Source: http://www.google.com/patents/US7253331?dq=6,757,682
Timestamp: 2017-11-19 17:12:23
Document Index: 211525468

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Patent US7253331 - Molecular sieve catalyst composition, its making and use in conversion processes - Google Patents
The invention relates to a molecular sieve catalyst composition, to a method of making or forming the molecular sieve catalyst composition, and to a conversion process using the catalyst composition. In particular, the invention is directed to a conversion process for producing olefin(s), preferably...http://www.google.com/patents/US7253331?utm_source=gb-gplus-sharePatent US7253331 - Molecular sieve catalyst composition, its making and use in conversion processes
Publication number US7253331 B2
Application number US 10/844,168
Also published as CN101018606A, CN101018606B, EP1753533A1, US20050256354, WO2005113145A1
Publication number 10844168, 844168, US 7253331 B2, US 7253331B2, US-B2-7253331, US7253331 B2, US7253331B2
Inventors Luc R. M. Martens, Marcel J. Janssen, Machteld M. Mertens, An Verberckmoes, Guang Cao
Patent Citations (28), Non-Patent Citations (5), Referenced by (21), Classifications (30), Legal Events (4)
US 7253331 B2
The invention relates to a molecular sieve catalyst composition, to a method of making or forming the molecular sieve catalyst composition, and to a conversion process using the catalyst composition. In particular, the invention is directed to a conversion process for producing olefin(s), preferably ethylene and/or propylene, from a feedstock, preferably an oxygenate containing feedstock in the presence of a molecular sieve having been synthesized in the presence of a flocculant.
(a) introducing a feedstock to a reactor system in the presence of a molecular sieve catalyst composition comprising a synthesized molecular sieve having been recovered in the presence of a polymeric amine flocculant;
2. The process of claim 1 wherein the feedstock comprises one or more oxygenates.
3. The process of claim 1 wherein the synthesized molecular sieve is synthesized from a synthesis mixture comprising a silicon source, a phosphorous source and an aluminum source, optionally in the presence of a templating agent.
4. The process of claim 1 wherein the formulated molecular sieve catalyst composition further comprises a binder and a matrix material.
5. The process of claim 1 wherein the flocculant has a molecular weight (MW) in the range of from 10,000 to 800,000.
6. The process of claim 1 wherein the flocculant is present in an amount of about 0.01 to 10 wt % flocculant based on the total weight of the synthesized molecular sieve.
7. The process of claim 1 wherein the flocculant is represented by the formula: (R—NH)x, where (R—NH) is a polymeric or monomeric unit where R contains from 1 to 20 carbon atoms, and x is an integer from 1 to 500,000.
8. The process of claim 1 wherein the flocculant is represented by the formula: (—NHCH2CH2—)m[—N(CH2CH2NH2)CH2CH2—]n), wherein m is from 10 to 20,000, and n is from 0 to 2,000.
9. The process of claim 1 wherein the synthesized molecular sieve is selected from one or more of the group consisting of: a metalloaluminophosphate, a silicoaluminophosphate, an aluminophosphate, a CHA framework-type molecular sieve, an AEI framework-type molecular sieve and a CHA and AEI intergrowth or mixed framework-type molecular sieve.
10. The process of claim 1 wherein the greater than 1000 Kg of one or more olefin(s) is being produced.
11. The process of claim 1 wherein the one or more olefin(s) include ethylene and propylene.
12. The process of claim 1 wherein the synthesized molecular sieve is formulated into a formulated molecular sieve catalyst composition, the formulated molecular sieve catalyst composition comprising the synthesized molecular sieve, a matrix material, and optionally a binder.
13. An integrated process for making one or more olefin(s), the integrated process comprising the steps of:
(c) converting the oxygenated feedstock into the one or more olefin(s) in the presence of a molecular sieve catalyst composition, the molecular sieve catalyst composition comprising a synthesized molecular sieve having been recovered in the presence of a polymeric amine flocculant.
14. The integrated process of claim 13 wherein the process further comprises the step of: (d) polymerizing the one or more olefin(s) in the presence of a polymerization catalyst into a polyolefin.
15. The integrated process of claim 13 wherein the oxygenated feedstock comprises methanol, the olefin(s) include ethylene and propylene, and the synthesized molecular sieve is a silicoaluminophosphate molecular sieve.
16. The integrated process of claim 13 wherein the flocculant has a molecular weight (MW) in the range of from 10,000 to 800,000.
17. The integrated process of claim 13 wherein the flocculant is present in an amount of about 0.01 to 10 wt % flocculant based on the total weight of the molecular sieve synthesized.
18. The integrated process of claim 13 wherein the flocculant is represented by the formula: (R—NH)x, where (R—NH) is a polymeric or monomeric unit where R contains from 1 to 20 carbon atoms, and x is an integer from 1 to 500,000.
19. The integrated process of claim 13 wherein the flocculant is represented by the formula: (—NHCH2CH2—)m[—N(CH2CH2NH2)CH2CH2—]n), wherein m is from 10 to 20,000, and n is from 0 to 2,000.
20. The integrated process of claim 13 wherein the flocculant is a polyethyleneimine.
21. The integrated process of claim 13 wherein the molecular sieve catalyst composition further comprises a matrix material, and optionally a binder.
22. The integrated process of claim 13 wherein the flocculant is present in an amount of about 0.01 to 10 wt % flocculant based on the total weight of the synthesized molecular sieve.
It is known that the way in which the molecular sieve catalyst compositions are made or formulated affects catalyst composition attrition. Molecular sieve catalyst compositions are formed by combining a molecular sieve and a matrix material usually in the presence of a binder. For example, PCT Patent Publication WO 03/000413 A1 published Jan. 3, 2003 discloses a low attrition molecular sieve catalyst composition using a synthesized molecular sieve that has not been fully dried, or partially dried, in combination in a slurry with a matrix material and/or a binder. Also, PCT Patent Publication WO 03/000412 A1 published Jan. 3, 2003 discusses a low attrition molecular sieve catalyst composition produced by controlling the pH of the slurry above the isoelectric point of the molecular sieve. U.S. Patent Application Publication No. U.S. 2003/0018228 published Jan. 23, 2003 shows making a low attrition molecular sieve catalyst composition by making a slurry of a synthesized molecular sieve, a binder, and optionally a matrix material, wherein 90 percent by volume of the slurry contains particles having a diameter less than 20 μm. U.S. patent application Ser. No. 10/178,455 filed Jun. 24, 2002, which is herein fully incorporated by reference, illustrates making an attrition resistant molecular sieve catalyst composition by controlling the ratio of a binder to a molecular sieve. U.S. Pat. No. 6,503,863 is directed to a method of heat treating a molecular sieve catalyst composition to remove a portion of the template used in the synthesis of the molecular sieve. U.S. Pat. No. 6,541,415 describes improving the attrition resistance of a molecular sieve catalyst composition that contains molecular sieve-containing recycled attrition particles and virgin molecular sieve and having been calcined to remove the template from the molecular sieve catalyst. U.S. Pat. No. 6,660,682 describes the use of a polymeric base to reduce the amount of templating agent required to produce a particular molecular sieve.
It is also known that in typical commercial processes that flocculants are used in the recovery of synthesized molecular sieves. These flocculants are known to facilitate the crystal recovery and to increase the yield of recovery of the synthesized molecular sieve typically in a large scale commercial process. However, the presence of a flocculate can affect the catalyst formulation, and in some cases flocculation can result in the formulation of catalyst compositions having lower attrition resistance and lower selectivity in various conversion processes.
Although these molecular sieve catalyst compositions described above are useful in hydrocarbon conversion processes, it would be desirable to have an improved molecular sieve catalyst composition having better selectivity to in particular prime olefins, especially ethylene and propylene.
This invention generally provides for a method of making or formulating a molecular sieve catalyst composition and to its use in a conversion process for converting a feedstock into one or more olefin(s).
In one embodiment the invention is directed to a process for producing one or more olefin(s), the process comprising the steps of: (a) introducing a feedstock to a reactor system in the presence of a formulated molecular sieve catalyst composition comprising a synthesized molecular sieve having been recovered in the presence of a flocculant; (b) withdrawing from the reactor system an effluent stream; and (c) passing the effluent stream through a recovery system recovering at least the one or more olefin(s). In one embodiment, the flocculent is a charged organic polymer. Preferably the synthesized molecular sieve is a metallo-aluminophosphate, a silicoaluminophosphate, an aluminophosphate, a chabazite (CHA) framework-type molecular sieve, or a CHA and AEI intergrowth or mixed framework-type molecular sieve.
In another preferred embodiment, the invention relates to a method for synthesizing a molecular sieve, the method comprising the steps of: (a) forming a synthesis mixture comprising two or more a silicon source, an aluminum source, a phosphorous source, and a templating agent; (b) introducing to the synthesis mixture a flocculent; and (c) recovering the synthesized molecular sieve. In one embodiment, the flocculant is a charged organic polymer. In another embodiment, the flocculant is selected from one or more of the group consisting of polyethylenimine. In yet another preferred embodiment, the synthesis mixture comprising three or more of a silicon source, an aluminum source, a phosphorous source, and a templating agent. In yet another embodiment, step (c) of recovering is one or more filtration step(s) or one or more filtration step(s) and washing step(s), or a combination of one or more of a centrifugation step(s), a washing step(s), and a filtration step(s). In yet another preferred embodiment of this embodiment, the amount of molecular sieve recovered in a single batch is greater than 250 Kg, preferably greater than 500 Kg, and most preferably greater than 1000 Kg.
The invention is directed toward a molecular sieve catalyst composition, its making, and to its use in the conversion of a feedstock into one or more olefin(s). A formulated molecular sieve catalyst composition is typically formed from a slurry of the combination of a molecular sieve, a matrix material, and optionally, most preferably, a binder. It has been discovered that when recovering a molecular sieve in the presence of a flocculant in a molecular sieve synthesis process, the synthesized molecular sieve exhibits improved selectivity for primarily ethylene and propylene in a conversion process of one or more alcohols, more specifically methanol.
Molecular sieves have various chemical and physical, framework, characteristics. Molecular sieves have been well classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature. A framework-type describes the connectivity, topology, of the tetrahedrally coordinated atoms constituting the framework, and making an abstraction of the specific properties for those materials. Framework-type zeolite and zeolite-type molecular sieves for which a structure has been established, are assigned a three letter code and are described in the Atlas of Zeolite Framework Types, 5th edition, Elsevier, London, England (2001), which is herein fully incorporated by reference. For additional information on molecular sieve types, structures and characteristics, see van Bekkum, et al., Introduction to Zeolite Science and Practice, Second Completely Revised and Expanded Edition, Volume 137, Elsevier Science, B. V., Amsterdam, Netherlands (2001), which is also fully incorporated herein by reference.
The small, medium and large pore molecular sieves have from a 4-ring to a 12-ring or greater framework-type. In a preferred embodiment, the molecular sieves have 8-, 10- or 12-ring structures or larger and an average pore size in the range of from about 3 Å to 15 Å. In the most preferred embodiment, the molecular sieves, preferably SAPO molecular sieves, have 8-rings and an average pore size less than about 5 Å, preferably in the range of from 3 Å to about 5 Å, more preferably from 3 Å to about 4.5 Å, and most preferably from 3.5 Å to about 4.2 Å.
Molecular sieves based on silicon, aluminum, and phosphorous, and metal containing molecular sieves thereof, have been described in detail in numerous publications including for example, U.S. Pat. No. 4,567,029 (MeAPO where Me is Mg, Mn, Zn, or Co), U.S. Pat. No. 4,440,871 (SAPO), European Patent Application EP-A-0 159 624 (ELAPSO where El is As, Be, B, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti or Zn), U.S. Pat. No. 4,554,143 (FeAPO), U.S. Pat. Nos. 4,822,478, 4,683,217, 4,744,885 (FeAPSO), EP-A-0 158 975 and U.S. Pat. No. 4,935,216 (ZnAPSO, EP-A-0 161 489 (CoAPSO), EP-A-0 158 976 (ELAPO, where EL is Co, Fe, Mg, Mn, Ti or Zn), U.S. Pat. No. 4,310,440 (AlPO4), EP-A-0 158 350 (SENAPSO), U.S. Pat. No. 4,973,460 (LiAPSO), U.S. Pat. No. 4,789,535 (LiAPO), U.S. Pat. No. 4,992,250 (GeAPSO), U.S. Pat. No. 4,888,167 (GeAPO), U.S. Pat. No. 5,057,295 (BAPSO), U.S. Pat. No. 4,738,837 (CrAPSO), U.S. Pat. Nos. 4,759,919, and 4,851,106 (CrAPO), U.S. Pat. Nos. 4,758,419, 4,882,038, 5,434,326 and 5,478,787 (MgAPSO), U.S. Pat. No. 4,554,143 (FeAPO), U.S. Pat. No. 4,894,213 (AsAPSO), U.S. Pat. No. 4,913,888 (AsAPO), U.S. Pat. Nos. 4,686,092, 4,846,956 and 4,793,833 (MnAPSO), U.S. Pat. Nos. 5,345,011 and 6,156,931 (MnAPO), U.S. Pat. No. 4,737,353 (BeAPSO), U.S. Pat. No. 4,940,570 (BeAPO), U.S. Pat. Nos. 4,801,309, 4,684,617 and 4,880,520 (TiAPSO), U.S. Pat. Nos. 4,500,651, 4,551,236 and 4,605,492 (TiAPO), U.S. Pat. Nos. 4,824,554, 4,744,970 (CoAPSO), U.S. Pat. No. 4,735,806 (GaAPSO) EP-A-0 293 937 (QAPSO, where Q is framework oxide unit [QO2]), as well as U.S. Pat. Nos. 4,567,029, 4,686,093, 4,781,814, 4,793,984, 4,801,364, 4,853,197, 4,917,876, 4,952,384, 4,956,164, 4,956,165, 4,973,785, 5,098,684 (MCM-41), 5,198,203 (MCM-48), 5,241,093, 5,304,363 (MCM-50), 5,493,066, 5,675,050, 6,077,498 (ITQ-1), 6,409,986 (ITQ-5), 6,419,895 (UZM-4), 6,471,939 (ITQ-12), 6,471,941 (ITQ-13), 6,475,463 (SSZ-55), 6,500,404 (ITQ-3), 6,500,998 (UZM-5 and UZM-6), 6,524,551 (MCM-58) and 6,544,495 (SSZ-57), 6,547,958 (SSZ-59), 6,555,090 (ITQ-36) and 6,569,401 (SSZ-64), all of which are herein fully incorporated by reference. Other molecular sieves are described in R. Szostak, Handbook of Molecular Sieves, Van Nostrand Reinhold, New York, N.Y. (1992), which is herein fully incorporated by reference.
wherein R represents at least one templating agent, preferably an organic templating agent; m is the number of moles of R per mole of (MxAlyPz)O2 and m has a value from 0 to 1, preferably 0 to 0.5, and most preferably from 0 to 0.3; x, y, and z represent the mole fraction of Al, P and M as tetrahedral oxides, where M is a metal selected from one of Group IA, IIA, IB, IIIB, IVB, VB, VIIB, VIIB, VIIIB and Lanthanide's of the Periodic Table of Elements, preferably M is selected from one of the group consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr. In an embodiment, m is greater than or equal to 0.2, and x, y and z are greater than or equal to 0.01. In another embodiment, m is greater than 0.1 to about 1, x is greater than 0 to about 0.25, y is in the range of from 0.4 to 0.5, and z is in the range of from 0.25 to 0.5, more preferably m is from 0.15 to 0.7, x is from 0.01 to 0.2, y is from 0.4 to 0.5, and z is from 0.3 to 0.5.
Synthesis of a molecular sieve, especially a SAPO molecular sieve, its formulation into a SAPO catalyst, and its use in converting a hydrocarbon feedstock into olefin(s), is shown in, for example, U.S. Pat. Nos. 4,499,327, 4,677,242, 4,677,243, 4,873,390, 5,095,163, 5,714,662 and 6,166,282, all of which are herein fully incorporated by reference. Non-limiting examples of SAPO and ALPO molecular sieves of the invention include one or a combination of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (U.S. Pat. No. 6,162,415), SAPO-47, SAPO-56, ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37, ALPO-46, and metal containing molecular sieves thereof. The more preferred molecular sieves include one or a combination of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, even more preferably one or a combination of SAPO-18, SAPO-34, ALPO-34 and ALPO-18, and metal containing molecular sieves thereof, and most preferably one or a combination of SAPO-34 and ALPO-18, and metal containing molecular sieves thereof.
In an embodiment, the molecular sieve is an intergrowth material having two or more distinct phases of crystalline structures within one molecular sieve composition. In particular, SAPO intergrowth molecular sieves are described in the U.S. patent application Ser. No. 09/924,016 filed Aug. 7, 2001, PCT Publication WO 02/070407 published Sep. 12, 2002 and PCT Publication WO 98/15496 published Apr. 16, 1998, which are herein fully incorporated by reference. For example, SAPO-18, ALPO-18 and RUW-18 have an AEI framework-type, and SAPO-34 has a CHA framework-type. In another embodiment, the molecular sieve comprises at least one intergrown phase of AEI and CHA framework-types, preferably the molecular sieve has a greater amount of CHA framework-type to AEI framework-type, and more preferably the molar ratio of CHA to AEI is greater than 1:1.
Generally, molecular sieves are synthesized by the hydrothermal crystallization of one or more of a source of aluminum, a source of phosphorous, a source of silicon, a templating agent, and a metal containing compound. Typically, a combination of sources of silicon, aluminum and phosphorous, optionally with one or more templating agents and/or one or more metal containing compounds, and are placed in a sealed pressure vessel, optionally lined with an inert plastic such as polytetrafluoroethylene, and heated, under a crystallization pressure and temperature, at static or stirred conditions, until a crystalline material is formed in a synthesis mixture. Then, in a commercial process in particular, one or more flocculant(s) is added to the synthesis mixture. A liquid portion of the synthesis mixture is removed, decanted, or reduced in quantity. The remaining synthesis mixture containing the crystalline molecular sieve is then, optionally, contacted with the same or a different fresh liquid, typically with water, in a washing step, from once to many times depending on the desired purity of the supernatant, liquid portion, of the synthesis mixture being removed. It is also optional to repeat this process by adding in additional flocculent followed by additional washing steps. Then, the crystallized molecular sieve is recovered by filtration, centrifugation and/or decanting. Preferably, the molecular sieve is filtered using a filter that provides for separating certain crystal sized molecular sieve particles from any remaining liquid portion that may contain different size molecular sieve crystals.
When commercially synthesizing any of the molecular sieves discussed above, typically one or more chemical reagents are added to the crystallization vessel or synthesis reactor after crystallization is substantially complete, preferably complete. Optionally, in another embodiment, the synthesis mixture is transferred to another vessel separate from the reaction vessel or the vessel in which crystallization occurs, and a flocculant is then added to this other vessel from which the crystalline molecular sieve is ultimately recovered. These chemical reagents or flocculants are used to increase the recovery rate of the molecular sieve crystals and increase the yield of the synthesized molecular sieve crystals. While not wishing to be bound to any particular theory, these flocculants act either as (1) a surface charge modifier that results in the agglomeration of very small particles into larger aggregates of molecular sieve particles; or (2) surface anchors that bridge many small particles to form aggregates of molecular sieve particles. The aggregates of the molecular sieve crystals are then easily recovered by well known techniques such as filtration or through a filter press process.
Flocculants can be added at any point during or with any other source or templating agent used in the synthesis of any one of the molecular sieves discussed above. In one embodiment, flocculants are added to a molecular sieve synthesis mixture comprising one or more of a silicon source, a phosphorous source, an aluminum source, and a templating agent depending on the molecular sieve being synthesized. In the most preferred embodiment, the flocculant is added to the synthesis mixture after crystallization has occurred from the combination of one or more of a silicon source, a phosphorous source, an aluminum source, and a templating agent. The synthesized molecular sieve is then recovered by filtration, however, optionally, the synthesized molecular sieve is washed and additional flocculant is used to further aggregate any remaining synthesized molecular sieve from the liquid portion of the synthesis mixture.
There are many types of flocculants both inorganic and organic flocculants. Inorganic flocculants are typically aluminum or iron salts that form insoluble hydroxide precipitates in water. Non-limiting examples such as aluminum sulfate, poly (aluminum chloride), sodium aluminate, iron (III)-chloride, sulfate, and sulfate-chloride, iron (II) sulfate, and sodium silicate (activated silica). The major classes of flocculants are: (1) nonionic flocculant, for example, polyethylene oxide, polyacrylamide (PAM), partially hydrolyzed polyacrylamide (HPAM), and dextran; (2) cationic flocculant, for example, polyethyleneimine (PEI), polyacrylamide-co-trimethylammonium, ethyl methyl acrylate chloride (PTAMC), and poly (N-methyl-4-vinylpyridinium iodide); and (3) anionic flocculant, for example, poly (sodium acrylate), dextran sulfates, alum (aluminum sulfate), and/or high molecular weight ligninsulfonates prepared by a condensation reaction of formaldehyde with ligninsulfonates, and polyacrylamide. In a preferred embodiment, where the synthesis mixture includes the presence of water, it is preferable that the flocculant used is water soluble. Additional information on flocculation is discussed in T. C. Patton, Paint Flow and Pigment Dispersion-A Rheological Approach to Coating and Ink Technology, 2nd Edition, John Wiley & Sons, New York, p. 270, 1979, which is fully incorporated by reference.
In another embodiment, the flocculant is added to the synthesis mixture after crystallization in an amount of 0.01 to 10 wt % flocculant based on expected solid molecular sieve product yield, preferably between 0.05 to 5 wt % flocculant based on expected solid molecular sieve product yield, more preferably from 0.05 to 3 wt % based on expected solid molecular sieve product yield. In yet another embodiment, it is preferable that the product slurry and/or flocculant are diluted to obtain a volume of product slurry to volume of flocculant of between 1:1 and 10:1. Good mixing between the product slurry and the flocculant is also preferred. One can recover the flocculated sieve starting from the total mixture by centrifugation or filtration or one can allow the mixture to settle, decant the liquid, re-slurry with water, eventually repeatedly decant and re-slurry, and finally recover by centrifugation or filtration. The settling of the sieve can take from seconds to days; however, the settling can be accelerated by adding additional flocculant. The flocculant is typically added to the slurry at room temperature, and is preferably added as a solution. Should a solid flocculant be used then it is preferable that a substantially homogeneous flocculant solution is prepared by dissolving the solid flocculant in a medium.
In one preferred embodiment, the flocculant is a polymeric imine such as polyethyleneimine. In another preferred embodiment, the flocculant is represented by the formula: (R—NH)x, where (R—NH) is a polymeric or monomeric unit where R contains from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms, and most preferably from 1 to 4 carbon atoms; x is an integer from 1 to 500,000.
In yet another embodiment, the flocculant is a polyethylenimine that is represented by the following general formula: (—NHCH2CH2—)m[—N(CH2CH2NH2)CH2CH2—]n), wherein m is from 10 to 20,000, and n is from 0 to 2,000, preferably from 1 to 2000.
In another embodiment, the flocculant of the invention, preferably a polyethyleneimine, has an average molecular weight from about 500 to about 1,000,000, preferably from about 10,000 to about 800,000, more preferably from about 20,000 to about 750,000, and most preferably from about 50,000 to about 750,000.
Non-limiting examples of polyethylenimine flocculants include: epichlorohydrin modified polyethylenimine, ethoxylated polyethylenimine, polypropylenimine diamine dendrimers (DAB-Am-n), poly (allylamine) [CH2CH(CH2NH2)]n, poly (1,2-dihydro-2,2,4-trimethylquinoline), and poly (dimethylamine-co-epichlorohydrin-co-ethylenediamine).
In one embodiment, the flocculant is in an a solution, preferably an aqueous solution. In a further embodiment, the flocculant in the aqueous solution is diluted with water. Without being bound to any particular theory, it has been found that dilution of the molecular sieve slurry, preferably one recovered using a flocculant, prevents dissolution of the molecular sieve in the slurry. This benefit provides for a further improvement in yield, and allows for the slurry to be stored for an extended period of time.
A synthesis mixture comprising a molecular sieve and a flocculant has a pH depending on the composition of the molecular sieve. In a preferred embodiment, the synthesis mixture has a pH in the range of from 2 to 10, preferably in the range of from 4 to 9, and most preferably in the range of from 5 to 8. Generally, the synthesis mixture is sealed in a vessel and heated, preferably under autogenous pressure, to a temperature in the range of from about 80° C. to about 250° C., and more preferably from about 150° C. to about 180° C. The time required to form the crystalline molecular sieve is typically from immediately up to several weeks, the duration of which is usually dependent on the temperature; the higher the temperature the shorter the duration. Typically, the crystalline molecular sieve product is formed, usually in a slurry state, and then a flocculant is introduced to this slurry, the synthesis mixture. The crystalline molecular sieve is then recovered by any standard technique well known in the art, for example centrifugation or filtration. Alternatively, in another embodiment, the flocculant is introduced into the synthesis mixture directly.
Determination of the percentage of liquid or liquid medium and the percentage of flocculant and/or template for purposes of this patent specification and appended claims uses a Thermal Gravimetric Analysis (TGA) technique as follows: An amount of a molecular sieve material, the sample, is loaded into a sample pan of a Cahn TG-121 Microbalance, available from Cahn Instrument, Inc., Cerritos, Calif. During the TGA technique, a flow of 114 cc/min (STP) air was used. The sample is then heated from 25° C. to 180° C. at 30° C./min, held at 180° C. for 3 hours or until the weight of this sample becomes constant. The weight loss the percentage to the starting molecular sieve material is then treated as the percentage of the liquid or liquid medium. Subsequently, the sample is heated at 30° C./min from 180° C. to 650° C. and held at 650° C. for 2 hours. This weight loss as a percentage of the original sample weight during this treatment is regarded as the weight loss of the templating agent. The total weight loss as a percentage in terms of the original first sample weight during this entire TGA treatment is defined as Loss-On-Ignition (LOI).
In one embodiment, the isolated or separated crystalline product, the synthesized molecular sieve, is washed, typically using a liquid such as water, from one to many times, or in a semi-continuous or continuous way for variable lengths of time. The washed crystalline product is then optionally dried, preferably in air to a level such that the resulting, partially dried or dried crystalline product or synthesized molecular sieve has a LOI in the range of from about 0 weight percent to about 80 weight percent, preferably the range is from about greater than 1 weight percent to about 80 weight percent, more preferably from about 10 weight percent to about 70 weight percent, even more preferably from about 20 to about 60 weight percent, and most preferably from about 40 weight percent to about 60 weight percent. This liquid containing crystalline product, synthesized molecular sieve or wet filtercake, is then used below in the formulation of the molecular sieve catalyst composition of the invention.
The amount of flocculant introduced to the reactor vessel depends on the quantity of molecular sieve being recovered, the type of molecular sieve, the pH of the synthesis mixture, etc. In one embodiment, the amount of molecular sieve recovered is the range of from about 100 Kg to about 20,000 Kg or greater, preferably in the range of from 250 Kg to about 20,000 Kg, more preferably from about 500 Kg to about 20,000 Kg, and most preferably from about 1000 Kg to about 20,000 Kg. In another embodiment, the reactor vessel is capable of synthesizing an amount of molecular sieve in one batch or at one time in the range from about 100 Kg to about 20,000 Kg or greater, preferably greater than about 250 Kg to about 20,000 Kg, more preferably from about 500 Kg to about 20,000 Kg, and most preferably from about 1000 Kg to about 20,000 Kg.
Once the molecular sieve is synthesized and heat treated as described above, depending on the requirements of the particular conversion process, the molecular sieve is then formulated into a molecular sieve catalyst composition, particularly for commercial use. The molecular sieves synthesized above are made or formulated into molecular sieve catalyst compositions by combining the synthesized molecular sieve(s), preferably after being thermally treated, with a binder, and optionally, but preferably, with a matrix material to form a formulated molecular sieve catalyst composition. It has been found that when thermally treating a synthesized molecular sieve having been recovered in the presence of a flocculant, prior to formulation, maintains or improves the formulated molecular sieve catalyst composition's resistance to attrition in various conversion processes.
This formulated composition is formed into useful shape and sized particles by well-known techniques such as spray drying, pelletizing, extrusion, and the like, spray drying being the most preferred. It is also preferred that after spray drying for example that the formulated molecular sieve catalyst composition is then calcined.
Aluminum chlorhydrate, a hydroxylated aluminum based sol containing a chloride counter ion, has the general formula of AlmOn(OH)oClp.x(H2O) wherein m is 1 to 20, n is 1 to 8, o is 5 to 40, p is 2 to 15, and x is 0 to 30. In one embodiment, the binder is Al13O4(OH)24Cl7.12(H2O) as is described in G. M. Wolterman, et al., Stud. Surf. Sci. and Catal., 76, pages 105-144 (1993), which is herein incorporated by reference. In another embodiment, the binders are alumina sols, predominantly comprising aluminum oxide, optionally including some silicon. In yet another embodiment, the binders are peptized alumina made by treating alumina hydrates such as pseudobohemite, with an acid, preferably an acid that does not contain a halogen, to prepare sols or aluminum ion solutions. Non-limiting examples of commercially available colloidal alumina sols include Nalco 8676 available from Nalco Chemical Co., Naperville, Ill., and Nyacol AL20DW, available from Nyacol Nano Technologies, Inc., Ashland, Mass.
Non-limiting examples of matrix materials include one or more of: rare earth metals, non-active, metal oxides including titania, zirconia, magnesia, thoria, beryllia, quartz, silica or sols, and mixtures thereof, for example silica-magnesia, silica-zirconia, silica-titania, silica-alumina and silica-alumina-thoria. In an embodiment, matrix materials are natural clays such as those from the families of montmorillonite and kaolin. These natural clays include sabbentonites and those kaolins known as, for example, Dixie, McNamee, Georgia and Florida clays. In one embodiment, the matrix material, preferably any of the clays, are subjected to well known modification processes such as calcination and/or acid treatment and/or chemical treatment. In one preferred embodiment, the matrix material is kaolin, particularly kaolin having an average particle size from about 0.1 μm to about 0.6 μm with a d90 particle size distribution of less than about 1 μm.
Upon combining the heat treated synthesized molecular sieve and the matrix material, optionally with a binder, in a liquid to form a slurry, mixing, preferably rigorous mixing, is needed to produce a substantially homogeneous mixture containing the heat treated synthesized molecular sieve. Non-limiting examples of suitable liquids include one or a combination of water, alcohol, ketones, aldehydes, and/or esters. The most preferred liquid is water. In one embodiment, the slurry is colloid-milled for a period of time sufficient to produce the desired slurry texture, sub-particle size, and/or sub-particle size distribution.
The liquid containing the heat treated synthesized molecular sieve and matrix material, and the optional binder, are in the same or different liquid, and are combined in any order, together, simultaneously, sequentially, or a combination thereof. In the preferred embodiment, the same liquid, preferably water is used.
In one embodiment, the weight ratio of the binder to the molecular sieve is in the range of from about 0.1 to 0.5, more preferably in the range of from 0.11 to 0.48, even more preferably from 0.12 to about 0.45, yet even more preferably from 0.13 to less than 0.45, and most preferably in the range of from 0.15 to about 0.4. See for example U.S. patent application Ser. No. 10/178,455 filed Jun. 24, 2002, which is herein fully incorporated by reference.
The molecular sieve catalyst composition particles contains some water, templating agent or other liquid components, therefore, the weight percents that describe the solid content in the slurry are preferably expressed in terms exclusive of the amount of water, templating agent and/or other liquid contained within the particle. The most preferred condition for measuring solids content is on a calcined basis as, for example, as measured by the LOI procedure discussed above. On a calcined basis, the solid content in the slurry, more specifically, the molecular sieve catalyst composition particles in the slurry, are from about 20 percent by weight to 45 percent by weight molecular sieve, 5 percent by weight to 20 percent by weight binder, and from about 30 percent by weight to 80 percent by weight matrix material. See for example U.S. Patent Application Publication No. U.S. 2003/0018228 published Jan. 23, 2003, which is herein fully incorporated by reference.
In another embodiment, the heat treated molecular sieve is combined with a binder and/or a matrix material forming a slurry such that the pH of the slurry is above or below the isoelectric point of the molecular sieve. Preferably the slurry comprises the molecular sieve, the binder and the matrix material and has a pH different from, above or below, preferably below, the IEP of the molecular sieve, the binder and the matrix material. In an embodiment, the pH of the slurry is in the range of from 2 to 7, preferably from 2.3 to 6.2; the IEP of the molecular sieve is in the range of from 2.5 to less than 7, preferably from about 3.5 to 6.5; the IEP of the binder is greater than 10; and the IEP of the matrix material is less than 2. See PCT Patent Publication WO 03/000412 A1 published Jan. 3, 2003, which is herein fully incorporated by reference.
As the slurry is mixed, the solids in the slurry aggregate preferably to a point where the slurry contains solid molecular sieve catalyst composition particles. It is preferable that these particles are small and have a uniform size distribution such that the d90 diameter of these particles is less than 20 μm, preferably less than 15 μm, more preferably less than 10 μm, and most preferably about 7 μm. The d90 for purposes of this patent application and appended claims means that 90 percent by volume of the particles in the slurry have a particle diameter lower than the d90 value. For the purposes of this definition, the particle size distribution used to define the d90 is measured using well known laser scattering techniques using a Honeywell (Microtrac Model 3000 particle size analyzer from Microtrac, Inc., Largo, Fla.).
In one embodiment, the slurry of the synthesized molecular sieve, binder and matrix material is mixed or milled to achieve a sufficiently uniform slurry of sub-particles of the molecular sieve catalyst composition to form a formulation composition that is then fed to a forming unit that produces the molecular sieve catalyst composition or formulated molecular sieve catalyst composition. In a preferred embodiment, the forming unit is a spray dryer. Typically, the forming unit is maintained at a temperature sufficient to remove most of the liquid from the slurry, and from the resulting molecular sieve catalyst composition. The resulting catalyst composition when formed in this way takes the form of microspheres.
During spray drying, the slurry is passed through a nozzle distributing the slurry into small droplets, resembling an aerosol spray into a drying chamber. Atomization is achieved by forcing the slurry through a single nozzle or multiple nozzles with a pressure drop in the range of from 100 psia to 1000 psia (690 kPaa to 6895 kPaa). In another embodiment, the slurry is co-fed through a single nozzle or multiple nozzles along with an atomization fluid such as air, steam, flue gas, or any other suitable gas. Generally, the size of the microspheres is controlled to some extent by the solids content of the slurry. However, control of the size of the catalyst composition and its spherical characteristics are controllable by varying the slurry feed properties and conditions of atomization.
Other methods for forming a molecular sieve catalyst composition is described in U.S. Pat. No. 6,509,290 (spray drying using a recycled molecular sieve catalyst composition), which is herein incorporated by reference.
In a preferred embodiment, once the molecular sieve catalyst composition is formed, to further harden and/or activate the formed catalyst composition, the spray dried molecular sieve catalyst composition or formulated molecular sieve catalyst composition is calcined. Typical calcination temperatures are in the range of from about 500° C. to about 800° C., and preferably from about 550° C. to about 700° C., preferably in a calcination environment such as air, nitrogen, helium, flue gas (combustion product lean in oxygen), or any combination thereof. Calcination time is typically dependent on the degree of hardening of the molecular sieve catalyst composition and ranges from about 15 minutes to about 20 hours at a temperature in the range of from 500° C. to 700° C.
In one embodiment, the attrition resistance of a molecular sieve catalyst composition is measured using an Attrition Rate Index (ARI), measured in weight percent catalyst composition attrited per hour. ARI is measured by adding 6.0 g of catalyst composition having a particle size distribution ranging from 53 microns to 125 microns to a hardened steel attrition cup. Approximately 23,700 cc/min of nitrogen gas is bubbled through a water-containing bubbler to humidify the nitrogen. The wet nitrogen passes through the attrition cup, and exits the attrition apparatus through a porous fiber thimble. The flowing nitrogen removes the finer particles, with the larger particles being retained in the cup. The porous fiber thimble separates the fine catalyst particles from the nitrogen that exits through the thimble. The fine particles remaining in the thimble represent the catalyst composition that has broken apart through attrition. The nitrogen flow passing through the attrition cup is maintained for 1 hour. The fines collected in the thimble are removed from the unit. A new thimble is then installed. The catalyst left in the attrition unit is attrited for an additional 3 hours, under the same gas flow and moisture levels. The fines collected in the thimble are recovered. The collection of fine catalyst particles separated by the thimble after the first hour are weighed. The amount in grams of fine particles divided by the original amount of catalyst in grams charged to the attrition cup expressed on per hour basis is the ARI, in weight percent per hour (wt. %/hr). ARI is represented by the formula: ARI=C/(B+C)/D multiplied by 100%, wherein B is weight of catalyst composition left in the cup after the attrition test, C is the weight of collected fine catalyst particles after the first hour of attrition treatment, and D is the duration of treatment in hours after the first hour attrition treatment.
In one embodiment, the molecular sieve catalyst composition or formulated molecular sieve catalyst composition has an ARI less than 10 weight percent per hour, preferably less than 5 weight percent per hour, more preferably less than 2 weight percent per hour, and most preferably less than 1 weight percent per hour.
The various feedstocks discussed above, particularly a feedstock containing an oxygenate, more particularly a feedstock containing an alcohol, is converted primarily into one or more olefin(s). The olefin(s) or olefin monomer(s) produced from the feedstock typically have from 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbons atoms, and most preferably ethylene and/or propylene. Non-limiting examples of olefin monomer(s) include ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 and decene-1, preferably ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 and isomers thereof. Other olefin monomer(s) include unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
The superficial gas velocity (SGV) of the feedstock including diluent and reaction products within the reactor system is preferably sufficient to fluidize the molecular sieve catalyst composition within a reaction zone in the reactor. The SGV in the process, particularly within the reactor system, more particularly within the riser reactor(s), is at least 0.1 meter per second (m/sec), preferably greater than 0.5 m/sec, more preferably greater than 1 m/sec, even more preferably greater than 2 m/sec, yet even more preferably greater than 3 m/sec, and most preferably greater than 4 m/sec. See for example U.S. patent application Ser. No. 09/708,753 filed Nov. 8, 2000, which is herein incorporated by reference. Other processes for converting an oxygenate to olefin(s) are described in U.S. Pat. No. 5,952,538 (WHSV of at least 20 hr−1 and a Temperature Corrected Normalized Methane Selectivity (TCNMS) of less than 0.016), EP-0 642 485 B1 (WHSV is from 0.01 hr−1 to about 100 hr−1, at a temperature of from about 350° C. to 550° C.), and PCT WO 01/23500 published Apr. 5, 2001 (propane reduction at an average catalyst feedstock exposure of at least 1.0), which are all herein fully incorporated by reference.
Other regeneration processes are described in U.S. Pat. Nos. 6,023,005 (coke levels on regenerated catalyst), 6,245,703 (fresh molecular sieve added to regenerator) and 6,290,916 (controlling moisture), U.S. patent application Ser. No. 09/587,766 filed Jun. 6, 2000 (cooled regenerated catalyst returned to regenerator), U.S. patent application Ser. No. 09/785,122 filed Feb. 16, 2001 (regenerated catalyst contacted with alcohol), and PCT WO 00/49106 published Aug. 24, 2000 (cooled regenerated catalyst contacted with by-products), which are all herein fully incorporated by reference.
Generally accompanying most recovery systems is the production, generation or accumulation of additional products, by-products and/or contaminants along with the preferred prime products. The preferred prime products, the light olefins, such as ethylene and propylene, are typically purified for use in derivative manufacturing processes such as polymerization processes. Therefore, in the most preferred embodiment of the recovery system, the recovery system also includes a purification system to remove various non-limiting examples of contaminants and by-products include generally polar compounds such as water, alcohols, carboxylic acids, ethers, carbon oxides, ammonia and other nitrogen compounds, chlorides, hydrogen and hydrocarbons such as acetylene, methyl acetylene, propadiene, butadiene and butyne.
The light olefin products, especially the ethylene and the propylene, are useful in polymerization processes that include solution, gas phase, slurry phase and a high pressure processes, or a combinations thereof. Particularly preferred is a gas phase or a slurry phase polymerization of one or more olefin(s) at least one of which is ethylene or propylene. These polymerization processes utilize a polymerization catalyst that can include any one or a combination of the molecular sieve catalysts discussed above, however, the preferred polymerization catalysts are those Ziegler-Natta, Phillips-type, metallocene, metallocene-type and advanced polymerization catalysts, and mixtures thereof. The polymers produced by the polymerization processes described above include linear low density polyethylene, elastomers, plastomers, high density polyethylene, low density polyethylene, polypropylene and polypropylene copolymers. The propylene based polymers produced by the polymerization processes include atactic polypropylene, isotactic polypropylene, syndiotactic polypropylene, and propylene random, block or impact copolymers.
LOI and ARI are specified in this patent specification.
There are numerous methods well known for making molecular sieves. The following is an example preparation of a molecular sieve, particularly a silicoaluminophosphate molecular sieve. Procedures for making a similar molecular sieve used in the examples below is described in PCT Publication WO 02/070407 published Sep. 12, 2002, which is fully incorporated by reference.
To a solution of 63.94 grams of phosphoric acid (85% in water) and 51.22 grams of de-mineralized water, 4.15 grams of Ludox AS 40 (40% silica) was added upon stirring. Then, 116.71 grams of TEAOH (35% in water) was added. Finally 37.75 grams of pseudoboehmite alumina (Condea Pural SB) was added together with 6.22 grams of de-mineralized water. This slurry solution, a synthesis mixture, had a composition expressed as the molar ratio:
This synthesis mixture was then mixed until homogeneous and put into a 300 ml stainless steel autoclave. The autoclave was mounted on a rotating axis in an oven. The axis was rotated at 60 rpm and the oven was heated in 8 hours to 175° C. The autoclave was kept at this temperature for 12 hours. After crystallization a milky suspension with a pH of 10 was obtained, the slurry was then homogenized before dividing into 3 Parts:
Comparative Part 1: 50.04 g of the slurry above. No flocculant was added. Part 2: 50.0 g of the slurry above and 19.26 g prepared 5 wt % PEI (polyethyleneimine) (MW 750,000) solution. (Preparation of 5 wt % PEI solution: 2 g of 50 wt % PEI (Aldrich, MW 750,000) and 18 g of bi-distilled water was mixed with a spatula until homogeneous). Part 3: 50.02 g of the slurry above and 19.69 g prepared 5 wt % lower molecular weight PEI (MW 50,000 to 60,000) solution. (Preparation of PEI solution: 2.07 g of 50 wt % PEI (Aldrich, MW 50,000 to 60,000) and 18.1 g of bi-distilled water was mixed with a spatula until homogeneous). Parts 2 and 3 with the PEI flocculant immediately became viscous after addition of the flocculent. Comparative Part 1 and Part 2 were stirred on a magnetic stirrer plate for 25 minutes before washing. During that time Part 3 was left without stirring on the bench and allowed to settle. This resulted in a thick white slurry settling to the bottom with a substantially clear liquid on top. Then, Part 3 was also stirred and washed.
Each of Comparative Part 1, Parts 2 and 3 were washed three (3) times with about 180 g of distilled water for 10 minutes in a centrifuge at 3500 rpm. The wash water of Comparative Part lwas hazy while that of Parts 2 and Parts 3 were clear and colorless. The recovered products, the synthesized molecular sieves, were dried overnight in air at 120° C. The dried weights of the synthesized molecular sieves were: Comparative Part 1: 11.81 g, Part 2: 15.15 g and Part 3: 15.05 g.
The three synthesized molecular sieves above, Comparative Part 1 and Parts 2 and 3, were tested in a conversion process where in the oxygenated feed stock was methanol, and the conversion conditions were 25 WHSV, 25 psig (172 kPag) pressure, and at a temperature 450° C. The results of which are reported in the following Table 1.
Products Part 1 Part 2 Part 3
C2═ (ethylene) 32.34 31.59 31.79
C3═ (propylene) 40.41 41.58 42.38
C2═ + C3═ 72.75 73.16 74.17
C30 (Propane) 0.77 0.58 0.54
2C4+ 23.59 23.60 23.04
1Life Time 19.01 17.15 17.26
1Life Time is measured as grams of methanol converted per gram of molecular sieve.
2C4+ includes butene-1, butene-2, and higher carbon number hydrocarbons.
While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to variations not necessarily illustrated herein. For example, it is contemplated that one or more molecular sieves are recoverable in the presence of one or more flocculants. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.
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U.S. Classification 585/640, 502/514, 585/638, 502/64, 502/60, 585/639, 502/439, 502/214, 423/DIG.30
International Classification B01J29/85, C07C1/00, C10G3/00, B01J29/04, B01J37/00, C07C1/20, B01J27/182
Cooperative Classification Y02P30/20, Y02P30/42, C10G3/56, C10G3/49, C10G3/62, C10G2300/1022, C10G2400/20, Y10S502/514, Y10S423/30, C07C1/20, B01J29/85
European Classification C07C1/20, B01J29/85, C10G3/00
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