H.sub.3PO.sub.4) (85%) and water, and stirring the resulting mixture for 10 minutes; [0300] ii. adding aluminum hydroxide, and allowing the resulting gel to homogenize for 3-4 hours; [0301] iii. adding fumed silica to the mixture; [0302] iv. adding an organic structure determining agent (OSDA); [0303] b. aging the resulting synthesis gel at room temperature for 20-24 hours; [0304] c. heating the aged synthesis gel to about 160-200? C. for about 3 days; [0305] d. washing the resulting powder with distilled water and acetone; [0306] e. drying the powder in a convection oven at about 80? C.
[0307] Aspect 9. The process of aspect 7 or aspect 8, further comprising thermally treating the powder that is the product of step e. under flowing air in a furnace by: [0308] a. heating to about 150? C. and holding for about 3 h; and then [0309] b. heating to about 580? C. and holding for about 12 h, or until complete combustion of any remaining OSDA has been accomplished.
[0310] Aspect 10. The process of any one of aspects 7-9, wherein the OSDA is DiQ-C.sub.4, DiQ-C.sub.5, or DiDABCO-C.sub.4.
[0311] Aspect 11. The process of any one of aspects 7-10, wherein the synthesis gel has a molar composition of: [0312] 0.06-0.15 SiO.sub.2; [0313] 0.44-0.5 Al.sub.2O.sub.3; [0314] 0.44-0.5 P.sub.2O.sub.5; [0315] 0.17-0.33 R(OH).sub.2 wherein R is DiQ-C.sub.4, DiQ-C.sub.5, or DiDABCO-C.sub.4; and [0316] 40-75 H.sub.2O
[0317] Aspect 12. The process of any one of aspects 7-10, wherein the synthesis gel has a molar composition of: [0318] SiO.sub.2; [0319] 0.44-0.5 Al.sub.2O.sub.3; [0320] 0.44-0.5 P.sub.2O.sub.5; [0321] 0.2-0.33 R(OH).sub.2 wherein R=DiDABCO-C.sub.4; and [0322] 40-75 H.sub.2O.
[0323] Aspect 13. The process of any one of aspects 7-10, wherein the synthesis gel has a molar composition of: [0324] 0.06-0.1 SiO.sub.2; [0325] 0.5 Al.sub.2O.sub.3; [0326] 0.45-0.5 P.sub.2O.sub.5; [0327] 0.17-0.33 R(OH).sub.2 wherein R=DiQ-C.sub.4; and [0328] 40-75 H.sub.2O.
[0329] Aspect 14. The process of any one of aspects 7-10, wherein the synthesis gel has a molar composition of: [0330] 0.06-0.15 SiO.sub.2; [0331] 0.5 Al.sub.2O.sub.3; [0332] 0.45-0.49 P.sub.2O.sub.5; [0333] 0.23-0.27 R(OH).sub.2 wherein R=DiQ-C.sub.5; and [0334] 40 H.sub.2O.
[0335] Aspect 15. A process for the production of propylene from a methanol-containing feed, the process comprising: passing the methanol-containing feed to a reactor, wherein the reactor comprises a catalyst comprising a SAPO-SAT molecular sieve, wherein the SAPO-SAT molecular sieve is substantially free of a non-SAPO-SAT phase, and wherein the reactor is operated at reaction conditions sufficient to generate an effluent stream comprising propylene and having a propylene to ethylene ratio between about 1.6 and about 4.2.
[0336] Aspect 16. A process for the production of propylene from a methanol-containing feed, the process comprising: passing, the methanol-containing feed to a reactor, wherein the reactor comprises a catalyst comprising a MeAPO-SAT molecular sieve, wherein the MeAPO-SAT molecular sieve is substantially free of a non-MeAPO-SAT phase, wherein Me is cobalt or magnesium, and wherein the reactor is operated at reaction conditions sufficient to generate an effluent stream comprising pro xylene and having a propylene to ethylene ratio between about 1.6 and about 4.2.
[0337] Aspect 17. The process of aspect 15 or aspect 16, wherein the reactor is a fluidized bed, fixed bed, or swing fixed bed reactor.
[0338] Aspect 18. The process of any one of aspects 15-17, wherein the process is operated at ambient pressure.
[0339] Aspect 19. The process of any one of aspects 15-18, wherein the methanol-containing feed flow rate provides a weight hourly space velocity (WHSV) of about 0.65 h.sup.?1 to about 2.6 h.sup.?1.
[0340] Aspect 20. The process of any one of aspects 15-19, wherein the reactor is operated at a temperature of about 350? C. about 600? C.
[0341] Aspect 21. The process of any one of aspects 15-20, wherein greater than 97% of the methanol in the methanol-containing feed is converted.
EXAMPLES
[0342] The following Examples are provided to illustrate some of the concepts described within this disclosure. While each Example is considered to provide specific individual embodiments of composition, methods of preparation and use, none of the Examples should be considered to limit the more general embodiments described herein.
Example 1
Synthesis of DiQ-C.SUB.4
[0343] DiQ-C.sub.4 was prepared from the reaction of quinuclidine (97%, Alfa Aesar) and 1,4-dibromobutane (99%, Sigma Aldrich). In a typical synthesis, quinuclidine (100 mmol) was mixed with 150 cm.sup.3 of methanol and stirred at room temperature for a few minutes. The solution was then heated to 45? C. in an oil bath. After reaching 45? C., 1,4-dibromobutane (35 mmol) was added dropwise to the quinuclidine-containing solution while stirring. After adding 1,4-dibromobutane, the reaction mixture was heated to 80? C. and refluxed for 6 days. Methanol was then evaporated using a rotary evaporator, and the solid product was filtered and washed with methanol, diethyl ether, and acetone. Following this, the solid was dried under vacuum at room temperature for 6-8 h. The .sup.13C NMR spectrum of DiQ-C.sub.4 OSDA in its bromide form is shown in
[0344] The OSDA was then converted to its hydroxide form, and its concentration was determined by titration. The OSDA above was first ion-exchanged into its hydroxide form by dissolving the organic salt in DI water and then adding DOWEX? Monosphere? 550A hydroxide ion-exchange resin. Specifically, for every 100 mmol of OSDA in the halide form, approximately 300 cm.sup.3 (by volume) of resin and 500 cm.sup.3 of DI water were added. The mixture was then stirred for 24 h at room temperature. After 24 h, the resin was separated by filtration, and the process was repeated a second time. The concentration of the OSDA, now in the hydroxide form, was quantified using a Mettler Toledo DL22 Potentiometric pH meter. Five readings were taken for each OSDA concentration, and these values were then averaged and used for gel calculations.
Example 2
Synthesis of DiQ-C.SUB.5
[0345] DiQ-C.sub.5 was prepared from the reaction of quinuclidine (97%, Alfa Aesar) and 1,5-dibromopentane (97%, Sigma Aldrich). In a typical synthesis, quinuclidine (100 mmol) was mixed with 150 cm.sup.3 of acetone and stirred at room temperature for a few minutes. The solution was then heated to 45? C. in an oil bath. After reaching 45? C., 1,5-dibromopentane (35 mmol) was added dropwise to the quinuclidine-containing solution while stirring. After adding 1,5-dibromopentane, the reaction mixture was heated to 80? C. and refluxed for 6 days. Acetone was then evaporated using a rotary evaporator, and the solid product was filtered and washed with diethyl ether and acetone. Following this, the solid was dried under vacuum at room temperature for 6-8 h. The .sup.13C NMR spectrum of DiQ-C.sub.5 OSDA in its bromide form is shown in
Example 3
Synthesis of DiDABCO-C.SUB.4
[0346] DiDABCO-C.sub.5 was prepared from the reaction of 1,4-diazabicyclo[2.2.2]octane (abbreviated as DABCO) (Sigma Aldrich) and 1,4-dibromobutane (99%, Sigma Aldrich). In a typical synthesis, DABCO (600 mmol) was mixed with 150 cm.sup.3 of methanol and stirred at room temperature for a few minutes. The solution was then heated to 45? C. in an oil bath. After reaching 45? C., 1,4-dibromobutane (75 mmol) was added dropwise to the DABCO-containing solution while stirring. After adding 1,4-dibromobutane, the reaction mixture was heated to 80? C. and refluxed for 6 days. Methanol was then evaporated using a rotary evaporator, and the solid product was filtered and washed with methanol, diethyl ether and acetone. Following this, the solid was dried under vacuum at room temperature for 6-8 h. The .sup.13C NMR spectrum of DiDABCO-C.sub.4 OSDA in its bromide form is shown in
Example 4
Synthesis of CIT-17
[0347] All CIT-17 materials were prepared in 23 cm.sup.3 stainless steel Parr autoclaves with Teflon liners. In a typical synthesis, a desired amount of phosphoric acid (H.sub.3PO.sub.4) (85%, MACRON) was mixed with an appropriate amount of water, and the mixture was stirred for 10 mins. Next, the aluminum source (Barcroft? 0250 dried aluminum hydroxide gel, SPI Pharma) was weighed separately and added to this mixture. This gel was allowed to homogenize for 3-4 hours before adding fumed silica (Cab-O-Sil?, ACROS). Following the addition of silica, the OSDA (DiQ-C.sub.5) was added, and the gel was aged at room temperature for 20-24 hours before being heated to 190? C. in a rotating oven (55-60 rpm) at autogenous pressure for 3 days. A synthesis gel molar composition for CIT-17 was: 0.15 SiO.sub.2: 0.5 Al.sub.2O.sub.3: 0.49 P.sub.2O.sub.5: 0.27 R(OH).sub.2: 40 H.sub.2O, where R=DiQ-C.sub.5. The resultant powder was washed carefully with distilled water and acetone and then dried in an 80? C. convection oven before being characterized using a battery of techniques.
Example 5
Characterization of As-Synthesized CIT-17
[0348] The dried CIT-17 sample from Example 4 was characterized using powder X-ray diffraction (XRD) on a Rigaku Miniflex II diffractometer with Cu Ka radiation (wavelength=1.5418 ?). The obtained powder XRD (PXRD) diffraction pattern of the as-synthesized CIT-17 product is shown in
Example 6
Characterization of Thermally Treated CIT-17
[0349] The CIT-17 sample from Example 4 was thermally treated (in a ceramic calcination boat) under flowing breathing-grade air in a Nabertherm DKN400 muffle furnace. The sample was initially heated to 150? C. at a heating rate of 1? C./min and held for 3 h before being heated to 580? C. (again at a heating rate of 1? C./min) and held for 12 h to ensure complete combustion of any remaining OSDA. Solid-state, magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy experiments were conducted on a Bruker 500 MHz spectrometer using a 4 mm ZrO.sub.2 rotor. In a typical experiment, the thermally treated sample was dehydrated under vacuum (10.sup.?2 Torr) at 400? C. for 10 h at a ramp rate of 2? C./min in a dehydration manifold after being pre-packed in an uncapped NMR rotor. The rotor was then capped while under vacuum and inside the dehydration manifold (to minimize sample exposure to moisture) and then loaded into the spectrometer. For .sup.29Si MAS NMR spectroscopy, this procedure was modified by introducing oxygen to the dehydrated sample to reduce the relaxation time before packing the rotor. The coordinations of Al, P, and Si in the thermally treated CIT-17 sample are shown in
Examples 7-53
Syntheses of CIT-17 Using Various OSDAs and Gel Compositions
[0350] Several SAT-type materials, including numerous CIT-17s, were synthesized based on the synthesis procedure from Example 4 with some modifications (e.g., Si/Al or Al/P content, type of oven, temperature, presence of seed, etc.). A summary of these results is shown in Table 1. Three OSDAs were tested (from Examples 1-3) at different gel compositions. The original STA-2 synthesis procedure was also reproduced (Examples 29-30). In cases where Co and Mg were used in the gel, cobalt (cobalt (II) acetate tetrahydrate, Sigma Aldrich) and magnesium acetate (Mg-acetate tetrahydrodate; 99%, Sigma-Aldrich) were used as Co and Mg sources, respectively. Following synthesis, the resultant powders were washed carefully with distilled water and acetone and then dried in an 80? C. convection oven before being characterized using PXRD. PXRD patterns of a select group of samples are shown in
TABLE-US-00002 TABLE 1 Products and gel chemical compositions of SAT-type molecular sieves. Temper- ature Time Seed Product Example Al.sub.2O.sub.3 P.sub.2O.sub.5 SiO.sub.2 Co Mg OSDA R.sub.(total).sup.[a] R(OH).sub.2 H.sub.2O (? C.) (h) Rotation.sup.[b] (1 wt %).sup.[b] XRD.sup.[c] 7 0.45 0.5 0.1 0 0 DiQ-C4 0.40 0.40 40 190 48 N N CIT-16P + SAT 8 0.5 0.45 0.1 0 0 DiQ-C4 0.24 0.24 40 190 72 Y N CIT-16P + SAT 9 0.5 0.45 0.08 0 0 DiQ-C4 0.24 0.24 40 190 72 Y N CIT-16P + SAT 10 0.5 0.45 0.15 0 0 DiQ-C4 0.21 0.21 40 190 72 Y N SAT + impurity 11 0.5 0.45 0.1 0 0 DiQ-C4 0.21 0.21 40 190 72 Y N SAT 12 0.5 0.45 0.08 0 0 DiQ-C4 0.21 0.21 40 190 72 Y N SAT 13 0.5 0.45 0.06 0 0 DiQ-C4 0.21 0.21 40 190 72 Y N SAT 14 0.5 0.45 0.08 0 0 DiQ-C4 0.21 0.21 40 180 96 Y N SAT 15 0.5 0.45 0.08 0 0 DiQ-C4 0.21 0.21 40 200 72 Y N SAT 16 0.5 0.45 0.12 0 0 DiQ-C4 0.19 0.19 40 190 72 Y N SAT + impurity 17 0.5 0.45 0.1 0 0 DiQ-C4 0.19 0.19 40 190 72 Y N SAT 18 0.5 0.45 0.08 0 0 DiQ-C4 0.19 0.19 40 190 72 Y N SAT 19 0.5 0.45 0.1 0 0 DiQ-C4 0.17 0.17 40 190 72 Y N SAT 20 0.5 0.45 0.08 0 0 DiQ-C4 0.17 0.17 40 190 72 Y N SAT 21 0.5 0.5 0.1 0 0 DiQ-C4 0.27 0.27 40 190 72 N N SAT + AFX 22 0.5 0.48 0.1 0 0 DiQ-C4 0.25 0.25 40 190 72 N N SAT 23 0.5 0.45 0.1 0 0 DiQ-C4 0.26 0.26 60 190 72 N N SAT 24 0.5 0.45 0.08 0 0 DiQ-C4 0.33 0.33 75 190 96 Y Y SAT 25 0.5 0.5 0.08 0 0 DiQ-C4 0.33 0.33 75 190 96 Y Y SAT 26 0.5 0.45 0.1 0 0 DiQ-C4 0.27 0.22 40 190 72 Y N SAT 27 0.5 0.45 0.1 0 0 DiQ-C4 0.27 0.19 40 190 72 Y N SAT 28 0.5 0.45 0.1 0 0 DiQ-C4 0.27 0.16 40 190 72 Y N SAT 29 0.45 0.5 0 0 0.1 DiQ-C4 0.4 0.4 40 190 48 N N MgAPO-SAT 30 0.45 0.5 0 0 0.1 DiQ-C4 0.4 0.4 40 190 72 N N MgAPO-SAT 31 0.45 0.5 0 0.1 0 DiQ-C4 0.27 0.27 40 190 72 N N CoAPO-SAT + CIT-16P 32 0.5 0.45 0.075 0.025 0 DiQ-C4 0.27 0.27 40 190 72 Y N CoSAPO-SAT 33 0.5 0.45 0.05 0.05 0 DiQ-C4 0.27 0.27 40 190 72 Y N CoAPO-SAT 34 0.45 0.525 0 0.08 0 DiQ-C4 0.4 0.4 75 190 72 Y Y CoAPO-SAT 35 0.45 0.55 0 0.08 0 DiQ-C4 0.4 0.4 75 190 72 Y Y CoAPO-SAT 36 0.5 0.49 0.2 0 0 DiQ-C5 0.27 0.27 40 190 72 Y N SAT + impurity 37 0.5 0.49 0.15 0 0 DiQ-C5 0.27 0.27 40 190 72 Y N SAT 38 0.5 0.49 0.1 0 0 DiQ-C5 0.27 0.27 40 190 72 Y N SAT 39 0.5 0.49 0.1 0 0 DiQ-C5 0.23 0.23 40 190 72 Y N SAT 40 0.5 0.45 0.08 0 0 DiQ-C5 0.23 0.23 40 190 72 Y N SAT 41 0.5 0.45 0.06 0 0 DiQ-C5 0.23 0.23 40 190 72 Y N SAT 42 0.5 0.49 0.05 0 0 DiQ-C5 0.23 0.23 40 190 72 Y N SAT + impurity 43 0.5 0.49 0.2 0 0 DiQ-C5 0.23 0.23 40 190 72 Y N SAT 44 0.45 0.5 0 0.03 0 DiDABCO- 0.4 0.4 75 190 96 Y N CoAPO-SAT C4 45 0.45 0.5 0 0.05 0 DiDABCO- 0.4 0.4 75 190 96 Y N CoAPO-SAT C4 46 0.5 0.5 0.08 0 0 DiDABCO- 0.33 0.33 75 190 120 Y Y SAT + C4 AFX (vs) 47 0.5 0.475 0.1 0 0 DiDABCO- 0.33 0.33 75 190 120 Y Y SAT C4 48 0.5 0.5 0.1 0 0 DiDABCO- 0.33 0.33 75 190 120 Y Y SAT C4 49 0.5 0.45 0.1 0 0 DiDABCO- 0.2 0.2 40 190 48 Y Y SAT C4 50 0.48 0.45 0.1 0 0 DiDABCO- 0.2 0.2 40 190 48 Y Y SAT C4 51 0.46 0.45 0.1 0 0 DiDABCO- 0.2 0.2 40 190 48 Y Y SAT C4 52 0.45 0.44 0.1 0 0 DiDABCO- 0.2 0.2 40 190 48 Y Y SAT C4 53 0.44 0.45 0.1 0 0 DiDABCO- 0.2 0.2 40 190 48 Y Y SAT C4 .sup.[a]R.sub.(total) refers to the total amount of OSDA placed in the gel, both in the bromide or hydroxide form. When R.sub.(total) = R(OH).sub.2 it indicates that the entirety of the OSDA was in the hydroxide form. When they are not, the difference between them is what was added in the R(Br).sub.2 form. .sup.[b]N indicates No whereas Y indicates Yes. .sup.[c]vs indicates very small.
Example 54
CIT-17 in the Methanol-to-Olefins Reaction
[0351] The thermally treated CIT-17 sample from Example 6 was tested as a catalyst in the methanol-to-olefins (MTO) reaction. Catalyst evaluation was carried out in a fixed-bed reactor at ambient pressure. Approximately 200 mg of dried CIT-17 catalyst (35-60 mesh size) was loaded between two layers of quartz wool in a 0.25?6 stainless steel tube reactor as a part of a BTRS Jr. continuous flow reactor (Parker Autoclave Engineers). The dry weight of the catalyst was estimated on the basis of thermogravimetric analysis (TGA). All catalysts were first pretreated in-situ by heating to 150? C. at 1? C./min, held for 3 h, and then heated further to 580? C. at 1? C./min and held for 12 h under flowing air (breathing-grade D, AirGas). Methanol was introduced via a liquid syringe pump (Harvard Apparatus Pump 11 Elite) at 4.0-5.0 ?L/min into a gas stream of an inert blend (95% He and 5% Ar; GC internal standard) at a volumetric flow rate of 30 cm.sup.3/min. The methanol flow rate was adjusted, depending on the actual weight of the dried catalyst loaded in the reactor, to achieve a weight hourly space velocity (WHSV) of 0.65 h.sup.?1. The reaction was performed at a WHSV of 0.65 h.sup.?1 and a temperature of 350? C. Effluent gases were evaluated using an on-stream Agilent GCMS (GC 6890 N/MSD5793N) equipped with a Plot-Q capillary column. Aliquots of product flow were analyzed every 16 min. All selectivity values were calculated on carbon-number basis. See
TABLE-US-00003 TABLE 2 Reaction results of SAT-type Molecular Sieves. Catalyst WHSV Averaged Selectivities Reaction from Si/T Temperature (MeOH) C2 + C3 C3=/ Example Material Example (EDS) (? C.) (1/h) C2= C3= Alkanes C4 C5+ C2= 56 SAPO-SAT 38 0.068 400 1.30 0.14 0.48 0.031 0.17 0.15 3.40 57 SAPO-SAT-C.sub.5 6 0.083 400 1.30 0.16 0.49 0.037 0.17 0.13 3.15 58 SAPO-SAT 36 0.094 400 1.30 0.19 0.47 0.047 0.16 0.12 2.47 59 SAPO-SAT-C.sub.4 11 0.072 400 1.30 0.13 0.47 0.021 0.17 0.15 3.62 60 SAPO-SAT 6 0.083 450 0.65 0.28 0.46 0.031 0.11 0.08 1.64 61 SAPO-SAT 6 0.083 400 0.65 0.18 0.40 0.033 0.17 0.09 2.22 62 SAPO-SAT 6 0.083 400 1.95 0.15 0.47 0.039 0.17 0.15 3.13 63 SAPO-SAT 6 0.083 400 2.60 0.14 0.49 0.047 0.15 0.15 3.50 64 SAPO-SAT 6 0.083 350 1.30 0.12 0.45 0.050 0.19 0.18 3.75 55 SAPO-SAT 6 0.083 350 0.65 0.12 0.50 0.034 0.2 0.12 4.17 65 SAPO-SAT 6 0.083 300 0.65 DME only 66 CoAPO-SAT 44 0.063 400 1.30 0.18 0.42 0.063 0.164 0.13 2.33 67 MgAPO-SAT 30 0.071 400 1.30 0.18 0.35 0.080 0.159 0.15 2.01
Example 55
Cyclic MTO Testing on CIT-17
[0352] The thermally treated CIT-17 sample from Example 6 was subjected to cyclic testing (reaction-reactivation). The first reaction cycle was performed similarly to the procedure outlined in Example 54. After the catalyst deactivates (either its conversion drops below 85% or DME selectivity surpasses 50%) the methanol was shut off and the catalyst was cooled to approximately 100? C. before being re-activated (air) under a similar procedure as described in Example 54. The catalyst behaves similarly following each re-activation for over 600 mins of reaction time.
Examples 56-67
Averaged Selectivities of Various SAT-type Molecular Sieves in MTO
[0353] Several more catalysts from Examples 11, 30, 36, 38, and 44 were tested in MTO. Their averaged selectivities when methanol conversion is greater than 97+% is shown in Table 2. The results demonstrate that lower temperatures and lower WHSVs lead to higher propylene-to-ethylene ratios in SAT-type materials, although at the expense of higher C.sub.4+. An averaged propylene-to-ethylene of approximately 4.2 was achieved.