CA2197454A1 - Synthesis of novel molecular sieves using a metal complex as a template - Google Patents
Synthesis of novel molecular sieves using a metal complex as a templateInfo
- Publication number
- CA2197454A1 CA2197454A1 CA002197454A CA2197454A CA2197454A1 CA 2197454 A1 CA2197454 A1 CA 2197454A1 CA 002197454 A CA002197454 A CA 002197454A CA 2197454 A CA2197454 A CA 2197454A CA 2197454 A1 CA2197454 A1 CA 2197454A1
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- CA
- Canada
- Prior art keywords
- molecular sieve
- sio2
- ion
- cobalt
- microcrystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/30—Alpo and sapo
Abstract
The synthesis and characterization of novel molecular sieves containing bis(pentamethylcyclopentadienyl)cobalt(III) ion are described. Several types of molecular sieves were prepared using the cobalt metal complex as a template that was shown to be incorporated as a guest molecule within the molecular sieve. Molecular sieves prepared using bis(pentamethylcylclopentadienyl)cobalt(III) ion as template were characterized as having a pore size at least as large as 7 Ä. Other molecular sieves were also prepared using bis(cyclopentadienyl)cobalt(III) templates.
The compounds are attractive as catalysts in a wide range of applications.
The compounds are attractive as catalysts in a wide range of applications.
Description
wog6~06n~2 ~ 1 9 745 ~ F~~ f ~n~aI~ OF NOVE~ Mnr,~C~T.~ 8IEVE8 U8ING A META~
COMPLE~ A8 A TEMPLATE
7~ )NI~ OF T~{E lh~l:.n.LlC~
~ Field of the Invention The invention relates generally to synthesis of molecular sieve complexes and more specifically to the use of certain bis(cyclopentadienyl) cobalt ion complexes as ~LIU~UL~ directing agents or templates.
DescriDtion of Rel~ted Ar~
The incuL~vL~tion of metal _ l oYos during the synthesis of molecular sieves is known to be useful for synthesis of zeolite "ship-in-a-bottle" complexes. NaX
zeolites have been synthesized around metal phthalocyanines (Balkus, et al., 1992; Balkus and 20 Kowalak, 1992). In a few cases the metal complex may also function as a structure directing agent during crystallization. The metal complex bis(cyclopentadienyl)cobalt(III) ion, q~co~, has been reported to be a template for isostructural ZSM-51 and Nonasil in hydroxide and fluoride media as well as ZSM-45 (Balkus and Shepelev, 1993A, 1993B; U.S. Patent No.
4,568,654). Nonasil is described in U.S. Patent No.
4,556,549 as an all-silica clathrasil type molecular sieve. The metal complex is completely Pnr~rsulated as indicated by the x-ray structure that shows the largest openings to the nonasil cages are 6 h~red rings (Behrens, et al., 1994).
The formation of many molecular sieves depends on the presence of template molecules that affect the gel chemistry and/or act as a void filler (R. Szostak, 1989).
Most of the templates that have been evaluated for WOg~l0~4~ 2 ~ S ~ PCT~9~ln6~C ~
molecular sieve synthesis are based on organic molecules, particularly aliphatic amines. By comparison, the structure directing properties of metal complexes are relatively unexplored. Cobalticinium ion, Cp2Co+, has been shown to be a te~plate for the clathrate type molecular aieves Nonasil and ZSM-51 as well as ZSM-45.
In the case of ZSM-51, the template claimed for its svr.thesis was bis(cyclopentadienyl) cobaltIIII) hexafluorophosphate More recently, Cp2CoO~ was shown to be a template for the aluminum phosphate molecular sieves AlP04-5 and AlP0~-16. Cp2Co+ has been reported to produce the all-silica clathrasils octadecasil and dodecasil.
Recer.t work has thus indicated that the role of the metal and the effect of functionalizing the bis (cyclopentadienyl) rings may lead to new types of molecular sieves when these agents are used as structure directing agents. However, the structure directing effects for syntnesis of molecular sieves are largely unpredictable and not well understood. The availability of novel molecular sieves would be beneficial in extending the range o~ zeolite type catalysts and in semiconductor applications.
COMPLE~ A8 A TEMPLATE
7~ )NI~ OF T~{E lh~l:.n.LlC~
~ Field of the Invention The invention relates generally to synthesis of molecular sieve complexes and more specifically to the use of certain bis(cyclopentadienyl) cobalt ion complexes as ~LIU~UL~ directing agents or templates.
DescriDtion of Rel~ted Ar~
The incuL~vL~tion of metal _ l oYos during the synthesis of molecular sieves is known to be useful for synthesis of zeolite "ship-in-a-bottle" complexes. NaX
zeolites have been synthesized around metal phthalocyanines (Balkus, et al., 1992; Balkus and 20 Kowalak, 1992). In a few cases the metal complex may also function as a structure directing agent during crystallization. The metal complex bis(cyclopentadienyl)cobalt(III) ion, q~co~, has been reported to be a template for isostructural ZSM-51 and Nonasil in hydroxide and fluoride media as well as ZSM-45 (Balkus and Shepelev, 1993A, 1993B; U.S. Patent No.
4,568,654). Nonasil is described in U.S. Patent No.
4,556,549 as an all-silica clathrasil type molecular sieve. The metal complex is completely Pnr~rsulated as indicated by the x-ray structure that shows the largest openings to the nonasil cages are 6 h~red rings (Behrens, et al., 1994).
The formation of many molecular sieves depends on the presence of template molecules that affect the gel chemistry and/or act as a void filler (R. Szostak, 1989).
Most of the templates that have been evaluated for WOg~l0~4~ 2 ~ S ~ PCT~9~ln6~C ~
molecular sieve synthesis are based on organic molecules, particularly aliphatic amines. By comparison, the structure directing properties of metal complexes are relatively unexplored. Cobalticinium ion, Cp2Co+, has been shown to be a te~plate for the clathrate type molecular aieves Nonasil and ZSM-51 as well as ZSM-45.
In the case of ZSM-51, the template claimed for its svr.thesis was bis(cyclopentadienyl) cobaltIIII) hexafluorophosphate More recently, Cp2CoO~ was shown to be a template for the aluminum phosphate molecular sieves AlP04-5 and AlP0~-16. Cp2Co+ has been reported to produce the all-silica clathrasils octadecasil and dodecasil.
Recer.t work has thus indicated that the role of the metal and the effect of functionalizing the bis (cyclopentadienyl) rings may lead to new types of molecular sieves when these agents are used as structure directing agents. However, the structure directing effects for syntnesis of molecular sieves are largely unpredictable and not well understood. The availability of novel molecular sieves would be beneficial in extending the range o~ zeolite type catalysts and in semiconductor applications.
2~ SUMMARY OF ~IE lNV~l~L~
The present invention addresses problems inherent in the art by providing novel molecular sieve compounds and prc,cesses for producing the novel compounds. The present 3~ wor.k shows that certain metal complexes can be employed as templates or structure-directing agents. Several new molecular sieve compounds have been produced. The compounds are microcrystalline and microporous and incorporate the templating agent metal used in the formation of the compound.
~'096/060~2 ~ PCT~59.$ll0~6 In particular, bis(cyclopentadienyl) cobalt(III) ior (Cp2Co+), has been shown to be a template for synthesis of the aluminum phosphate molecular sieves exemplified by AlPO4-5 and AlPO4-lS. This is an unexpected finding to the extent that this metal complex will provide a ~ template for both channel ~AlPO4-5) and cage ~AlPO4-16) molecular sieves. The Cp2Co+ complex is relatively rigid, unlike many typical organic templates. This provides an opportunity to evaluate the effects of size, shape and symmetry on the structure directing properties of the complex by the modifying the Cp ring(s1 with different substituents.
Employing a fully methylated derivative, bis(pentamethylcyclopentadienyl) cobalt(III) ion (CP2 Co+), the inventor has produced five new molecular sieves. It is contemplated that other new molecular sieves can be produced by altering the template; for example, any combination of alkyl groups on the cyclopentane ring such as methyl, ethyl, propyl, etc. as well as various metal species such as Ni2+, Fe2+, and other Group ~III metal ions. Nevertheless, the properties of these templates would be expected to differ from the bis pentamethylcyclopentadienyl species employed in the present invention.
The different metal complexes so far studied have unique structure directing properties, such that bis(cyclopentadienyl)cobalt(III) ion does not promote formation of the same structures as bis (pentamethylcyclopentadienyl)cobalt(III) ion. This is li~ely due to the different features of each complex, including size, shape and charge distribution.
Overall, and in general, the invention discloses novel microcrystalline molecular sieves prepared from template directing metallo organic complexes. In WO~C1~6~42 2 ~ ~ 7 4 ~ ~ PCTlUSgS/10646 particular embodiments, a metal microcrystallire silica molecular sieve with a nominal pore diameter of at least 7.~ A is formed. Such silica molecular sieves incorporate the positively charged metal ion as a guest molecule. Among the unique 8tructures produced using the ~Cp2~2O+) ion is a microcrystalline silica molecular sieve characterized as a yellow crystalline producs, UTD-1. UTD-1 was prepared as a single phase product employing bis(pentamethylcyclopentadienylj cobalt(III~
ion as template. The crystalline ~aterial was formed from a gel containing sodium hydroxide, the organic metal template and fumed silica. UTD-1 is formed from a gel with the approximate molecular ratio of water to sio~ of about 60, sodium ion to SiO2 of about o.l, hydroxyl ion to silica SiO2 of about 0.2 and the bis(pentamethylcyclopentadienyl) cobalt~III) ion template ratio to sio2 of about 0.~. The x-ray diffraction powder patterns for the UTD-1 as synthesized and the calcined material indicate the uniqueness of the molecular sieve.
2s As expected, there is decomposition of the organic portion of the template after calcination at 500~ C. The o~erall structure, however, is quite stable. The bright yellow color of lJTD-1 indicates that the pentacyclodienyl metal ion complex is entrapped in the crystals as a guest molecule. The metal complex template is relatively large and is not remo~ed by either aqueous or organic extraction procedures. Channels or cages within the molecular complex therefore are at least as large as the Cp rings that measure approximately 7.2 A. UTD-l is also a relati~ely large pore material as suggested by the low angle reflections obtained on x-ray crystallographic measurement.
~hile UTD-1 is quite stable, there is an indication o' decomposition at approximately 350~ C. Calcination is accompar.ied by a change in color from yellow to pale green. It is likely that this change of color represents _ _ _ _ _ _ W096106042 ~ 4 ~ ~ PCT~S95/10646 decomposition of the organic portion of the metal complex with concomitant formation of metal oxide. There was no evidence of framework substitution by the cobalt durirg formation of the molecllar sieve.
Yet another embodiment of the present invention is illustrated in the formation of the molecular sieve UTD-2. This compound also incorporates Cp 2Co as a guest molecule but is different in structure in incorporating aluminum and phosphorous as part of the framework. UTD-2 is also obtained as a single phase product from a gel having molar ratios of 1:0.5:0.4:0.86:0.025:50 for the components A12O3:P2O5:SiO2:(TPA~zO:Cp 2Co)2O:H2O. Of course, these ratios may oe varied somewhat. The preferred Al2O3/SiO2 molar ratio is 2.5, although ranges as high as 4 or as low as 1 are also suitable. Using ratios outside of the range 4~2.5~1 typically results in an amorphous material. A convenient procedure for the preparation of UTD-2 and similar molecular sieves is to prepare two mixtures; mixture 1 from aluminum hydroxide and phosphoric acid and mixture 2 from silica, preferably fumed silica, CP~2Co~ hydroxide, and tetrapropylammonium hydroxide. Of course, one may vary not only the ratios but the type of quaternary ammonium compound employed;
for example, other tetra alkyl ammonium hydroxides.
UTD-2 is conveniently formed after mixing mixture 1 and mixture 2, heating for a period of time at approximately 200C C. cooling, dilutirg and separatins the crystalline mate-ial. UTD-2, like UTD-l, is yellow indicating inclusion of the metal template within the molecular sieve.
The novel compound UTD-2 may also be prepared using only Cp 2CoOH as template. The preserce of tetrapropyl ammonium hydroxide, however, appears to be conducive to obtaining better yields of UTD-2. When using only Cp~2CoOH as the template, gels with molar ratios of about W0'36/O~Z ~ 5 ~ ~CT~Sg~l~K46 _ Al2o3:p2os:sio2(cp 2Coj20:X2Q may be employed as preferred ratios. Variations of Al203~SiO2 ma~ be employed as pre~iously discussed, preferably in t.he range of 4~2.5~1. 9 A new component, UTD-5, also resulted from the single template synthetic procedure used to obtain UTD-2.
The new material UTD-5 was distinguishable from UT5-2 in its x-ray pattern as synthesized from the gel mixture and also after calc~nation at 500~ C. The unusual dark sreen color of the calclned UTD-5 suggested formation of cobalt oxide and/or possibly the free metal.
Yel another embodiment of the present inven~ion, t~e unsubstituted form of bis(cyclopentadienyl~ cobalt(III), was used as a template to form UTD-3/SAP0 compound. The cobalt ion template was used in combination with tetrapropylammonium hydroxide. This compound was prepared using procedures analogous to those used to prepare UTD-2 except that the second mixture incorporated Cp2CoOX rather than Cp 2CoOX. Preferred molar ratios for Al2O3 P20s:siO2:~TPA)2O:(CP2~o)2O:x2o were about 1:0.9:0.4:0.86:0.025:48. The new UTD-3 SAPO compound was yellow in color~ microcrystalline, and like the other compounds, changed color after calcination at 500~ C.
The new compound had a unique x-ray powder diffraction pattern. The calcined sample was a sky-blue color after heating for several hours at. 500~ C. UTD-3 could also be prepared as a s~ngle phase from the gel containing cobalt(II) ions instead of silica and Cp2CoO~ as the only tempiate. This UTD-3 compound is a modification of the UTD-3 to the extent that it is isolated as a dark blue-green product; ho~ever, it is single phase and has an x-ray diffra~tion pattern cubstantially the same as UTD-3.
UTD-3-CoAP0 is prepared by mixing phncrhnric acid, a cobalt salt, preferably cobalt sulfate, then adding aluminum hydroxide and the bis(cyclopentadienyl) ~ wo 96,~6042 ~ ~ ~ 7 ~ ~ ~ PCT~S~/10646 cobalt(III) hydroxide template, mix1ng the gel for several hours, e.g., approximately four hours, and then heating at about 200~ C for about a day, i.e., 18 to 24 ~ hours, to provide a single phase product. Preferred molar ratios for Al203:P2O5:CoO:(Cp2Co)2O:H2O are about 0.8:1:0.4:0.75:53. However, the ratios may employed within this general range to obtain UTD-3 CoAPO.
Yet another embodiment of the present invention UTD-6 may be prepared again employing the bis(pentamethylcyclopentadienyl~ cobalt(III~ template.
In a particular embodiment, UTD-6 was prepared using two templates, the bis(cyclopentadienyl) complex ar.d tetrabutylammonium hvdroxide. The compound was prepared from a silicoaluminum phosphate gel. The preferred component molar ratios were about 1:0.9:0.4:0.86:0.16:75 for Al203:P2O5:SiO2:(TBA)2O:H2O. UTD-6 was conveniently prepared by ~ ; ng two mixtures; the first containing aluminum hydroxide and phosphoric acid; and the second containing fumed silica and the two templates.
The five new molecular sieve compounds described above are illustrative of the types of new compounds that may be prepared using a metal organic complex. For the first time, the inventors have shown the structure directing properties of cobalticirium ion complexes and that have demonstrated molecular sieves can be formed without an organo cation. The present invention illustrates the general types of novel structures that may be produced in the presence of bis~pentamethylcyclopentadienyl) cobalt(III) ion as the template. It is possible that even larger pore materials may be produced by increasing the bulkiness of the complex cobalt(III) ion; for example, by appropriate substituer.t groups on the cyclopentane rings.
WOg6~0~4~ 21 g ~ ~ 5 4 PCT~S9~110646 -While the complete range of reactions and properties of the new microcrystalline metal molecular sieves has not been explored, it ls recognized that related compounds have been well utilized as catalysts. ~ore specifically, such compounds have been used in catalytic hydrofining, cracking, and as selecti~e adsorbants. Mar.y of these uses are described in more detail in U.S. Patent No. 4,g40,87l incorporated herein by reference where it is noted that in general silicon aluminum phosphate molecular sieves are similar to zeolite catalysts in several of their properties.
By analogy with the Cp~Co+/nonasil complexes, t.he new molecular sieves are expected to exhibit special ~5 optical effects that could be exploited in memory storage devices. Molecular sieves are increasingly being developed as sensors in semiconductor devices.
BRIEF DESCRIPTION OE ~E DRAWINGS
2~
FIG. lA. Powder x-ray diffraction pattern of UTD-l as synthesized.
FI5. lB Powder x-ray diffraction pattern of UTB-l after Z5 calcination (500~C, 4 hr) samples. CaF2 was used as an internal standard.
FIC-. Z. Scarnln5 electron micrograph of UTD-l.
~0 FIG. 3A. FT-IR spectra for UTD-l as synthesized. Sample prepared as KBr pellet.
FIG. 3B. FT-IR spectrum for UTD-l after calcination ~500~C, Sample prepared as KBr pellet.~5 W096/06042 ~1~ 7 ~ ~ ~ PCT~S95/l0646 DETAI~ED DESCRIPTION OF THE ~K~'~KK~ EMsODrMENTS
The templating ability of metallocenes in the synthesis of crystalllne microporous metal oxides is the general focus of the present invention. The inventors have prepared and characterized a series of novel silica type molecular sieves, desigr.ated as "~T~" compounds.
The novel structures are produced in the presence of bis(pentamethylcyclopentadienyl~cobalt(III) ion, Cp 2Co+, as the template. Since the less bulky Cp2Co+ appeared to favor formation of the smaller pore clathrate type molecular sieves, the inventors have reasoned that addition of methyl groups to the cyclopentadienyl rings will encourage the crystallization of larger pore materials.
It is known that the crystallization of zeolite molecular sieves in the presence of metal chelates may result in encapsulation of the complexes ~U.S. Patent No.
5,167,942). This is a viable method for the preparation of zeolite ship-in-a-bottle complexes ~salkus and Gabrielov, 1994); however, the metal complex may also serve as a structure directing agent. The formation of many molecular sieves depends on the presence of template molecules that affect the gel chemistry and/or act as a void filler.
Most of the templates that have been evaluated for molecular sieve synthesis are based on organic molecules, especially aliphatic amines. By comparison, the structure directing properties of metal complexes are virtually unknown. Cobalticir.ium ion, Cp2Co~, has been shown to be a template for the clathrate type molecular sieves Nonasil and ZSM-51 (Balkus and Shepelev, 1993;
Balkus and Shepelev, 1993B; U.S. Patent No. 4,568,564).
More recently, wor.k in the inventors~ laboratory showed that Cp2CoOH acts as a template for the production of Wog~ 2 ~ 7 ~ ~ 4 PCT/US9~l~
- ~10 -AlPO4-16 and SAPO-16. Molecular sieves of this type had previously required an organo-cation to form and, specifically in the case of AlPO4-1~ or SAPO-i6, only quinuclidene was known to generate this topology.
s The following examples are provided for purposes of clarification and should not be considered as iimitir,g.
One skilled in the art would recognize in light of the pre.sent disclosure that although the specified materials and conditions are important in practicing the invention, unspecified materials and conditions are not excluded as long as they do not prevent the benefits of the invention from being realized.
EXAMP~3 1 This example illustrates the preparation of an all-silica molecular sieve using a bis~pentamethylcyclopentadienyl~cobalt(III) ion as a template. The microcrystalline silica molecular sieve incorporates the complexed cobalt ion, apparently as a guest molecule.
Preparation of U~D-1 The metal complex Cp~zCoPF~ was prepared ~ocording to the literature procedure (Kolle and Khouzami, 1581).
The complex was converted to the chloride derivative over Dowex-50W cation exchange resin by first adsorbing the Cp 2Co+ ion followed by ell~tion with lM HC1. The Cp~CoCl was then transformed to the hydroxide form over an aqueous slurry of silver oxide at 70C. The concentration of the brown Cp 2CoOX solution was determined by potentiometric titration. The solution was then used in the molecular sieve synthesis.
~ W096/06042 21 ~ 4 PCT~S9~/10646 UTD-l was prepared as a single phase product by combining NaOH, a 31.6~ a~ueous Cp~2CoO~ solution and fumed silica to form a gel with the following molar ratios.
H2~/Si~2 60 Na+/SiO2 0.1 OH-/SiO2 0.2 Cp~2Co+/SiO2 ~ . 1 The gel was aged with stirring for 1 hour and then transferred to a 23 mL Teflon-lined pressure reactor (Parr). The reactor was heated at 175~C under static conditions for 2 days. The resulting yellow crystalline produce was washed with deionized water, suction filtered and then dried at 90~C for 2 hours.
FIG. lA shows the X-ray diffraction ~XRD) powder pattern data for UTD-l as synthesized. FIG. lB shows the XRD of calcined UTD-l. Although there are changes in peak intensity after calcination at 500~C and decomposition of the tempiate occurs, the structure appears quite st.able. FIG. 2 shows the bundles of recsangular shaped crystals obtained after synthesis.
These results support a single phase material. The bright yellow color of UTD-l indicated that the Cp 2Co+
template was entrapped in the crystals as a guess molecule. The metal complex cannot be removed by aqueous or organic extraction. This implied that the channels or cages were at least as large as the Cp~ rings (7.2 A) in order to accommodate the complexes. The low angle reflections in ~IG. lA and FIG. lB also suggested a large pore material. Additionally, preliminary adsorption experiments using calcined UTD-l indicated a -20~ by weight increase upon exposure to cyclohexane (kinetic diameter 6.0 A). Pore size determination by more direct adsorption methods is complicated by the occluded cobalt species.
W(~96/Obll42 213 7 4 ~ 4 Pcrlu8~s~l0~
- i2 -TA'3LE lA
~ d s~acinc (A) and relative intensit~ for ~TD-1 a~
svnthesized:
14.686 (4B), llwas.742 (44), 8.068 (6), 5 512 (23~, 6.058 (53), 5.872 (8), 6.459 ~50), 5.911 (50', 4.365 (10), 5.443 (100), 4.~31 (57), 3.946 ~25), 3.913 (15j, 3.829 (5), 3.710 (5), 3.668 (41), 3.611 (34), 3.448 (4), 3.390 (23), 3.206 ~5~, 3.084 ~11), 3.006 (23), 2.79g (8), 2.763 (18), 2.738 (3), 2.637 (4), 2.509 (4), 2.489 (3), 2.445 (7), 2.406 (3), TABLE lB
Calcined at 500~C
calcined (500 C): 14.609 (lO0), 11.50g (64), g.466 ~6), 6.094 (10), 4.8~32 (13), 4.478 (23), 4.384 (7), 4.211 (45)l 4.049 (10), 3.955 (6), 3.843 (5)l 3.735 (2), 3.659 (17~, 3.560 ~14~, 3.400 (9), 3.066 (3), 2.986 (5), 2.769 (6), 2.646 (1), 2.553 (1), 2.466 (1), 2.436 (2), 2.374 (2).
There was no evidence of complex decomposition durin~ synthesis from spectroscopic analysis o~
encapsulated and free complexes. The W-Vis spectrum of a UTD-1 nujol mull was broadened and slightly red shifted (~15 nm) compared to an aqueous solution of Cp ~CoOH
(290, 338sh, 406sh nm). However, this shift to lower energy was also noted for Cp2Co+ in Nonasil and AlPO4_5 molecular sieves (Balkus and Shepelev, 1993A).
Thermogravimetric analysis (TG) of Cp 2CoPF6 indicated the onset of decomposition at -350~C, which is significantly higher than the UTD-1 synthesis temperature (175~C). Similarly, UTD-1 begins to lose weight at ~350~C with a change in color from yellow to pale green.
~'096/06042 ~l~ 7 4 ~ A PCT~9511U646 measured up to 900~C. The small change is consistent with loss of the organics and probable formation of occluded oxides.
There was no evidence of framework substitution by cobalt. The FT-IR spectrum of UT~-1 also indicated the presence of intact Cp 2Co+ as evidenced by the uc~ at 2915 cm~1 that can be compared to the free Cp*2CoPF6 complex with a C-~ band at 2920 cm~l. Similarly, a C-C stretch iO at 1476 cm~1 for the free complex appeared at 1480 cm~1 in UTD-1. There were a variety of other bands that might be ascribed to the encapsulated metal complex; however, they were either masked by the bands associated with the mojlecular sieve or were quite weak.
FIG. 3A shows the FT-IR spectrum in the region 1500-400 cm~1 for UT~-1 as synthesized. FIG. 3B shows the FT-IR spectrum after calcination at 500~C. There are two strong bands at 1237 and 1092 cm~l that are typical of the asymmetric Si-O stretches observed for crystalline silicates. There are no significant shifts for these bands after calcinationj however, two shoulders are resolved at 1140 and io76 cm~1. The bands that appear in the symmetric stretching region ~812, 787, 642 cm~1), as well as the more .structure sensitive region (612, 582 and 537 cm~1), appear quite different from known silicate phases.
The results indicate that an all-silica phase UTD-1 can be synthesized using the metal complex Cp~2CoO~ as a template that becomes incorporated as a guest molecule.
The data indicate that UTD-1 is a large pore material l~7 A) Wo ~106042 2 1 ~ 7 ~ ~ PCT~S~.~110646 Another new molecular sieve was prepared as illustrated in the following example. ~his compound/
like UTD-1, also incorporates the template Cp 2Co+ as a guest molecule but differs in including aluminum ard phosphorus as part of the framework.
Preparation of UTD-2 UTD-2 was obtained as a single phase product from a gel having molar ratios Al2o3:P2O5:SiO2:(TPAl2O:(CP 2co~2o H2o ~
1:0.9:0.4:0.86:0.025:50. The preferred A12O3/SiO2 molar ratio is 2.5. Taking the Al2O3/SiO2 ratios out of the range 4~2.5>1 may result in an amorphous material. The procedure involves first preparing two mixtures as follows.
Mixture 1 was prepared by slowly adding 2 g of aluminum hydroxide (Pfaltz & Bauer, LOT 039789, 83.34 wt~j to a solution of 2.22 g 35 wt% H3PO4 (Fisher~ and 2.0 g of deionized water with magnetic stirring. After adding about 1.3 g of the hydroxide, the gel became extremely viscous and was stirred with a Teflon rod for 1 hour.
Mixture 2 was prepared by adding 0.256 g fumed silica (0.007 ~, Aldrich) to a mixture of 0.58 g of a 30 wt~ Cp 2CoOH solution in water and 9.28 g of 40 wt~
tetrapropylammonium hydroxide iTPAOH~ obtained from Alfa~
Mixture 2 was not viscous and easily obtained homogeneity.
Mixture 2 was added slowly to mixture 1 and the final mixture was stirred for approximately 6 hours in order to achieve a homogeneous gel. The gel was -~ W096/OC042 2 ~ ~ 7 4 5 ~ PCT~595llU646 transferred into a 25 cm3 Teflon-lined pressure reactor (Parr) that was subsequently placed in an oven ha~ing a constant temperature of 200~C. After 20 hrs heating at ~ autogenous pressure, the mixture was cooled to room temperature and diluted with 100 mL of deionized water.
~ The bright yellow crystals were separated from a white amorphous material by centrifugation and/or sedimentation, washed with deionized water and isolated by filtering through a nitrocellulose membrane (2 ~mj under suction. The solid yellow residue was dried at room temperature for 24 hrs. UTD-2 appeared on SEM
images as a single phase.
X-rav ~ttern for UTD-2 a sYnthesized # 2 theta d, A (rel.int., ~) 1. 6.270 14.085 ~100) 2. 11.307 7.819 (4) 3 11.720 7.545 (3) 4. 12.542 7.052 (g) 5. 18.844 4.705 (27) 6. 19.272 4.602 (50) 7. 20.267 4.378 (23) 8. 23.014 3.8~1 (2) 9. 25.215 3.529 (61) lO. 27.062 4.274 (6) 11. 31.903 2.893 ~3~
12. 33.695 2.658 (12) - 13. 34.283 3.393 (7) 14. 36.014 2.492 (11 15. 38.165 2.356 (1) ~09~l06042 2 1 ~ 7 4~ ~ PCT~S9~tO6~6 EXhNPL~ 3 UTD-2 could be also obtained using only Cp~2CoOH as template, as sho~r. in the following example.
Sinqle Tem~lste SYnthesis of UTD-2 The single template synthesis of UTD-2 was sub~stantially the same as that described in Example 2 except that mixture 2 was prepared by adding 0.256 g fumed silica to 7.76 g of a 30 wt% Cp~2CoO~ solution in water. The final gel had molar ratios A1203:P205:
SiO2:iCp 2Co)20:~20 - 1:0.9:0.4:0.32:50. The x-ray pattern of the yellow sample obtained after crystalli~ation and purification indicated the presence of UTD-2 ~about 30~ and a second component, UTD-5. Most of the peaks of UTD-5 are broad. UTD-5 was isolated by sedimentation and~or centrifugation of the more dense layer.
W096/06042 219 7 4 S 4 PCT~S95ll0646 X-ray Pattern for UTD-5 as SYnthesized A # 2 theta d, A (rel.int., ~) 1 6.51 13.57 (24) S 2 10.89 8.12 il6) 3 12.31 7.18 (21) 4 12.92 6.85 (31 13.12 4.74 6 16.78 5.28 (55) 7 20.88 4.25 (100) 8 22.12 4.02 (71) 9 23.13 3.84 (25) 26.51 3.36 (24) 11 29.21 3.06 (31) 12 32.07 2.79 (20) X-ray Pattern for UTD-5 calcined at 500~C (dark qreen) # 2 theta d, A (rcl.int., %) 1 6.48 13.62 (92) 2 7.52 11.74 (46) 3 12.45 7.10 (42~
4 21.04 4.22 (96) 21.30 4.17 (100) 6 22.30 3.98 (62~
7 24.48 3.63 (33) 2~7~5~
WOsC106042 PC~/1199~10G46 This example illustrates the formation of a novel microcrystallir.e molecule sieve using bis(cyclopentadienyl)cobalt~III) ion as the template.
Pre~aration of ~TD-3-SAPo Mixture l was prepared as described in Example 2.
~is~cyclopentadienyl~cobalt~III) hydroxide (Cp2CoO:~) was used as a template in combination with.
tetrapropylammonium hydroxide ~TPAOH).
Mixture 2 was prepared by adding 0.Z56 g fumed silica to a mixturé of 0.354 g of a 31 wt~ Cp2CoOH solutior, ir.
water and 9.28 g of 40 wt~ tetrapropylammonium hydroxide.
The molar ratios were as follows:
Al2O3:P2O5:SiO2:~TPA)2O ~Cp2Co~2o H2o =
1:0.9:0.~:0.86:0.025:48. The crystallization and purification procedures were similar to those described in Example 2. The top and bottom layers ~white material~
were separated from the intermediate bright yellow fraction by sedimentation and~or centrifugation. The yellow fraction was isolated as UTD-3. The yellow sample turned sky-blue after calcination at 500~C. X-ray powder diffraction patterns for UTD-3 are shown in Table 5 for the synthesized compound and in Table 6 after calcination.
~ W096/06042 21 9745~ PCT~S9~110646 X-rav pattern for UTD-3 as svnthe~ized (vellow~
# 2 theta d, A (rel.int., ~) 1 8.588 10.288 (3) 2 10.898 8.112 (5) 3 15.936 5.557 (11) 4 17.279 5.128 (80) 17.694 5.001 (14) 6 20.805 4.266 (23) 7 21.919 4.052 (100) 8 23,278 3.818 (37) 9 24.790 3.589 (4) 26.g38 3.307 (6) 11 28.22~ 3.159 (20) 12 31.313 2.854 (4) 13 32.171 2.780 (24) 14 34.202 2.620 (14) 34.956 2.565 (8) 16 35.881 2.501 (5) ~o g~OC042 2 ~ g ~ ~ S 4 PCT~59~10~C
X-raY ~attern ~or UTD-3 cal~;n~A 550~~ (blue color) # 2 theta d, A (rel.ir.
1 8.639 10,277 ~15~
2 10.926 8.091 (49) 3 13.466 6.570 ~51) 4 15.903 5.568 (15) 17.2gZ 5.124 (78) 6 17.642 5.023 ~13) 7 20.832 4.261 (44) 8 21,946 5.254 ~100) 9 23.279 1.818 (31) 24,885 3.575 (13) 11 26,991 3.3Ql (15 12 28.226 3.159 ~20) 13 2~.316 3.044 (11~
14 32.229 2.775 ~24) 32.375 2.763 (25) 16 34.264 2.615 (13) 17 37.714 2.383 (11~
W096/060~2 ~i 9 ~S ~ PCT~S9~/1Oh46 UTD-3 can be prepared as a single phase from the gel c~nt~;n;ng Co2+ ions instead of silica and Cp2CoOH as the ~ only template.
s Svnthesis of UTD-3-CoAPO
3.4 g H20 and 3.10 g 85~ H3PO~ were mixed with 1.5 g CoS04 7H20 and stirred for thirty minutes. 2.0 g Al (OH)3 (83.34~ was slowly added to the solution and mixed for 1 hr. Then, 13.4 g of a 26.6~ Cp2CoOH solution was added to the mixture. The molar ratios were A1203:P205:CoO:(Cp2Co)20:H20 = 0.8:1:0.4:0.75:53. The gel was mixed for 4 hrs, and then placed in an oven at 200~C
for 19 hours. The dark blue-green product was a pure single phase. The x-ray pattern was similar to thas of UTD-3 shown in Table 5.
The compound described in the following example was prepared using two templates, one of which was Cp~2CoOH.
Pre~aration of UTD-6 ~rD-6 was prepared from silicoalum num phosphate gel using a Cp 2CoOH and tetrabutylammonium hydroxide (TBAOH~
as templates. The molar ratios were A1203:P205:SiO2:(TBA)20:H20 = 1:0.9:0.4:0.86:0.16:75.
~ixture 1 was prepared by slow addition of 2 g of aluminum hydroxide (Pfaltz & Bauer, LOT 039789, 83.34 wt ~ to a solution of 2.22 g 85 wt ~ H3PO4 (Fisher) and 2.0 g of deionized water with magnetic stirring. After addition of about 1.3 g of the hydroxide, the gel became extremely viscous and was stirred with a Teflon rod for l hour.
W09~i/060~ ~lg~ ~ 4 PCT~951~06 Mixture 2 was prepared by adding 0.256 g fumed silica (0.007 m, Aldrich~ to a mixture of 4.34 g of a 26.6 wt Cp ~CoO~ solution in water and 11.92 g of 40 wt~ T~3AOH
~obtained from Alfal. Mixture 2 was not viscous and S easily obtained homogeneity.
Mixture 2 was added slowly to mixture 1 and the final mixture was stirred for approximately 6 hrs in order to achieve a homogeneous gel. The gel was transferred into a 25 cm3 Teflon-lined pressure reactor (Parr) that was subsequently placed in an oven having a constant temperature of 200~C. After 20 hours heating at autogenous pressure, the mixture was cooled to room temperature and diluted with 100 m~ of deionlzed water.
The yellow product was isolated by filtration and washed with copious amounts of water.
X-rav pattern for ~TD-6 a~ 8YTl~he~ 7~
# 2 theta d, A~rel.int., %) 1 5.35 16.49 ~lOo) 2 6.44 13.72 ~61) 3 ll.sQ 7.43 (21~
4 17.49 5.07 (71) 19.77 4.45 (43) 6 29.03 3.07 (50) 7 30.91 2.89 (25) 8 35.30 2.54 (32) 9 35.74 2.51 (21~
35.81 2.50 (21) W096/U6U42 ~1 g 7 4 ~ ~ PCT~S95110646 ~rr -The following references to the extent that they provide exe~plary procedural or other details supplementary to those set forth herein are specifically incuL~orGted herein by reference.
K.J. Balkus, Jr. and S. Kowalak, U.S. Patent No.
5,167,942, 1992.
K.J. Balkus, Jr. and S. Shepelev, Nicropor. Mater., 1993A, 1, 383.
K.J. Balkus, Jr. and S. Shepelev, Petrol. Preprints, 1993B, 38, 512.
Behrens, P., et al. "Metal-Organic Compleses ans New Templates for the Synthesis of Clathrasils," 8th International Symposium, p. 53, 1994.
E.W. Valyecsik, U.S. Patent No. 4,568,654, 1986.
Valyecsik, E.W., U.S. Patent No. 4,556,549 (Decem~er 3, 1985).
U. Kolle and F. Khouzami, Chem. Ber., 1981, 114, 2529.
Balkus, K.J., Jr., Hargis, C.D. and Kowalak, S., ACS
Symp. Ser., 449, 348 (1992).
Szostak, R. n Molecular Sieves, Van Nostrand, New York, New York, p. 79, 84, 1989.
The present invention addresses problems inherent in the art by providing novel molecular sieve compounds and prc,cesses for producing the novel compounds. The present 3~ wor.k shows that certain metal complexes can be employed as templates or structure-directing agents. Several new molecular sieve compounds have been produced. The compounds are microcrystalline and microporous and incorporate the templating agent metal used in the formation of the compound.
~'096/060~2 ~ PCT~59.$ll0~6 In particular, bis(cyclopentadienyl) cobalt(III) ior (Cp2Co+), has been shown to be a template for synthesis of the aluminum phosphate molecular sieves exemplified by AlPO4-5 and AlPO4-lS. This is an unexpected finding to the extent that this metal complex will provide a ~ template for both channel ~AlPO4-5) and cage ~AlPO4-16) molecular sieves. The Cp2Co+ complex is relatively rigid, unlike many typical organic templates. This provides an opportunity to evaluate the effects of size, shape and symmetry on the structure directing properties of the complex by the modifying the Cp ring(s1 with different substituents.
Employing a fully methylated derivative, bis(pentamethylcyclopentadienyl) cobalt(III) ion (CP2 Co+), the inventor has produced five new molecular sieves. It is contemplated that other new molecular sieves can be produced by altering the template; for example, any combination of alkyl groups on the cyclopentane ring such as methyl, ethyl, propyl, etc. as well as various metal species such as Ni2+, Fe2+, and other Group ~III metal ions. Nevertheless, the properties of these templates would be expected to differ from the bis pentamethylcyclopentadienyl species employed in the present invention.
The different metal complexes so far studied have unique structure directing properties, such that bis(cyclopentadienyl)cobalt(III) ion does not promote formation of the same structures as bis (pentamethylcyclopentadienyl)cobalt(III) ion. This is li~ely due to the different features of each complex, including size, shape and charge distribution.
Overall, and in general, the invention discloses novel microcrystalline molecular sieves prepared from template directing metallo organic complexes. In WO~C1~6~42 2 ~ ~ 7 4 ~ ~ PCTlUSgS/10646 particular embodiments, a metal microcrystallire silica molecular sieve with a nominal pore diameter of at least 7.~ A is formed. Such silica molecular sieves incorporate the positively charged metal ion as a guest molecule. Among the unique 8tructures produced using the ~Cp2~2O+) ion is a microcrystalline silica molecular sieve characterized as a yellow crystalline producs, UTD-1. UTD-1 was prepared as a single phase product employing bis(pentamethylcyclopentadienylj cobalt(III~
ion as template. The crystalline ~aterial was formed from a gel containing sodium hydroxide, the organic metal template and fumed silica. UTD-1 is formed from a gel with the approximate molecular ratio of water to sio~ of about 60, sodium ion to SiO2 of about o.l, hydroxyl ion to silica SiO2 of about 0.2 and the bis(pentamethylcyclopentadienyl) cobalt~III) ion template ratio to sio2 of about 0.~. The x-ray diffraction powder patterns for the UTD-1 as synthesized and the calcined material indicate the uniqueness of the molecular sieve.
2s As expected, there is decomposition of the organic portion of the template after calcination at 500~ C. The o~erall structure, however, is quite stable. The bright yellow color of lJTD-1 indicates that the pentacyclodienyl metal ion complex is entrapped in the crystals as a guest molecule. The metal complex template is relatively large and is not remo~ed by either aqueous or organic extraction procedures. Channels or cages within the molecular complex therefore are at least as large as the Cp rings that measure approximately 7.2 A. UTD-l is also a relati~ely large pore material as suggested by the low angle reflections obtained on x-ray crystallographic measurement.
~hile UTD-1 is quite stable, there is an indication o' decomposition at approximately 350~ C. Calcination is accompar.ied by a change in color from yellow to pale green. It is likely that this change of color represents _ _ _ _ _ _ W096106042 ~ 4 ~ ~ PCT~S95/10646 decomposition of the organic portion of the metal complex with concomitant formation of metal oxide. There was no evidence of framework substitution by the cobalt durirg formation of the molecllar sieve.
Yet another embodiment of the present invention is illustrated in the formation of the molecular sieve UTD-2. This compound also incorporates Cp 2Co as a guest molecule but is different in structure in incorporating aluminum and phosphorous as part of the framework. UTD-2 is also obtained as a single phase product from a gel having molar ratios of 1:0.5:0.4:0.86:0.025:50 for the components A12O3:P2O5:SiO2:(TPA~zO:Cp 2Co)2O:H2O. Of course, these ratios may oe varied somewhat. The preferred Al2O3/SiO2 molar ratio is 2.5, although ranges as high as 4 or as low as 1 are also suitable. Using ratios outside of the range 4~2.5~1 typically results in an amorphous material. A convenient procedure for the preparation of UTD-2 and similar molecular sieves is to prepare two mixtures; mixture 1 from aluminum hydroxide and phosphoric acid and mixture 2 from silica, preferably fumed silica, CP~2Co~ hydroxide, and tetrapropylammonium hydroxide. Of course, one may vary not only the ratios but the type of quaternary ammonium compound employed;
for example, other tetra alkyl ammonium hydroxides.
UTD-2 is conveniently formed after mixing mixture 1 and mixture 2, heating for a period of time at approximately 200C C. cooling, dilutirg and separatins the crystalline mate-ial. UTD-2, like UTD-l, is yellow indicating inclusion of the metal template within the molecular sieve.
The novel compound UTD-2 may also be prepared using only Cp 2CoOH as template. The preserce of tetrapropyl ammonium hydroxide, however, appears to be conducive to obtaining better yields of UTD-2. When using only Cp~2CoOH as the template, gels with molar ratios of about W0'36/O~Z ~ 5 ~ ~CT~Sg~l~K46 _ Al2o3:p2os:sio2(cp 2Coj20:X2Q may be employed as preferred ratios. Variations of Al203~SiO2 ma~ be employed as pre~iously discussed, preferably in t.he range of 4~2.5~1. 9 A new component, UTD-5, also resulted from the single template synthetic procedure used to obtain UTD-2.
The new material UTD-5 was distinguishable from UT5-2 in its x-ray pattern as synthesized from the gel mixture and also after calc~nation at 500~ C. The unusual dark sreen color of the calclned UTD-5 suggested formation of cobalt oxide and/or possibly the free metal.
Yel another embodiment of the present inven~ion, t~e unsubstituted form of bis(cyclopentadienyl~ cobalt(III), was used as a template to form UTD-3/SAP0 compound. The cobalt ion template was used in combination with tetrapropylammonium hydroxide. This compound was prepared using procedures analogous to those used to prepare UTD-2 except that the second mixture incorporated Cp2CoOX rather than Cp 2CoOX. Preferred molar ratios for Al2O3 P20s:siO2:~TPA)2O:(CP2~o)2O:x2o were about 1:0.9:0.4:0.86:0.025:48. The new UTD-3 SAPO compound was yellow in color~ microcrystalline, and like the other compounds, changed color after calcination at 500~ C.
The new compound had a unique x-ray powder diffraction pattern. The calcined sample was a sky-blue color after heating for several hours at. 500~ C. UTD-3 could also be prepared as a s~ngle phase from the gel containing cobalt(II) ions instead of silica and Cp2CoO~ as the only tempiate. This UTD-3 compound is a modification of the UTD-3 to the extent that it is isolated as a dark blue-green product; ho~ever, it is single phase and has an x-ray diffra~tion pattern cubstantially the same as UTD-3.
UTD-3-CoAP0 is prepared by mixing phncrhnric acid, a cobalt salt, preferably cobalt sulfate, then adding aluminum hydroxide and the bis(cyclopentadienyl) ~ wo 96,~6042 ~ ~ ~ 7 ~ ~ ~ PCT~S~/10646 cobalt(III) hydroxide template, mix1ng the gel for several hours, e.g., approximately four hours, and then heating at about 200~ C for about a day, i.e., 18 to 24 ~ hours, to provide a single phase product. Preferred molar ratios for Al203:P2O5:CoO:(Cp2Co)2O:H2O are about 0.8:1:0.4:0.75:53. However, the ratios may employed within this general range to obtain UTD-3 CoAPO.
Yet another embodiment of the present invention UTD-6 may be prepared again employing the bis(pentamethylcyclopentadienyl~ cobalt(III~ template.
In a particular embodiment, UTD-6 was prepared using two templates, the bis(cyclopentadienyl) complex ar.d tetrabutylammonium hvdroxide. The compound was prepared from a silicoaluminum phosphate gel. The preferred component molar ratios were about 1:0.9:0.4:0.86:0.16:75 for Al203:P2O5:SiO2:(TBA)2O:H2O. UTD-6 was conveniently prepared by ~ ; ng two mixtures; the first containing aluminum hydroxide and phosphoric acid; and the second containing fumed silica and the two templates.
The five new molecular sieve compounds described above are illustrative of the types of new compounds that may be prepared using a metal organic complex. For the first time, the inventors have shown the structure directing properties of cobalticirium ion complexes and that have demonstrated molecular sieves can be formed without an organo cation. The present invention illustrates the general types of novel structures that may be produced in the presence of bis~pentamethylcyclopentadienyl) cobalt(III) ion as the template. It is possible that even larger pore materials may be produced by increasing the bulkiness of the complex cobalt(III) ion; for example, by appropriate substituer.t groups on the cyclopentane rings.
WOg6~0~4~ 21 g ~ ~ 5 4 PCT~S9~110646 -While the complete range of reactions and properties of the new microcrystalline metal molecular sieves has not been explored, it ls recognized that related compounds have been well utilized as catalysts. ~ore specifically, such compounds have been used in catalytic hydrofining, cracking, and as selecti~e adsorbants. Mar.y of these uses are described in more detail in U.S. Patent No. 4,g40,87l incorporated herein by reference where it is noted that in general silicon aluminum phosphate molecular sieves are similar to zeolite catalysts in several of their properties.
By analogy with the Cp~Co+/nonasil complexes, t.he new molecular sieves are expected to exhibit special ~5 optical effects that could be exploited in memory storage devices. Molecular sieves are increasingly being developed as sensors in semiconductor devices.
BRIEF DESCRIPTION OE ~E DRAWINGS
2~
FIG. lA. Powder x-ray diffraction pattern of UTD-l as synthesized.
FI5. lB Powder x-ray diffraction pattern of UTB-l after Z5 calcination (500~C, 4 hr) samples. CaF2 was used as an internal standard.
FIC-. Z. Scarnln5 electron micrograph of UTD-l.
~0 FIG. 3A. FT-IR spectra for UTD-l as synthesized. Sample prepared as KBr pellet.
FIG. 3B. FT-IR spectrum for UTD-l after calcination ~500~C, Sample prepared as KBr pellet.~5 W096/06042 ~1~ 7 ~ ~ ~ PCT~S95/l0646 DETAI~ED DESCRIPTION OF THE ~K~'~KK~ EMsODrMENTS
The templating ability of metallocenes in the synthesis of crystalllne microporous metal oxides is the general focus of the present invention. The inventors have prepared and characterized a series of novel silica type molecular sieves, desigr.ated as "~T~" compounds.
The novel structures are produced in the presence of bis(pentamethylcyclopentadienyl~cobalt(III) ion, Cp 2Co+, as the template. Since the less bulky Cp2Co+ appeared to favor formation of the smaller pore clathrate type molecular sieves, the inventors have reasoned that addition of methyl groups to the cyclopentadienyl rings will encourage the crystallization of larger pore materials.
It is known that the crystallization of zeolite molecular sieves in the presence of metal chelates may result in encapsulation of the complexes ~U.S. Patent No.
5,167,942). This is a viable method for the preparation of zeolite ship-in-a-bottle complexes ~salkus and Gabrielov, 1994); however, the metal complex may also serve as a structure directing agent. The formation of many molecular sieves depends on the presence of template molecules that affect the gel chemistry and/or act as a void filler.
Most of the templates that have been evaluated for molecular sieve synthesis are based on organic molecules, especially aliphatic amines. By comparison, the structure directing properties of metal complexes are virtually unknown. Cobalticir.ium ion, Cp2Co~, has been shown to be a template for the clathrate type molecular sieves Nonasil and ZSM-51 (Balkus and Shepelev, 1993;
Balkus and Shepelev, 1993B; U.S. Patent No. 4,568,564).
More recently, wor.k in the inventors~ laboratory showed that Cp2CoOH acts as a template for the production of Wog~ 2 ~ 7 ~ ~ 4 PCT/US9~l~
- ~10 -AlPO4-16 and SAPO-16. Molecular sieves of this type had previously required an organo-cation to form and, specifically in the case of AlPO4-1~ or SAPO-i6, only quinuclidene was known to generate this topology.
s The following examples are provided for purposes of clarification and should not be considered as iimitir,g.
One skilled in the art would recognize in light of the pre.sent disclosure that although the specified materials and conditions are important in practicing the invention, unspecified materials and conditions are not excluded as long as they do not prevent the benefits of the invention from being realized.
EXAMP~3 1 This example illustrates the preparation of an all-silica molecular sieve using a bis~pentamethylcyclopentadienyl~cobalt(III) ion as a template. The microcrystalline silica molecular sieve incorporates the complexed cobalt ion, apparently as a guest molecule.
Preparation of U~D-1 The metal complex Cp~zCoPF~ was prepared ~ocording to the literature procedure (Kolle and Khouzami, 1581).
The complex was converted to the chloride derivative over Dowex-50W cation exchange resin by first adsorbing the Cp 2Co+ ion followed by ell~tion with lM HC1. The Cp~CoCl was then transformed to the hydroxide form over an aqueous slurry of silver oxide at 70C. The concentration of the brown Cp 2CoOX solution was determined by potentiometric titration. The solution was then used in the molecular sieve synthesis.
~ W096/06042 21 ~ 4 PCT~S9~/10646 UTD-l was prepared as a single phase product by combining NaOH, a 31.6~ a~ueous Cp~2CoO~ solution and fumed silica to form a gel with the following molar ratios.
H2~/Si~2 60 Na+/SiO2 0.1 OH-/SiO2 0.2 Cp~2Co+/SiO2 ~ . 1 The gel was aged with stirring for 1 hour and then transferred to a 23 mL Teflon-lined pressure reactor (Parr). The reactor was heated at 175~C under static conditions for 2 days. The resulting yellow crystalline produce was washed with deionized water, suction filtered and then dried at 90~C for 2 hours.
FIG. lA shows the X-ray diffraction ~XRD) powder pattern data for UTD-l as synthesized. FIG. lB shows the XRD of calcined UTD-l. Although there are changes in peak intensity after calcination at 500~C and decomposition of the tempiate occurs, the structure appears quite st.able. FIG. 2 shows the bundles of recsangular shaped crystals obtained after synthesis.
These results support a single phase material. The bright yellow color of UTD-l indicated that the Cp 2Co+
template was entrapped in the crystals as a guess molecule. The metal complex cannot be removed by aqueous or organic extraction. This implied that the channels or cages were at least as large as the Cp~ rings (7.2 A) in order to accommodate the complexes. The low angle reflections in ~IG. lA and FIG. lB also suggested a large pore material. Additionally, preliminary adsorption experiments using calcined UTD-l indicated a -20~ by weight increase upon exposure to cyclohexane (kinetic diameter 6.0 A). Pore size determination by more direct adsorption methods is complicated by the occluded cobalt species.
W(~96/Obll42 213 7 4 ~ 4 Pcrlu8~s~l0~
- i2 -TA'3LE lA
~ d s~acinc (A) and relative intensit~ for ~TD-1 a~
svnthesized:
14.686 (4B), llwas.742 (44), 8.068 (6), 5 512 (23~, 6.058 (53), 5.872 (8), 6.459 ~50), 5.911 (50', 4.365 (10), 5.443 (100), 4.~31 (57), 3.946 ~25), 3.913 (15j, 3.829 (5), 3.710 (5), 3.668 (41), 3.611 (34), 3.448 (4), 3.390 (23), 3.206 ~5~, 3.084 ~11), 3.006 (23), 2.79g (8), 2.763 (18), 2.738 (3), 2.637 (4), 2.509 (4), 2.489 (3), 2.445 (7), 2.406 (3), TABLE lB
Calcined at 500~C
calcined (500 C): 14.609 (lO0), 11.50g (64), g.466 ~6), 6.094 (10), 4.8~32 (13), 4.478 (23), 4.384 (7), 4.211 (45)l 4.049 (10), 3.955 (6), 3.843 (5)l 3.735 (2), 3.659 (17~, 3.560 ~14~, 3.400 (9), 3.066 (3), 2.986 (5), 2.769 (6), 2.646 (1), 2.553 (1), 2.466 (1), 2.436 (2), 2.374 (2).
There was no evidence of complex decomposition durin~ synthesis from spectroscopic analysis o~
encapsulated and free complexes. The W-Vis spectrum of a UTD-1 nujol mull was broadened and slightly red shifted (~15 nm) compared to an aqueous solution of Cp ~CoOH
(290, 338sh, 406sh nm). However, this shift to lower energy was also noted for Cp2Co+ in Nonasil and AlPO4_5 molecular sieves (Balkus and Shepelev, 1993A).
Thermogravimetric analysis (TG) of Cp 2CoPF6 indicated the onset of decomposition at -350~C, which is significantly higher than the UTD-1 synthesis temperature (175~C). Similarly, UTD-1 begins to lose weight at ~350~C with a change in color from yellow to pale green.
~'096/06042 ~l~ 7 4 ~ A PCT~9511U646 measured up to 900~C. The small change is consistent with loss of the organics and probable formation of occluded oxides.
There was no evidence of framework substitution by cobalt. The FT-IR spectrum of UT~-1 also indicated the presence of intact Cp 2Co+ as evidenced by the uc~ at 2915 cm~1 that can be compared to the free Cp*2CoPF6 complex with a C-~ band at 2920 cm~l. Similarly, a C-C stretch iO at 1476 cm~1 for the free complex appeared at 1480 cm~1 in UTD-1. There were a variety of other bands that might be ascribed to the encapsulated metal complex; however, they were either masked by the bands associated with the mojlecular sieve or were quite weak.
FIG. 3A shows the FT-IR spectrum in the region 1500-400 cm~1 for UT~-1 as synthesized. FIG. 3B shows the FT-IR spectrum after calcination at 500~C. There are two strong bands at 1237 and 1092 cm~l that are typical of the asymmetric Si-O stretches observed for crystalline silicates. There are no significant shifts for these bands after calcinationj however, two shoulders are resolved at 1140 and io76 cm~1. The bands that appear in the symmetric stretching region ~812, 787, 642 cm~1), as well as the more .structure sensitive region (612, 582 and 537 cm~1), appear quite different from known silicate phases.
The results indicate that an all-silica phase UTD-1 can be synthesized using the metal complex Cp~2CoO~ as a template that becomes incorporated as a guest molecule.
The data indicate that UTD-1 is a large pore material l~7 A) Wo ~106042 2 1 ~ 7 ~ ~ PCT~S~.~110646 Another new molecular sieve was prepared as illustrated in the following example. ~his compound/
like UTD-1, also incorporates the template Cp 2Co+ as a guest molecule but differs in including aluminum ard phosphorus as part of the framework.
Preparation of UTD-2 UTD-2 was obtained as a single phase product from a gel having molar ratios Al2o3:P2O5:SiO2:(TPAl2O:(CP 2co~2o H2o ~
1:0.9:0.4:0.86:0.025:50. The preferred A12O3/SiO2 molar ratio is 2.5. Taking the Al2O3/SiO2 ratios out of the range 4~2.5>1 may result in an amorphous material. The procedure involves first preparing two mixtures as follows.
Mixture 1 was prepared by slowly adding 2 g of aluminum hydroxide (Pfaltz & Bauer, LOT 039789, 83.34 wt~j to a solution of 2.22 g 35 wt% H3PO4 (Fisher~ and 2.0 g of deionized water with magnetic stirring. After adding about 1.3 g of the hydroxide, the gel became extremely viscous and was stirred with a Teflon rod for 1 hour.
Mixture 2 was prepared by adding 0.256 g fumed silica (0.007 ~, Aldrich) to a mixture of 0.58 g of a 30 wt~ Cp 2CoOH solution in water and 9.28 g of 40 wt~
tetrapropylammonium hydroxide iTPAOH~ obtained from Alfa~
Mixture 2 was not viscous and easily obtained homogeneity.
Mixture 2 was added slowly to mixture 1 and the final mixture was stirred for approximately 6 hours in order to achieve a homogeneous gel. The gel was -~ W096/OC042 2 ~ ~ 7 4 5 ~ PCT~595llU646 transferred into a 25 cm3 Teflon-lined pressure reactor (Parr) that was subsequently placed in an oven ha~ing a constant temperature of 200~C. After 20 hrs heating at ~ autogenous pressure, the mixture was cooled to room temperature and diluted with 100 mL of deionized water.
~ The bright yellow crystals were separated from a white amorphous material by centrifugation and/or sedimentation, washed with deionized water and isolated by filtering through a nitrocellulose membrane (2 ~mj under suction. The solid yellow residue was dried at room temperature for 24 hrs. UTD-2 appeared on SEM
images as a single phase.
X-rav ~ttern for UTD-2 a sYnthesized # 2 theta d, A (rel.int., ~) 1. 6.270 14.085 ~100) 2. 11.307 7.819 (4) 3 11.720 7.545 (3) 4. 12.542 7.052 (g) 5. 18.844 4.705 (27) 6. 19.272 4.602 (50) 7. 20.267 4.378 (23) 8. 23.014 3.8~1 (2) 9. 25.215 3.529 (61) lO. 27.062 4.274 (6) 11. 31.903 2.893 ~3~
12. 33.695 2.658 (12) - 13. 34.283 3.393 (7) 14. 36.014 2.492 (11 15. 38.165 2.356 (1) ~09~l06042 2 1 ~ 7 4~ ~ PCT~S9~tO6~6 EXhNPL~ 3 UTD-2 could be also obtained using only Cp~2CoOH as template, as sho~r. in the following example.
Sinqle Tem~lste SYnthesis of UTD-2 The single template synthesis of UTD-2 was sub~stantially the same as that described in Example 2 except that mixture 2 was prepared by adding 0.256 g fumed silica to 7.76 g of a 30 wt% Cp~2CoO~ solution in water. The final gel had molar ratios A1203:P205:
SiO2:iCp 2Co)20:~20 - 1:0.9:0.4:0.32:50. The x-ray pattern of the yellow sample obtained after crystalli~ation and purification indicated the presence of UTD-2 ~about 30~ and a second component, UTD-5. Most of the peaks of UTD-5 are broad. UTD-5 was isolated by sedimentation and~or centrifugation of the more dense layer.
W096/06042 219 7 4 S 4 PCT~S95ll0646 X-ray Pattern for UTD-5 as SYnthesized A # 2 theta d, A (rel.int., ~) 1 6.51 13.57 (24) S 2 10.89 8.12 il6) 3 12.31 7.18 (21) 4 12.92 6.85 (31 13.12 4.74 6 16.78 5.28 (55) 7 20.88 4.25 (100) 8 22.12 4.02 (71) 9 23.13 3.84 (25) 26.51 3.36 (24) 11 29.21 3.06 (31) 12 32.07 2.79 (20) X-ray Pattern for UTD-5 calcined at 500~C (dark qreen) # 2 theta d, A (rcl.int., %) 1 6.48 13.62 (92) 2 7.52 11.74 (46) 3 12.45 7.10 (42~
4 21.04 4.22 (96) 21.30 4.17 (100) 6 22.30 3.98 (62~
7 24.48 3.63 (33) 2~7~5~
WOsC106042 PC~/1199~10G46 This example illustrates the formation of a novel microcrystallir.e molecule sieve using bis(cyclopentadienyl)cobalt~III) ion as the template.
Pre~aration of ~TD-3-SAPo Mixture l was prepared as described in Example 2.
~is~cyclopentadienyl~cobalt~III) hydroxide (Cp2CoO:~) was used as a template in combination with.
tetrapropylammonium hydroxide ~TPAOH).
Mixture 2 was prepared by adding 0.Z56 g fumed silica to a mixturé of 0.354 g of a 31 wt~ Cp2CoOH solutior, ir.
water and 9.28 g of 40 wt~ tetrapropylammonium hydroxide.
The molar ratios were as follows:
Al2O3:P2O5:SiO2:~TPA)2O ~Cp2Co~2o H2o =
1:0.9:0.~:0.86:0.025:48. The crystallization and purification procedures were similar to those described in Example 2. The top and bottom layers ~white material~
were separated from the intermediate bright yellow fraction by sedimentation and~or centrifugation. The yellow fraction was isolated as UTD-3. The yellow sample turned sky-blue after calcination at 500~C. X-ray powder diffraction patterns for UTD-3 are shown in Table 5 for the synthesized compound and in Table 6 after calcination.
~ W096/06042 21 9745~ PCT~S9~110646 X-rav pattern for UTD-3 as svnthe~ized (vellow~
# 2 theta d, A (rel.int., ~) 1 8.588 10.288 (3) 2 10.898 8.112 (5) 3 15.936 5.557 (11) 4 17.279 5.128 (80) 17.694 5.001 (14) 6 20.805 4.266 (23) 7 21.919 4.052 (100) 8 23,278 3.818 (37) 9 24.790 3.589 (4) 26.g38 3.307 (6) 11 28.22~ 3.159 (20) 12 31.313 2.854 (4) 13 32.171 2.780 (24) 14 34.202 2.620 (14) 34.956 2.565 (8) 16 35.881 2.501 (5) ~o g~OC042 2 ~ g ~ ~ S 4 PCT~59~10~C
X-raY ~attern ~or UTD-3 cal~;n~A 550~~ (blue color) # 2 theta d, A (rel.ir.
1 8.639 10,277 ~15~
2 10.926 8.091 (49) 3 13.466 6.570 ~51) 4 15.903 5.568 (15) 17.2gZ 5.124 (78) 6 17.642 5.023 ~13) 7 20.832 4.261 (44) 8 21,946 5.254 ~100) 9 23.279 1.818 (31) 24,885 3.575 (13) 11 26,991 3.3Ql (15 12 28.226 3.159 ~20) 13 2~.316 3.044 (11~
14 32.229 2.775 ~24) 32.375 2.763 (25) 16 34.264 2.615 (13) 17 37.714 2.383 (11~
W096/060~2 ~i 9 ~S ~ PCT~S9~/1Oh46 UTD-3 can be prepared as a single phase from the gel c~nt~;n;ng Co2+ ions instead of silica and Cp2CoOH as the ~ only template.
s Svnthesis of UTD-3-CoAPO
3.4 g H20 and 3.10 g 85~ H3PO~ were mixed with 1.5 g CoS04 7H20 and stirred for thirty minutes. 2.0 g Al (OH)3 (83.34~ was slowly added to the solution and mixed for 1 hr. Then, 13.4 g of a 26.6~ Cp2CoOH solution was added to the mixture. The molar ratios were A1203:P205:CoO:(Cp2Co)20:H20 = 0.8:1:0.4:0.75:53. The gel was mixed for 4 hrs, and then placed in an oven at 200~C
for 19 hours. The dark blue-green product was a pure single phase. The x-ray pattern was similar to thas of UTD-3 shown in Table 5.
The compound described in the following example was prepared using two templates, one of which was Cp~2CoOH.
Pre~aration of UTD-6 ~rD-6 was prepared from silicoalum num phosphate gel using a Cp 2CoOH and tetrabutylammonium hydroxide (TBAOH~
as templates. The molar ratios were A1203:P205:SiO2:(TBA)20:H20 = 1:0.9:0.4:0.86:0.16:75.
~ixture 1 was prepared by slow addition of 2 g of aluminum hydroxide (Pfaltz & Bauer, LOT 039789, 83.34 wt ~ to a solution of 2.22 g 85 wt ~ H3PO4 (Fisher) and 2.0 g of deionized water with magnetic stirring. After addition of about 1.3 g of the hydroxide, the gel became extremely viscous and was stirred with a Teflon rod for l hour.
W09~i/060~ ~lg~ ~ 4 PCT~951~06 Mixture 2 was prepared by adding 0.256 g fumed silica (0.007 m, Aldrich~ to a mixture of 4.34 g of a 26.6 wt Cp ~CoO~ solution in water and 11.92 g of 40 wt~ T~3AOH
~obtained from Alfal. Mixture 2 was not viscous and S easily obtained homogeneity.
Mixture 2 was added slowly to mixture 1 and the final mixture was stirred for approximately 6 hrs in order to achieve a homogeneous gel. The gel was transferred into a 25 cm3 Teflon-lined pressure reactor (Parr) that was subsequently placed in an oven having a constant temperature of 200~C. After 20 hours heating at autogenous pressure, the mixture was cooled to room temperature and diluted with 100 m~ of deionlzed water.
The yellow product was isolated by filtration and washed with copious amounts of water.
X-rav pattern for ~TD-6 a~ 8YTl~he~ 7~
# 2 theta d, A~rel.int., %) 1 5.35 16.49 ~lOo) 2 6.44 13.72 ~61) 3 ll.sQ 7.43 (21~
4 17.49 5.07 (71) 19.77 4.45 (43) 6 29.03 3.07 (50) 7 30.91 2.89 (25) 8 35.30 2.54 (32) 9 35.74 2.51 (21~
35.81 2.50 (21) W096/U6U42 ~1 g 7 4 ~ ~ PCT~S95110646 ~rr -The following references to the extent that they provide exe~plary procedural or other details supplementary to those set forth herein are specifically incuL~orGted herein by reference.
K.J. Balkus, Jr. and S. Kowalak, U.S. Patent No.
5,167,942, 1992.
K.J. Balkus, Jr. and S. Shepelev, Nicropor. Mater., 1993A, 1, 383.
K.J. Balkus, Jr. and S. Shepelev, Petrol. Preprints, 1993B, 38, 512.
Behrens, P., et al. "Metal-Organic Compleses ans New Templates for the Synthesis of Clathrasils," 8th International Symposium, p. 53, 1994.
E.W. Valyecsik, U.S. Patent No. 4,568,654, 1986.
Valyecsik, E.W., U.S. Patent No. 4,556,549 (Decem~er 3, 1985).
U. Kolle and F. Khouzami, Chem. Ber., 1981, 114, 2529.
Balkus, K.J., Jr., Hargis, C.D. and Kowalak, S., ACS
Symp. Ser., 449, 348 (1992).
Szostak, R. n Molecular Sieves, Van Nostrand, New York, New York, p. 79, 84, 1989.
Claims (21)
1. A metal microcrystalline silica molecular sieve having a nominal pore diameter greater than about 7.2 .ANG.
that incorporates a cobalticinium ion as a guest molecule.
that incorporates a cobalticinium ion as a guest molecule.
2. The metal microcrystalline silica molecular sieve of claim 1 that is prepared from a gel having the molar ratios:
(a) about 60 for H2O/SiO2;
(b) about 0.1 for Na+/SiO2;
(c) about 0.2 for OH-/SiO2;
(d) about 0.1 for Cp2Co+/SiO2 wherein Cp2Co+ is bis(pentamethylcyclopentadienyl) Cobalt III ion.
(a) about 60 for H2O/SiO2;
(b) about 0.1 for Na+/SiO2;
(c) about 0.2 for OH-/SiO2;
(d) about 0.1 for Cp2Co+/SiO2 wherein Cp2Co+ is bis(pentamethylcyclopentadienyl) Cobalt III ion.
3. The metal microcrystalline silica molecular sieve of claim 1 that as synthesized has an X-ray powder diffraction pattern that includes at least the lines as set forth in Table 1A.
4. The metal microcrystalline silica molecular sieve of claim 1 that after calcination has at least an x-ray powder diffraction pattern that includes at least the lines as set forth in Table 1B.
5. A metal microcrystalline silicoaluminophosphate molecular sieve having a nominal pore diameter greater than about 7.2 Ä and having a ratio of Al2O3/SiO2 in the range of 4>2.5>1 that is prepared from a gel that incorporates a cobalticinium ion as a guest molecule.
6. The metal microcrystalline silicoaluminophosphate molecular sieve of claim 5 wherein the Al2O3/SiO2 ratio is about 2.5.
7. The metal microcrystalline silicoaluminophosphate molecular sieve of claim 5 wherein said compound is prepared from a gel having the composition Al2O3:P2O5:SiO2: (TPA)2O: (Cp*2Co)2O:H2O wherein Cp*2Co is bis(pentamethylcyclopentadienyl) cobalt(III) ion and TPA
is tetrapropylammonium ion.
is tetrapropylammonium ion.
8. The metal microcrystalline silica molecular sieve of claim 7 wherein the gel composition ratio of Al2O3:P2O5:SiO2:(TPA)2O:(Cp*2Co)2:H2O is about 1:0.9:0.4:0.86:0.025:50.
9. The microcrystalline silicoaluminophosphate molecular sieve of claim 5 that has an X-ray powder diffraction pattern that includes at least the lines set forth in Table 2.
10. The metal microcrystalline silicoaluminophosphate molecular sieve of claim 5 that is prepared from a gel with a Al2O3:P2O5:SiO2:(Cp*2Co)2O:H2O composition where (Cp*2Co)2 is bis(pentamethylcyclopentadienyl) cobalt(III) ion.
11. The metal microcrystalline silica molecular sieve of claim 10 wherein the molar ratio of Al2O3:P2O5:SiO2:(Cp*2Co)2O:H2O is 1:0.9:0.4:0.32:50.
12. A microcrystalline silicoaluminophosphate molecular sieve prepared from a gel wherein the molar ratio of Al2O3:P2O5:SiO2:(TPA)2O:(CP2Co)2:H2O is about bis(cyclopentadienyl) cobalt(III) ion and TPA is tetrapropylammonium ion.
13. The microcrystalline silicoaluminophosphate molecular sieve of claim 12 as synthesized that has an X-ray powder diffraction pattern that includes at least the lines set forth in Table 5.
14. The microcrystalline silicoaluminophosphate molecular sieve of claim 12 that after calcination has an X-ray powder diffraction that includes at least the lines set forth in Table 611.
15. A microcrystalline silicoaluminum phosphate molecular sieve that is prepared from a gel having a molar ratio of Al2O3:P2O5:CoO:(Cp2Co)2O:H2O equal to about 0.8:1:0.4:0.75:53 wherein (Cp2Co)2 is bis(cyclopentadienyl) cobalt(III) ion that is included within the molecular sieve.
16. The metal microcrystalline silica molecular sieve of claim 11 that has a yellow color and an X-ray powder diffraction pattern as synthesized exhibiting at least the lines set forth in Table 3.
17. The metal microcrystalline silica molecular sieve of claim 11 that has the X-ray diffraction pattern after calcination exhibiting at least the lines set forth in Table 4 and a dark green color.
18. The metal microcrystalline silica molecular sieve of claim 1 wherein the molar ratio of Al2O3:P2O5:SiO2:(TBA)2O:(Cp2Co)2O:H2O is 1:0.9:0.4:0.86:0.16:75 where TBA is tetrabutylammonium ion and (Cp2Co)2 is bis(pentamethylcyclopentadienyl) cobalt(III) ion.
19. The metal microcrystalline silica molecular sieve of claim 18 that as has an X-ray powder diffraction pattern that includes at least the lines set forth in Table 7.
20. A process for the synthesis of a metal microcrystalline molecular sieve having a nominal pore size of at least 7.2 Ä comprising admixing a bis(pentamethylcyclopentadienyl) cobalt(III) salt with appropriate amounts of components selected from the group consisting essentially of an aluminum salt, a silicon oxide, a phosphorus oxide and an ammonium salt to form a cobalticinium enclosed molecular sieve.
21. A process for the synthesis of a metal microcrystalline molecular sieve comprising admixing a bis(cyclopentadienyl) cobalt(III) salt with components selected from the group consisting essentially of an aluminum salt, a silicon oxide, a phosphorus oxide and an ammonium salt to form a cobalticinium enclosed molecular sieve.
Applications Claiming Priority (2)
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|---|---|---|---|
| US08/296,488 | 1994-08-24 | ||
| US08/296,488 US5489424A (en) | 1994-08-24 | 1994-08-24 | Synthesis of novel molecular sieves using a metal complex as a template |
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| US (3) | US5489424A (en) |
| EP (1) | EP0777627B1 (en) |
| JP (1) | JPH10507730A (en) |
| AU (2) | AU688579B2 (en) |
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| US5830429A (en) * | 1996-02-06 | 1998-11-03 | Board Of Regents, The University Of Texas System | Metal silicate compositions and catalysts |
| US6103215A (en) * | 1996-06-07 | 2000-08-15 | Chevron U.S.A. Inc. | Zeolite Me-UTD-1 |
| US6306362B1 (en) | 1996-06-26 | 2001-10-23 | Exxonmobil Oil Corporation | Aluminosilicate molecular sieve |
| WO1998056718A1 (en) * | 1997-06-12 | 1998-12-17 | Shell Internationale Research Maatschappij B.V. | Aluminosilicate of utd-1 structure type |
| JP4168214B2 (en) | 1998-10-15 | 2008-10-22 | 三菱瓦斯化学株式会社 | Methylamine production catalyst and method for producing the catalyst |
| JP4745523B2 (en) * | 2000-04-13 | 2011-08-10 | エヌ・イーケムキャット株式会社 | Structure directing agent for the synthesis of crystalline oxides |
| US6468501B1 (en) | 2000-09-14 | 2002-10-22 | Chevrontexaco Corporation | Method for heteroatom lattice substitution in large and extra-large pore borosilicate zeolites |
| US6620401B1 (en) * | 2001-07-13 | 2003-09-16 | Chevron U.S.A. Inc. | Zeolite SSZ-60 composition of matter and synthesis thereof |
| US6464956B1 (en) * | 2001-07-13 | 2002-10-15 | Chevron U.S.A. Inc. | Zeolite SSZ-59 composition of matter and synthesis thereof |
| WO2003006364A2 (en) * | 2001-07-13 | 2003-01-23 | Chevron U.S.A. Inc. | Zeolite ssz-59 |
| JP4477871B2 (en) * | 2001-07-13 | 2010-06-09 | シェブロン ユー．エス．エー． インコーポレイテッド | Zeolite SSZ-60 |
| US7578993B2 (en) * | 2003-10-31 | 2009-08-25 | Uop Llc | Process for preparing crystalline aluminosilicate compositions using charge density matching |
| US20080170986A1 (en) * | 2004-08-09 | 2008-07-17 | Hideki Kitamura | Zeolite Including Oxygen-Activated Metal Complex And Gas Decomposition Agent |
| CN1295149C (en) * | 2004-12-01 | 2007-01-17 | 长春理工大学 | MCM-41 molecular sieve and titanium nanometer composite material, preparation thereof |
| DE102007063604A1 (en) | 2007-05-24 | 2008-12-04 | Süd-Chemie AG | Metal-doped zeolite and process for its preparation |
| DE102007024125A1 (en) * | 2007-05-24 | 2008-11-27 | Süd-Chemie AG | Metal-doped zeolite for use as catalyst material for use in cleaning of exhaust gases, particularly for reduction of nitrogen oxides, has doping metal, which is present in zeolites as monomeric or dimeric species |
| DE102009034850A1 (en) * | 2009-07-27 | 2011-02-10 | Süd-Chemie AG | Process for the preparation of a silico-aluminophosphate |
| WO2020072157A1 (en) * | 2018-10-05 | 2020-04-09 | Exxonmobil Research And Engineering Company | Zeolite syntheses and directing agents |
| JP2023551057A (en) | 2020-11-26 | 2023-12-06 | 安徽▲澤▼欧新材料技▲術▼有限公司 | Supermacroporous ZEO-1 molecular sieve, its synthesis method and its use |
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| US4100262A (en) * | 1977-08-15 | 1978-07-11 | Mobil Oil Corporation | Synthesis of zeolite ZSM-5 |
| US4310440A (en) * | 1980-07-07 | 1982-01-12 | Union Carbide Corporation | Crystalline metallophosphate compositions |
| EP0125355B1 (en) * | 1981-11-12 | 1987-07-08 | Mobil Oil Corporation | Process for the preparation of zsm-5 or mordenite utilizing transition metal complexes during crystallization |
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| US5334367A (en) * | 1982-09-27 | 1994-08-02 | Mobil Oil Corp. | Zeolite ZSM-45 |
| US4568654A (en) * | 1982-11-03 | 1986-02-04 | Mobil Oil Corporation | Zeolite ZSM-51 composition |
| US4556549A (en) * | 1983-11-29 | 1985-12-03 | Mobil Oil Corporation | Process for making zeolite ZSM-45 with an organocobalt complex |
| US4744970A (en) * | 1984-04-13 | 1988-05-17 | Union Carbide Corporation | Cobalt-aluminum-phosphorus-silicon-oxide molecular sieves |
| US5106801A (en) * | 1988-10-20 | 1992-04-21 | Chevron Research And Technology Company | Zeolite SSZ-31 |
| US5091073A (en) * | 1990-07-13 | 1992-02-25 | Mobil Oil Corp. | Crystalline molecular sieve compositions mcm-37 |
| US5167942A (en) * | 1990-11-21 | 1992-12-01 | Board Of Regents, The University Of Texas System | Methods for the preparation of molecular sieves, including zeolites, using metal chelate complexes |
| US5094828A (en) * | 1990-12-31 | 1992-03-10 | Mobil Oil Corporation | Synthesis of large-pore |
| US5316753A (en) * | 1992-10-09 | 1994-05-31 | Chevron Research And Technology Company | Zeolite SSZ-35 |
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| AU7007798A (en) | 1998-08-13 |
| US5648058A (en) | 1997-07-15 |
| EP0777627B1 (en) | 2000-05-03 |
| US5489424A (en) | 1996-02-06 |
| JPH10507730A (en) | 1998-07-28 |
| AU688579B2 (en) | 1998-03-12 |
| DE69516698D1 (en) | 2000-06-08 |
| EP0777627A1 (en) | 1997-06-11 |
| AU3410995A (en) | 1996-03-14 |
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