Patent Application
20100196261
The present invention relates to a highly pure ATO molecular sieve framework and method of preparation of said ATO molecular sieve framework. The ATO molecular sieve framework obtained by the process of the present invention is without any contamination of AEL framework.
Crystalline molecular sieves have 3-dimensional, microporous frameworks having tetrahedrally coordinated cation [TO4]. Generally, frameworks comprising oxygen tetrahedra of aluminium and silicon cations lead to the formation of microporous aluminosilicate framework commonly known as zeolites. On the other hand, 3-dimensional microporous aluminophosphate (AlPOs) frameworks classified as zeo-type molecular sieves are composed of oxygen tetrahedra of Al and P cations whereas silicoaluminophosphate (SAPOs) type molecular sieves composed of oxygen tetrahedra of Si, Al and P cations.
Molecular sieves are usually synthesized under hydrothermal conditions from a reactive gel comprising of aluminum, silica and/or phosphorous sources in the presence of an organic structure directing agent, such as an organic nitrogen compound in the temperature range of 100-200° C. Commonly used nitrogen compounds are amines, diamines and quaternary ammonium salts.
In general crystallization of molecular sieves performed under hydrothermal conditions requires prolonged crystallization time for phase formation. This sometimes leads to the formation of thermodynamically stable dense phases such as tridymite, cristobalite, berlinite, quartz as impure phases. This is due to the metastable nature of zeolitic framework under crystallization conditions. Furthermore, conventional hydrothermal approach is often found to be energy intensive.
To overcome such limitation, a microwave-assisted synthesis approach has been developed which offers many distinct advantages over conventional synthesis (Komarneni, et. al. Mater. Res. Bull. 1992, 27, 1393; Ionics 1995, 21, 95).
Crystalline (silico)aluminophosphate(SAPOs) molecular sieves are particularly useful as molecular sieve adsorbents and in hydrocarbon conversion processes. The use of such molecular sieves for catalytic dewaxing has been disclosed in U.S. Pat. Nos. 6,833,065, 5,833,837 and 7,077,947. Like wise, they are effectively used in methanol to olefin (MTO) conversion process, as described in U.S. Pat. Nos. 6,486,219, 7,214,844, 6,989,470, and 6,995,111. In the aforementioned patent literature, it is disclosed that one of the preferred SAPO molecular sieves for use in the therein described processes is SAPO-31 whose preparation and characterization is disclosed in U.S. Pat. No. 4,440,871. However, it is also known in the art that the synthesis of SAPO-31 demands seeding with AlPO-31 crystals up to 10 wt % (Examples 51 and 53; U.S. Pat. No. 4,440,871) to avoid co-crystallization of impure phases. Accordingly, heretofore, the art is not able to prepare substantially pure SAPO-31 without the addition of significant amounts of AlPO-31 seed crystals.
In view of the above, attempts have been made in the literature to obtain substantially pure AlPO-31 and/or SAPO-31 without any addition of AlPO-31 seeds. In this context, very few successful attempts are reported in the literature.
Among them, synthesis of AlPO-31 and/or SAPO-31 has been disclosed (U.S. Pat. No. 5,230,881) using di-n-propylamine as a structure directing agent and mineral acid (HNO3), if required, to manipulate the final reaction medium pH in the range of 4.5-5.5 in the temperature range of 150-200° C. for 5-7 days. The criticality of the final pH is found to be an important parameter in the disclosed art to obtain pure phase of SAPO-31. AlPO-11 (AEL) has been noticed as a common impurity with a lowering of final reaction medium pH. However, as per the disclosed art (.U.S Pat. No. 5,230,881), the crystallized SAPO-31 phase is found to have less than 5 wt % of other crystalline phases.
On similar lines, a successful crystallization of pure AlPO-3 land/or SAPO-31 has been reported (Abbad et.al., Micro. Meso. Mater. 21,1998, pg 13-18) using di-n-propylamine as a structure directing agent and mineral acid (HF) at 200° C. within 24 h. Like wise, crystallization of pure phase of AlPO-31 is disclosed in U.S. Pat. No. 5,552,132 using mixture of trimethyl sulfonium iodide and di-n-propylamine as structure directing agent.
More recently, specific templates have been reported for synthesis of pure ATO framework. A report by Kikhtyanin et.al. (Proceedings of the 12th International Zeolite Conference Vol. III p. 1743) discloses use of di-n-pentylamine as a specific structure directing agent for ATO (AlPO-31) framework synthesis at 200° C. within 24 h. However, crystallinity of the crystallized ATO framework using such template is found to be highly dependent on reaction medium pH. Typically, reaction medium having a pH of less than about 8.0 has been reported to favor crystallization of ATO framework with lower crystallinity.
Extending such approach, use of di-n-hexylamine (Hu et.al. Chem. Letters, 33, 2004, 1510) is reported to favor crystallization of pure SAPO-31 phase. Likewise, use of hexamethyleneimine, as a specific structure directing agent, has been recently disclosed (US patent application 2006/0147364). The use of such template is found to favor crystallization of AlPO-31 at 200 ° C. within 15 days.
In view of the aforementioned successful attempts and their limitation especially in terms of pH and crystallization time, the present invention discloses a novel structure directing agent favoring faster crystallization of a pure ATO framework at pH below 4.5 h.
The primary object of the present invention is to provide a specific structure directing templating agent favoring crystallization of ATO framework from a reaction medium having a pH below 4.5 and free of any mineral acid
Another object of the present invention is to disclose a process for preparing crystalline ATO type molecular sieve framework using such specific structure directing templating agent.
Yet another object of the present invention is to provide a rapid synthesis approach using such specific structure directing agent for crystallization of pure and highly crystalline ATO framework
Still another object of the present invention is to synthesize a ATO framework completely free of commonly observed major impurity phase, namely AEL framework.
The present invention discloses a process for the synthesis of ATO molecular sieve framework comprising forming a reaction medium comprising of reactive sources Al2O3, P2O5 and /or silica and a templating agent and subjecting said reaction medium to microwave hydrothermal heating until crystals of ATO framework are formed.
In one embodiment of the present invention the silica in the reaction medium is SiO2, Ludox AS-30 or tetraethyl orthosilicate and the templating agent is a long chain quaternary salt of organic moity comprising of a functional group R1, two anions at the terminal carbon atoms and trimethylamine.
In another embodiment of the present invention the functional group R1 is C5-C10 linear chain alkane, alkene or alkyl preferably, C6 and/or C7 linear chain alkane, alkene or alkyl.
In still another embodiment of the present invention the anions at the terminal carbon atom is an organic anion or an inorganic anion wherein said inorganic anion is selected form a group comprising of phosphate, halogens, sulfate, bisulfate, bisulfate, carbonate, bicarbonate, hexafluorophosphate, nitrate, oxyhalogen, such as chlorate, ClO3− or perchlorate, ClO4−, and wherein said organic anion is selected from as group comprising of carboxylate, R—COO−, amide, RCON−, alkoxide, R3 CO−, or etherate, RO−.
In yet another embodiment of the present invention the templating agent is synthesized by stirring at temperature of 50 to 80° C., preferably 60 to 80° C. in a non-aqueous solvent wherein said non-aqueous solvent is selected from the group comprising of methanol, ethanol, propanol, toluene or tetrahydrofuran for 4 to 24 hours to obtain crystals of said templating agent; cooling in a water-ice bath; separating said crystals of templating agent by filtration or centrifugation; washing said crystals with a solvent wherein said solvent is selected from the group comprising of methanol, absolute ethanol or ethanol; further washing with an anhydrous diethyl ether; and drying said crystals. In another embodiment of the present invention the reactive sources in the reaction medium are in the molar oxide ratios of 1.0 Al2O3:1.0-1.2 P2O5:0.3-1.2 R: 10-100 H2O preferably in the molaroxide ratios of 1.0 Al2O3:1.0-1.2 P2O5:0.5-1.0 R:40-75 H2O.
In still another embodiment of the present invention the reactive sources in the reaction medium are in the molar oxide ratios of Al2O3:P2O5:0-0.6 SiO2:R:40/50 H2O.
In yet another embodiment of the present invention the microwave-hydrothermal heating comprises heating at a temperature of at least 100° C., preferably between 150° C. and 200° C., most preferably between 150° C. to 180° C. for a period of 5 to 360 mins. In another embodiment of the present invention the crystals of ATO framework are recovered by filtration or centrifugation washed with water and dried at a temperature between 20° C. and 120° C.
In still another embodiment of the present invention the crystals of ATO phase are subjected to calcination at a temperature in the range of 200-800° C., preferably in the range of 300-600° C. for a period of 2-24 h.
In still another embodiment of the present invention the ATO molecular sieve framework obtained by the process of the present invention is pure and free from impurity phase wherein said impurity phase is AEL framework.
In one embodiment of the present invention the ATO molecular sieve framework is contacted with hydrocarbon component.
In another embodiment of the present invention the ATO molecular sieve framework is in hydrogen form and comprises at least one group VIII metal in the range of 0.05-0.3 wt %.
In yet another embodiment of the present invention the ATO molecular sieve framework is shaped in the form of extrudates or beads using binders selected from the group comprising alumina, clay or combination thereof in the range of 0-80 wt % preferably in the range of 20-50 wt %.
In yet another embodiment the present invention discloses an ATO molecular sieve framework comprising of reactive sources Al2O3, P2O5 and for silica and a templating agent as hereinbefore described.
The microporous aluminophosphate, having ATO type framework disclosed in the present invention is produced by microwave-hydrothermal crystallization from a reaction mixture containing reactive sources of phosphorus and aluminum and an organic structure directing agent (Diquat-hydroxide), and, optionally, additional divalent metals or sources of silica. The preparative process typically comprises forming a reaction mixture which in terms of mole ratios is:
where R is the structure directing agent namely diquat-hydroxide.
The reaction mixture is placed in a teflon vessel inert towards the reaction mixture and heated under microwave-hydrothermal conditions (MARS-5, CEM Corp, USA) until crystallized, under static conditions at a temperature of at least about 100° C., preferably between 150° C. and 200° C. for a period of 5 to 360 mins. The solid crystalline reaction product is then recovered by any convenient method, such as filtration or centrifugation, washed with water and dried in air at a temperature between ambient and about 120° C.
In a preferred crystallization method, the source of phosphorus is phosphoric acid, and the source of aluminum is a hydrated aluminum oxide of the trade name Catapal (Sasol), the temperature is 150° C. to 180° C., the crystallization time is from 15 to 180 mins, and the ratio of compounds in the reaction mixture is 1.0 Al2O3:1.0-1.2 P2O5:0.5-1.0R:40-75 H2O.
The templating agent is diquat-hydroxide and is present in the reaction mixture in an amount ranging from about 0.5 to 1.0 moles per mole of alumina. Additionally silica may also be introduced into the reaction. The preferred source of silica is either Ludox AS-30 or tetraethyl orthosilicate.
The structure directing agent used is known as Diquat compounds. The organic cation R+, also designated herein as Diquat-6/7, is derived from the Diquat-6/7 hydroxide or organic or inorganic salt of Diquat-6/7. The salts of Diquat-6/7 are obtained by reacting a suitable precursor salt containing the functional group R1, e.g., a hexyl/ heptyl derivative, containing two anions at the terminal carbon atoms, such as, 1,7-dibromoheptane/1,6-dibromohexane, with a stoichiometrically required amount of trimethylamine to form a diquaternary salt of the organic cation. The synthesis of the original salt of Diquat-6/7 can be carried out with an organic or inorganic precursor salt containing the functional group R1. The R1 group of the organic cation may be heptyl/hexyl or it may have one or more double or triple unsaturated bonds. Thus, for example, R1 may have one double unsaturated bond, or two or three consecutive or non-consecutive double unsaturated bonds. Alternatively, the R1 group may contain at least one triple unsaturated bond. However, in the most preferred embodiment, the R1 group is heptyl/hexyl.
The precursor salt contains two anions at the terminal carbon atoms of the functional group R1. Thus, the precursor salt has a formula A-R1-A, wherein R1 is as defined above and A is an organic or inorganic anion. Suitable inorganic anions are phosphate, halogens, e.g., fluoride, chloride, bromide or iodide, sulfate, bisulfate, bisulfite, carbonate, bicarbonate, hexafluorophosphate, nitrate, oxyhalogen, such as chlorate, ClO3− or perchlorate, ClO4−. Representative suitable organic anions are carboxylate, R—COO−, amide, RCON−, alkoxide, R3CO−, or etherate, RO−.
The synthesis of the Diquat-6/7 salt is conducted with a continuous stirring at a temperature of about 50 to about 80° C., preferably about 60° C. to about 80° C., at autogenous pressure in a suitable non-aqueous solvent, such as alcohol, e.g., ethanol, toluene or tetrahydrofuran, until crystals of the Diquat-6/7 salt are formed, usually for about 4 to about 24 hours. The crystals of the product settle to the bottom, the reaction mixture is cooled e.g., in a water-ice bath, and the product is separated from the reaction mixture by any suitable means, e.g., by filtration or centrifugaton. The crystals are then washed with a suitable solvent, e.g., absolute ethanol, followed by a wash with an anhydrous diethyl ether. The Diquat-6/7 salt crystals are then dried. The hydroxide form of Diquat-7 is obtained in any conventional manner from the salt of Diquat-6/7, such as by ion exchanging the salt of Diquat-7 with a suitable hydroxide in any conventional manner, e.g., in an ion-exchange column. Any of the conventional ion-exchange techniques is used to replace the original anions with the hydroxide anion, as will be obvious to those skilled in the art. Representative of such ion exchange techniques are those disclosed in a wide variety of patents, e.g., U.S. Pat. Nos. 3,140,249, 3,140,251 and 3,140,253.
The Diquat-6/7 hydroxide, when used as per the present invention leads to crystallization of AlPO-31/SAPO-31 phase having a characteristic X-ray diffraction pattern, set forth below in Table 1.
The crystallized ATO phase is subjected to post synthesis treatment namely calcination in the temperature range of 200-800° C., more preferably in the range of 300-600° C. to remove the entrapped organic moieties for the period of 2-24 h in air. Thus obtained calcined form is also found to have similar X-ray diffraction pattern as set forth in Table 1. The calcined form of the ATO phase is subjected to Nitrogen uptake measurement at −196° C. to estimate its surface area and micropore volume as per ASTM method 4365 applicable for microporous solids. Furthermore, the uptake of various probe molecules such as m-xylene, p-xylene, n-hexane, n-octane, n-heptane, cyclohexane is measured over the calcined phase at 20° C. to judge the adsorption crystallinity of the phase crystallized as per the art disclosed in the present invention.
As noted above, SAPO-31 functions well as a molecular sieve adsorbent. Additionally, catalysts containing SAPO-31 in admixture with at least one hydrogenation component, such as platinum, palladium, tungsten, vanadium, molybdenum, nickel, cobalt, chromium, and manganese, are excellent dewaxing catalysts (sometimes referred to as “catalysts”). Combinations of these metals such as cobalt-molybdenum, cobalt-nickel, nickel-tungsten or cobalt-nickel-tungsten, are also useful with such catalysts. Such catalysts generally comprise SAPO-31 and from about 0.01% to 10%, preferably from about 0.1% to about 5% of the hydrogenation component by weight of SAPO-31. Preferred hydrogenation components are platinum and palladium and, when employed, are preferably employed between about 0.1 percent and 1.5 percent by Weight of SAPO-31.
The physical form of SAPO-31 depends on the type of catalytic reactor being employed and may be in the form of a granule or powder, and is desirably compacted into a more readily usable form (e.g., larger agglomerates), with a silica or alumina binder for fluidized bed reaction, or pills, prills, spheres, extrudates, or other shapes of controlled size to accord adequate catalyst-reactant contact.
The present invention is further illustrated and supported by the following examples. These are merely representative examples and optimization details and are not intended to restrict the scope of the present invention in any way.
The Diquat-6/7 dihydroxide salt used to crystallize molecular sieve AlPO-31 and/or SAPO-31 is prepared by reacting 1,7-dibromoheptane/1,6-dibromohexane and trimethylamine in accordance with the following stoichiometric equation:
The procedure used is as follows:
50 grams of 1,7-dibromoheptane (Sigma-Aldrich Chemical Company) is weighed out and transferred directly to a two-liter, three-necked reaction flask equipped with a stirrer. 100 ml absolute ethanol is added to the reaction flask while the contents of the flask are stirred continuously. Then, 100 grams (excess) of trimethylamine solution (25% in methanol, Sigma-Aldrich Chemical Company) is transferred directly to the two-liter reaction flask. The two-liter reaction flask is fitted with a dry-ice condenser to minimize (CH3)3N loss during reflux.
The reaction mixture is refluxed for about 14 hours. White crystals of Diquat-7 dibromide are formed and separated from the reaction solution at the end of the reflux period. The reaction flask is cooled by immersion in water-ice bath. The product is then filtered on a Buchner funnel. Product crystals are washed on the funnel several times with absolute ethanol, then several times with anhydrous diethyl ether. The Diquat-7 dibromine product crystals are dried by air stream on the Buchner funnel after the ether wash. Thus obtained dibromide salt of diquat-7 is subjected to ion exchange procedure to convert it to dihydroxide form using anion exchange resion Dowex 8X. Typically, aqueous solution of 50 wt % of dibromide salt of Diquat-6/7 is slurried in 1 L water containing 20 g of resin for 20 h to obtain dihydroxide salt of Diquat-6/7.
AlPO-31 is crystallized from a reaction mixture prepared by combining 2.3 grams of Psedoboehmite (Catapal vista B, Sasol) with 3.7 grams of 85 wt.% orthophosphoric acid (H3PO4)and 5.0 grams of water and stirred until homogeneous. To this mixture is added 8 grams of Diquat-7 hydroxide solution (22% in water) and the mixture further stirred. The composition of the final reaction mixture in molar oxide ratios is:
This homogenised reaction mixture is placed in a stainless steel pressure vessel lined with an inert plastic material and heated in under microwave-hydrothermal conditions by employing MARS-5 (CEM,USA) unit at 180° C. at autogenous pressure for 3 hours. The solid reaction product is recovered by filtration, washed with water, and dried in air at 120° C. Thus obtained product is subjected physicochemical characterization. X-ray diffraction pattern of as-synthesized form displaying the characteristic peaks of ATO phase as listed in Table 1. The morphology of the sample is investigated by means of scanning electron microscope (SEM, Leica, Cambridge, Model 440,
AlPO-31 is crystallized from a reaction mixture prepared by combining 2.3 grams of Psedoboehmite (Catapal vista B, Sasol) with 3.7 grams of 85 wt. % orthophosphoric acid (H3PO4)and 5.0 grams of water and stirred until homogeneous. To this mixture is added 8 grams of Diquat-6 hydroxide solution (22% in water) and the mixture further stirred. The composition of the final reaction mixture in molar oxide ratios is:
This homogenised reaction mixture is placed in a stainless steel pressure vessel lined with an inert plastic material and heated in under microwave-hydrothermal conditions by employing MARS-5 (CEM,USA) unit at 180° C. at autogenous pressure for 3 hours. The solid reaction product is recovered by filtration, washed with water, and dried in air at 120° C. Thus obtained product is subjected physicochemical characterization. X-ray diffraction pattern of as-synthesized form displaying the characteristic peaks of ATO phase as listed in Table 1.
SAPO-31 is crystallized from a reaction mixture prepared by combining 2.0 grams of Psedoboehmite (Catapal vista B, Sasol) with 3.2 grams of 85 wt. % orthophosphoric acid (H3PO4) and 4.0 grams of water and stirred until homogeneous. To this mixture is added 1.12 grams of an aqueous sol of 30 wt. % SiO2 and the mixture is further stirred until homogeneous. To this mixture is added 7 grams of Diquat-7 hydroxide solution and the mixture is stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios is:
A portion of this reaction mixture is placed in a stainless steel pressure vessel lined with an inert plastic material and heated in under microwave-hydrothermal conditions by employing MARS-5 (CEM,USA) unit at 160° C. at autogenous pressure for 4 hours. The solid reaction product is recovered by filtration, washed with water, and dried in air at 120° C. Thus obtained product is subjected physicochemical characterization. X-ray diffraction pattern of as-synthesized form displaying the characteristic peaks of ATO phase as listed in Table 1.
Calcination of ATO Framework:
The material from Example 1 is calcined in air in the following manner. A thin bed of material is heated in a tubular quartz reactor from room temperature to 120° C. at a rate of 1° C. per minute and held at 120° C. for two hours. The temperature is then ramped up to 540° C. at the same rate and held at this temperature for 10 hours.
The calcined form of AlPO-31 as prepared in Example-5 has a micropore volume (t-plot) of about 0.20 cc/gm with surface area of about 275 m2/g based on adsorption isotherm at 77 K recorded on AS-1C unit from Quantachrome. The nitrogen adsorption isotherm is analyzed using the non linear density function theory (NLDFT) approach (J. Phys. Chem. B.; 2001 105(29); 6817) and the conventional t-plot method (J. Catalysis, 1965, 4, 319). The DFT analysis also shows that calcined form AlPO-31 has a pore size of about 0.53 nm.
The acidity for the alumino/ silicoaluminophosphate ATO framework is measured using ammonia-TPD technique. Typically, 50 mg of samples prepared as per examples 2 and 4 and treated as per example 5 are exposed to 6% ammonia/helium mixture and ammonia desorption is recorded as a function of temperature using Alta-Mira AMI200 unit. The measured TPD curves (
Adsorption capacities are measured on this calcined product using a standard McBain-Bakr gravimetric adsorption apparatus. The following data (Table 2) is obtained on a sample activated at 300° C.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1234/MUM/2007 | Jun 2007 | IN | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/IN2007/000424 | 9/17/2007 | WO | 00 | 4/12/2010 |
