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WO1990011827A1 - Procede d'intercalation de chalcogenure metallique en couches a gonflement organique, avec un chalcogenure polymere, par des traitements multiples a l'aide d'un precurseur de chalcogenure polymere - Google Patents

Procede d'intercalation de chalcogenure metallique en couches a gonflement organique, avec un chalcogenure polymere, par des traitements multiples a l'aide d'un precurseur de chalcogenure polymere Download PDF

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Publication number
WO1990011827A1
WO1990011827A1 PCT/US1989/001571 US8901571W WO9011827A1 WO 1990011827 A1 WO1990011827 A1 WO 1990011827A1 US 8901571 W US8901571 W US 8901571W WO 9011827 A1 WO9011827 A1 WO 9011827A1
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WO
WIPO (PCT)
Prior art keywords
chalcogenide
polymeric
layered
layered metal
organic
Prior art date
Application number
PCT/US1989/001571
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English (en)
Inventor
Brent Allen Aufdembrink
Original Assignee
Mobil Oil Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to JP50007489A priority Critical patent/JPH03505445A/ja
Priority to PCT/US1989/001571 priority patent/WO1990011827A1/fr
Priority to EP19890910745 priority patent/EP0419581A4/en
Publication of WO1990011827A1 publication Critical patent/WO1990011827A1/fr
Priority to DK294890A priority patent/DK294890D0/da

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/049—Pillared clays

Definitions

  • the present invention relates to a method for preparing layered metal chalcogenides containing interspathic polymeric chalcogenides .
  • the invention relates to layered metal oxides which contain interspathic metal oxides , e .g . , layered titanium oxides which contain interspathic silica.
  • interspathic metal oxides e .g .
  • titanium oxides which contain interspathic silica.
  • the term "metal" can be considered to include the elements boron, silicon, phosphorus and arsenic.
  • three-dimensional solid is formed by stacking such planes on top of each other.
  • the interactions between the planes are weaker than the chemical bonds holding an individual plane together.
  • the weaker bonds generally arise from interlayer attractions such as Van der Waals forces, electrostatic interactions , and hydrogen bonding .
  • the layered structure has electronically neutral sheets interacting with each other solely through Van der
  • a high degree of lubricity is manifested as the planes slide across each other without encountering the energy barriers that arise with strong interlayer bonding .
  • Graphite is an example of such a material.
  • the silicate layers of a number of clay materials are held together by electrostatic attraction mediated by ions located between the layers.
  • hydrogen bonding interactions can occur directly between complementary sites on adjacent layers , or can be mediated by interlamellar bridging molecules .
  • Laminated materials such as clays may be modified to increase their surface area. In particular, the distance between the interlamellar layers can be increased substantially by
  • the extent of interlayer separation can be estimated by using standard techniques such as X-ray diffraction to determine the basal spacing, also known as “repeat distance” or “d-spacing".
  • the interlayer spacing can be determined by subtracting the layer thickness from the basal spacing .
  • Layered metal chalcogenide materials enjoying thermal stability can be prepared by a method described in Biropean Patent Application 0 205 711, published 30 December 1986.
  • the method comprises: treating a layered chalcogenide , e.g . , oxide , of at least one element having an atomic number of 4 , 5 , 12 to 15 , 20 to 33 , 38 to 51 , 56 to 83 and greater than 90 , inclusive, which contains ion exchange sites having interspathic cations associated therewith, with an organic compound which is a cationic species, e.g . , n-alkylammonium or capable of forming a cationic species e.g . , n-alkylamine , to effect exchange with said interspathic cations in order to swell the layered material.
  • chalcogenide e.g . , tetraethylorthosilica te
  • chalcogenide e.g . , tetraethylorthosilica te
  • organic- swelled layered material which is contacted once with electrically neutral organic compound capable of conversion to polymeric chalcogenide to form a pillared product.
  • chalcogenide can be prepared even from layered materials which have been difficult to treat by conventional techniques.
  • the method comprises intercalating an organic-swelled layered metal
  • Water may be added to the layered metal chalcogenide to effect further hydrolysis of the polymeric chalcogenide precursor .
  • step a) serves to remove excess organic swelling agent and hydrolysis by-products from the organic-swelled layered material which allows for incorporation of increased amounts of polymeric chalcogenide precursor between the layers.
  • polymeric chalcogenides are considered to include chalcogenides of two or more repeating units , preferably three or more repeating units , say four or more or even five or more repeating units.
  • the extent of polymerization of the interspathic polymeric chalcogenide is believed to affect the ultimate interlayer separation of the pillared layered metal oxide product.
  • the layered chalcogenide material which is organic-swelled to form the organic-swelled starting material employed in the present invention can be a layered oxide, sulfide, selenide or telluride, preferably a layered oxide material of elements other than those of Group VIB of the Periodic Table, i.e. , O, S, etc.
  • Suitable layered oxide materials include layered oxides of Group IVA metals such as titanium, zirconium and hafnium, e.g . , layered trititanates, such as Na 2 Ti 3 O 7 comprising Ti 3 O 7 -2 layers
  • silicotitanates Upon intercalation with polymeric sil ica, such tritanates are known as silicotitanates.
  • Other layered chalcogenide materials in which the present invention may be used to facilitate intercalation include KTiTaO 5 and
  • the present invention can facilitate intercalation of layered silicates known as high sil ica alkali silicates whose layers lack octahedral sheets .
  • These silicates can be prepared hydro thermally from an aqueous reaction mixture containing sil ica and caustic at relatively moderate temperatures and pressures contain tetra coordinate framework atoms other than Si.
  • magadiite natrosilite
  • kenyaite makatite
  • nekoite kanemite
  • okenite dehayelite
  • macdonaldite macdonaldite and rhodes ite , preferably their acid-exchanged forms.
  • a of charge m wherein m is an integer between 1 and 3 , preferably 1.
  • A is a large alkali metal cation selected from the group consisting of Cs, Rb and K and M is a divalent or trivalent metal cation selected from at least one Mg, Sc, Mn, Fe, Cr, Ni, Cu, Zn, In, Ga and Al.
  • M can be both In and Ga.
  • these metal oxides are believed to consist of layers of (M, [ ] , or Z)O 6 octahedra which are trans edge-shared in one dimension and cis edge-shared in the second dimension forming double octahedral layers which are separated by cations in the third dimension.
  • These materials can be prepared by high temperature fusion of a mixture of 1) metal oxide, 2) alkali metal carbonate or nitrate and 3) tetravalent metal dioxide , e.g . , titanium dioxide or by fusion of a mixture of alkali metallate and tetravalent metal dioxide.
  • Such fusion can be carried out in air in ceramic crucibles at temperatures ranging between 600 to 1100 °C after the reagents have been ground to an homogeneous mixture.
  • the resulting product is ground to 0.853 to 0.066 ran (20 to 250 mesh) , prior to the organic swell ing and polymeric oxide intercalation steps.
  • layered metal oxides as the layered starting material permits inclusion of different metal atoms into the layered starting material being treated which allows potential catalytically active sites to be incorporated in the stable layer itself .
  • variable amounts of metal atoms may be added to provide a catalyst with optimum activity for a particular process.
  • the infinite trans-edge shared layer structure of the titanometallates-type layered metal oxides instead of the sheared 3-block structure of, for example, Na 2 Ti 3 O 7 , may reduce or
  • titanometallate-type materials may possess-even greater thermal stabil ity than sil icotitanate molecular sieves .
  • variable charge density on the oxide layer possible for these layered metal oxides due to the various oxidation states of metal oxides, the incorporated metal atom and the varying stoichiometry of the materials may allow variation in the amount of the organic cationic species which can be exchanged into the material . This , in turn, permits variation of the ultimate
  • the metal oxide product contains 0.5 to 20 weight percent of said element M, preferably 1 to 10 weight percent.
  • Vacancy -containing materials are particularly suited for treatment by the present method.
  • the ti tan ometallate-type layered metal oxide product after intercalation with polymeric chalcogenide according to the present invention comprises a layered titancmetallate-type layered metal oxide and interspathic polymeric chalcogenide of at least one element, separating the layers of the metal oxide.
  • such materials after pillaring are thermally stable, i .e. , capable of withstanding calcination at a temperature of 450 °C for at least 2 hours without significant reduction (e.g . , not greater than 10 or
  • the organic swelling agent used to swell the layered starting material employed in the present invention comprises a source of organic cation such as organoammonium, which source may include the cation itself, in order to effect an exchange of the interspathic cations resulting in the layers of the starting material being propped apart.
  • a source of organic cation such as organoammonium, which source may include the cation itself, in order to effect an exchange of the interspathic cations resulting in the layers of the starting material being propped apart.
  • organoammonium which source may include the cation itself, in order to effect an exchange of the interspathic cations resulting in the layers of the starting material being propped apart.
  • protonated alkylamines are preferred.
  • alkylamm ⁇ nium cations include
  • the source of organic cation in those instances where the interspathic cations include hydrogen or hydronium ions may include a neutral compound such as organic amine which is converted to a cationic analogue during the swelling or "propping" treatment.
  • these materials are C 3 to C 10 , preferably C 6 to C 6 alkylamines, preferably n-alkylamines, or
  • n-alkanols n-alkanols.
  • the present method has been found particularly useful in pillaring materials which do not contain interspathic alkali metals, e.g. , layered material having ammonium (NH 4 + ) ions
  • Interspathic polymeric chalcogenide pillars are then formed between the layers of the organic-swollen layered metal chalcogenide starting material and may include a chalcogenide, preferably a polymeric chalcogenide, of zirconium or titanium or more preferably of an element selected from Group IVB of the Periodic Table (Fischer Scientific Company Cat. No. 5-702-10 , 1978) , other than carbon, i .e. , silicon, germanium, tin and lead.
  • a chalcogenide preferably a polymeric chalcogenide, of zirconium or titanium or more preferably of an element selected from Group IVB of the Periodic Table (Fischer Scientific Company Cat. No. 5-702-10 , 1978) , other than carbon, i .e. , silicon, germanium, tin and lead.
  • a chalcogenide preferably a polymeric chalcogenide, of zirconium or titanium or more preferably of an element selected from Group IVB of
  • chalcogenides include those of Group VA, e .g. , V, Nb, and Ta, those of Group IIA, e.g. , Mg or those of Group IIIB, e.g . , B.
  • the pillars include polymeric silica.
  • the chalcogenide pillars may include an element which provides
  • catalytically active acid sites in the pillars preferably aluminum.
  • the chalcogenide pillars are formed from a precursor material which is preferably introduced between the layers of the organic "propped" species as a cationic, or more preferably, electrically neutral, hydrolyzable compound of the desired elements, e.g . , those of group IVB.
  • the precursor material is preferably an organometallic compound which is a liquid under ambient conditions.
  • hydrolyzable compounds e.g . , alk oxides
  • the desired elements of the pillars are utilized as the precursors .
  • Suitable polymeric sil ica precursor materials include
  • tetraalkylsilicates e.g. , tetrapropylorthosilicate
  • pillars are also required to include a different polymeric metal oxide, e.g . , alumina or titania, a hydrolyzable compound of said metal can be contacted with the organic "propped" species before, after or simultaneously with the contacting of the propped titanometallate with the sil icon
  • the hydrolyzable aluminum compound employed is an aluminum alkoxide, e.g . , aluminum isopropoxide.
  • a hydrolyzable titanium compound such as titanium alkoxide, e.g . , titanium isopropoxide, may be used.
  • the chalcogenide precursor may contain zeolite precursors such that exposure to conversion conditions results in the formation of interspathic zeolite material as at least part of the chalcogenide pillars. Pillars of polymeric sil ica and polymeric alumina or polymeric silica and polymeric titania are particularly preferred.
  • the final pillared product may contain residual exchangeable cations.
  • Such residual cations in the layered material can be ion exchanged by known methods with other catioric species to provide or alter the catalytic activity of the pillared product.
  • Suitable replacement cations include cesium, cerium, cobalt, nickel, copper, zinc , manganese, platinum, lanthanum, aluminum, ammonium, hydronium and mixtures thereof .
  • Silica-pillared products exhibit thermal stabil ity at temperatures of 500°C or even higher as well as substantial sorption capacities (as much as 10 to 25 wt % for H 2 O and C 6 hydrocarbon).
  • Silica-pillared products possess interlayer separations of greater than 12A and surface areas greater that 250 m 2 /g when divalent metal atoms , e.g . , Mg, Ni , Cu and Zn, are present as the metal M of the product.
  • Silica-pillared products incorporating trivalent metal atoms e.g . , Sc , Mn, Fe, Cr, In, Ga and Al can possess interlayer separations of 6 to 15A.
  • layered materials containing interspathic polymeric chalcogenide can be improved when their preparation includes conditions which facilitate removal of organic hydrolysis by-products produced during conversion to polymeric chalcogenides .
  • organic hydrolysis by-products produced during conversion to polymeric chalcogenides .
  • alkanols are produced during hydrolysis.
  • TEOS tetraethylorthosilicate
  • ethanol is a hydrolysis by-product.
  • polymeric chalcogenide precursor incorporation and hydrolysis at 50 to 170°C, preferably 75 to 85 °C, say about 80°C, pillared products having enhanced crystall ini ty and interlayer spacings are prepared.
  • organic hydrolysis by-products removal can be facilitated by conducting hydrolysis in a system which permits release of the organic hydrolysis by-products from the system.
  • a system contains a means for preventing the introduction of water from outside the system , for example, an outlet tube connected to a silicone fluid bubbler or a
  • the inert atmosphere can be any non-reactive gas, e.g. , helium or nitrogen, with nitrogen especially preferred.
  • the non-reactive atmosphere should be substantially free of moisture, say less than 0.5%, preferably less than 0.011 water in order to prevent extralaminar hydrolysis from occurring.
  • the non-reactive atmosphere may be either static or dynamic. However, where a dynamic system is employed, the flow of inert gas should be low enough to prevent undesired levels of evaporation of the organic polymeric chalcogenide precursor, e.g. , tetraethylorthosilicate.
  • the present invention is illustrated further by the following Examples . In these examples , X-ray diffraction data were obtained by standard techniques using K-alpha doublet of copper radiation. Nitrogen BET surface areas are reported in m 2 /g. EXAMPLE 1
  • Reagents , reagent stoichiometries , reaction temperatures , and dwell times are displayed in Table 1 above.
  • the reactions were carried out by thoroughly grinding the reagents to homogenous mixtures and firing in ceramic crucibles. In cases where potassium was used as the alkali metal cation, regrinding and refiring was required to obtain the layered phase in reasonable purity for further
  • the stiff powders obtained were ground to roughly 0.152 mm (100 mesh) before further reactions.
  • Example 2 The materials of Example 1 containing alkali metal cation were then exchanged with ammonium ion by refluxing three times in 1M NH 4 NO 3 for 16-24 hr, using from 7-10 ml 1M NH 4 NO 3 /g layered alkali titanometallate. Analytical data is summarized in Table 2.
  • the reaction mixture was cooled, filtered , and washed with hot distilled H 2 O (about 2 times the volume of the reaction solution).
  • the solid was air dried at room temperature.
  • Example la Samples from Example la were swollen by stirring in neat refluxing octylamine for 16-24 h using at least 5 g octylamine/g solid. The reactions were filtered, washed with 90% EtOH, and air dried. The d-spacings observed for propped materials are summarized in Table 3.
  • Example 2a The octylammonium-swollen solids of Example 2a were stirred in H 2 O for 2-4 h, followed by filtration and drying in air. The solids were then stirred in tetraethylorthosilicate (TEOS) at 80°C for 24 h, filtered and air dried. This sequence was repeated until a very sharp low angle line was observed in the x-ray powder diffraction pattern of the product calcined in air at 500-510°C (5°C/min) for 3 h. Results are set out below in Table 4.
  • TEOS tetraethylorthosilicate
  • a sample of Na 2 Ti 3 O 7 was prepared by calcining an intimate mixture of 1000 g Ti0 2 and 553g Na 2 C0., in air at
  • the octylammonium swollen trititanate had the following composition (wt%):
  • TEOS tetraethylorthosilicate

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

On intercale des chalcogénures métalliques en couches à gonflement organique, par exemple des titanométallates ou des silicotitanates, avec un chalcogénure polymère, par des traitements multiples à l'aide d'un précurseur de chalcogénure polymère hydrolysable, électriquement neutre, par exemple du tétraéthylorthosilicate, afin de produire des produits ayant une surface spécifique améliorée.
PCT/US1989/001571 1989-04-13 1989-04-13 Procede d'intercalation de chalcogenure metallique en couches a gonflement organique, avec un chalcogenure polymere, par des traitements multiples a l'aide d'un precurseur de chalcogenure polymere WO1990011827A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP50007489A JPH03505445A (ja) 1989-04-13 1989-04-13 重合体状カルコゲニドプレカーサーによる複数の処理によって重合体状カルコゲニドを有機の膨潤層の金属カルコゲニドの間にはさむ方法
PCT/US1989/001571 WO1990011827A1 (fr) 1989-04-13 1989-04-13 Procede d'intercalation de chalcogenure metallique en couches a gonflement organique, avec un chalcogenure polymere, par des traitements multiples a l'aide d'un precurseur de chalcogenure polymere
EP19890910745 EP0419581A4 (en) 1989-04-13 1989-04-13 Method for intercalating organic-swelled layered metal chalcogenide with a polymeric chalcogenide by plural treatments with polymeric chalcogenide precursor
DK294890A DK294890D0 (da) 1989-04-13 1990-12-12 Fremgangsmaade til interkalatering af et organisk opkvaeldet lagdelt metalchalcogenid med et polymert chalcogenid ved gentagne behandlinger med polymer chalcogenik-praekursor

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PCT/US1989/001571 WO1990011827A1 (fr) 1989-04-13 1989-04-13 Procede d'intercalation de chalcogenure metallique en couches a gonflement organique, avec un chalcogenure polymere, par des traitements multiples a l'aide d'un precurseur de chalcogenure polymere

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8343455B2 (en) 2005-08-25 2013-01-01 Otsuka Chemical Co., Ltd. Flaky titanic acid having polymerizable functional groups, suspension of the same, and coating films made therefrom

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4831006A (en) * 1984-12-28 1989-05-16 Mobil Oil Corporation Method for intercalating organic-swelled layered metal chalcogenide with polymer chalcogenide by treatment with organic, hydrolyzable, polymeric chalcogenide precursor wherein organic hydrolysis by-products are removed

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859648A (en) * 1984-12-28 1989-08-22 Mobil Oil Corporation Layered metal chalcogenides containing interspathic polymeric chalcogenides
NZ214538A (en) * 1984-12-28 1989-04-26 Mobil Oil Corp Layered product having layers separated by polymeric pillars

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4831006A (en) * 1984-12-28 1989-05-16 Mobil Oil Corporation Method for intercalating organic-swelled layered metal chalcogenide with polymer chalcogenide by treatment with organic, hydrolyzable, polymeric chalcogenide precursor wherein organic hydrolysis by-products are removed
US4831005A (en) * 1984-12-28 1989-05-16 Mobil Oil Company Method for intercalating organic-swelled layered metal chalcogenide with a polymeric chalcogenide by plural treatments with polymeric chalcogenide precursor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0419581A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8343455B2 (en) 2005-08-25 2013-01-01 Otsuka Chemical Co., Ltd. Flaky titanic acid having polymerizable functional groups, suspension of the same, and coating films made therefrom

Also Published As

Publication number Publication date
DK294890A (da) 1990-12-12
EP0419581A1 (fr) 1991-04-03
DK294890D0 (da) 1990-12-12
JPH03505445A (ja) 1991-11-28
EP0419581A4 (en) 1991-09-11

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