EP0466709A1 - Synthese von schichtsilikatmaterial von kenyait-typ und verbrücken des materials - Google Patents

Synthese von schichtsilikatmaterial von kenyait-typ und verbrücken des materials

Info

Publication number
EP0466709A1
EP0466709A1 EP90904165A EP90904165A EP0466709A1 EP 0466709 A1 EP0466709 A1 EP 0466709A1 EP 90904165 A EP90904165 A EP 90904165A EP 90904165 A EP90904165 A EP 90904165A EP 0466709 A1 EP0466709 A1 EP 0466709A1
Authority
EP
European Patent Office
Prior art keywords
silicate
mixture
layered silicate
kenyaite
compound
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.)
Withdrawn
Application number
EP90904165A
Other languages
English (en)
French (fr)
Inventor
Ernest William Valyocsik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
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 Corp filed Critical Mobil Oil Corp
Publication of EP0466709A1 publication Critical patent/EP0466709A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/04—Esters of silicic acids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type

Definitions

  • This invention relates to the synthesis of a Kenyaite-type layered crystalline silicate and to pillaring of the resultant product.
  • the fundamental unit of crystalline silicate structures is a tetrahedral complex consisting of the Si cation in a tetrahedral coordination with four oxygens.
  • the tetrahedra link to form chains which result in fibrous or needlelike morphologies. Single chains result when SiO ⁇ tetrahedra are joined at two oxygen atoms.
  • the tetrahedra are linked in layers or sheets as in mica minerals. Similar arrangements of the tetrahedra are found in clay minerals wherein two types of sheets may exist, one consisting of aluminum, iron or magnesium ions in a six-fold coordination with oxygens.
  • the layer or sheet structures result from linking between three corners of each tetrahedron to neighboring tetrahedra. Breck, Zeolite Molecular Sieves, John Wiley . Sons, New York, London, Sydney, Toronto, p.
  • Kenyaite-type layered crystalline silicates have, until now, been found in natural deposits (H.P. Eugster, ' ⁇ ydrous Sodium Silicate From Lake Magadii, Kenya; Precursors in Bedded Chert", Science, 157, 1177-1180 (1967)) or have been synthesized from inorganic systems (K. Beneke and G. Lagaly, "Kenyaite-Synthesis and Properties", Amer. Mineralogist, 6 , 818-826 (1983), and WO88/00091).
  • the present invention provides an improved, economical and reproducible method for preparing synthetic Kenyaite-type layered crystalline silicate exhibiting high crystallinity and purity, catalytic activity and other valuable properties.
  • the invention resides in a method for synthesizing a crystalline Kenyaite-type silicate which comprises (i) preparing a mixture capable of forming said silicate, said mixture comprising sources of alkali metal cations (AM), silica, a non-alkali metal (M) of valence n, water and an organic compound (R) selected from an alkylamilne, a trialkylamine, a tetraalkylammonium compoung and trimethylhexamethylene diamine, said alkyl having 1 to 12 carbon atoms, and having a composition, in terms of mole ratios, within the following ranges:
  • AM alkali metal cations
  • M non-alkali metal
  • R organic compound selected from an alkylamilne, a trialkylamine, a tetraalkylammonium compoung and trimethylhexamethylene diamine, said alkyl having 1 to 12 carbon atoms, and having a composition, in terms of mo
  • the invention further resides in a method for pillaring the resulting layered silicate.
  • the Kenyaite-type silicate prepared by the method of the invention has a characteristic X-ray diffraction pattern including the lines listed in Table 1 below: Table 1
  • X-ray diffraction data were collected with a Rigaku diffraction system, equipped with a graphite diffracted beam monochromator and scintillation counter, using copper K-alpha radiation.
  • the diffraction data were recorded by step-scanning at 0.02 degrees of two-theta, where theta is the Bragg angle, and a counting time of 1 second for each step.
  • the interplanar spacings, d's were calculated in Angstrom units (A), and the relative intensities of the lines, I/I 0 , where I is one-hundredth of the intensity of the strongest line, above background, were derived with the use of a profile fitting routine (or second derivative algorithm).
  • the intensities are uncorrected for Lorentz and polarization effects.
  • crystallographic changes can include minor changes in unit cell parameters and/or a change in crystal symmetry, without a change in topology of the structure. These minor effects, including changes in relative intensities, can also occur as a result of differences in cation content, framework composition, nature and degree of pore filling, and thermal and/or hydrothermal history.
  • Synthesis of a Kenyaite-type layered silicate according to the invention comprises (i) preparing a mixture capable of forming the layered silicate, said mixture comprising sources of alkali metal cations (AM), silica, non-alkali metal (M), water and an organic compound (R), and having a composition, in terms of mole ratios, within the following ranges:
  • n is the valence of M, (ii) maintaining said mixture under sufficient conditions until crystals of said silicate are formed, and (iii) recovering said silicate having a highly crystalline Kenyaite-type layered structure.
  • the quantity of OH " is calculated only from inorganic sources of alkali without any organic base contribution.
  • Metal M may include any one or more of metals from Periodic Table Groups IVB (e.g. titanium), IIIA (e.g. aluminum, gallium, indium and thallium), VIB (e.g. chromium), IVA (e.g. germanium, tin and lead) and VIII (e.g. iron).
  • Organic R may include any organic which acts as a mineralizer to promote crystallization from the above reaction mixture. Examples of such organic agents include alkylamine, trialkylamine, tetraalkylammonium compound wherein alkyl has 1 to about 12 carbon atoms, e.g. tetrapropylammoniura, and trimethylhexamethylene diamine.
  • Hydrothermal reaction conditions for crystallizing the present product from the above mixture include heating the reaction mixture to a temperature of 60°C to 250°C for a period of time of 6 hours to 60 days.
  • a more preferred temperature range is from 100°C to 200°C with the amount of time at a temperature in such range being from 8 hours to 5 days.
  • the reaction is carried out until a fully crystalline product is formed.
  • the solid product comprising highly crystalline Kenyaite-type layered silicate is recovered from the reaction medium, such as by cooling the whole to room temperature, filtering and water washing.
  • the reaction mixture composition for the synthesis of synthetic crystalline silicate hereby can be prepared utilizing materials which can supply the appropriate oxide.
  • Such compositions include metal (M) salts or oxides and, when a separate source of aluminum is desired, aluminates or alumina; and silicates, silica hydrosol, silica gel, silicic acid and hydroxides.
  • M metal
  • silicates silica hydrosol, silica gel, silicic acid and hydroxides.
  • each oxide component utilized in the reaction mixture for preparing the present silicate can be supplied by one or more essential reactants and they can be mixed together in any order.
  • any oxide can be supplied by an aqueous solution, sodium hydroxide or by an aqueous solution of a suitable silicate.
  • the reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time for the product composition comprising the present silicate will vary with the exact nature of the reaction mixture employed.
  • Useful sources of silicon for the reaction mixture of the present invention include solid silicas or silica precursors. Such sources are cost effective and allow high solids loading of the reaction mixture.
  • a solid silica e.g. Ultrasil (a precipitated, spray dried silica) or HiSil (a precipitated hydrated Si0 2 containing about 6 weight percent free H-,0 and about 4.5 weight percent bound H 2 0 of hydration and having a particle size of about 0.02 micron) as the oxide of silicon source provides economic synthesis.
  • Such solid silica sources are commercially available.
  • the silica precursor source of silicon for the present reaction mixture is an amorphous silica precipitate made from a solution of a soluble silica source.
  • the solution is an aqueous solution of a pH ranging from 9 to 12.
  • the source of silica can be any soluble silicate and is preferably sodium silicate.
  • the silica precursor is formed by its continuous precipitation from the solution phase. Accordingly, precipitation comprises initiating precipitation and maintaining said precipitation.
  • the composition of the solution of soluble silica source is undertaken by introducing a precipitating reagent.
  • the precipitating reagent is a source of acid, conveniently a solution of a mineral acid, such as H 2 S0., HC1, and HNO, typically having a pH ranging from essentially 0 to about 6.
  • a mineral acid such as H 2 S0., HC1, and HNO
  • precipitation of the silica precursor can be effected by acid neutralization of a basic solution of a silicate.
  • the silica can be precipitated alone in the absence of sources of other framework elements, e.g. aluminum. In this fashion, both the precipitating reagent and the solution of silica source can be free of intentionally added alumina or alumina source.
  • silica precipitation reaction mixture no aluminum is deliberately added to the silica precipitation reaction mixture, in this embodiment; however, aluminum is ubiquitous and the presence of such a material in minor amounts is due to impurities in the precursors of the reactants or impurities extracted from the reaction vessel.
  • the amount of alumina in the silica precursor precipitate will be less than about 0.5 weight percent, and generally less than 0.2 weight percent.
  • the amount of alumina in the silica precursor precipitate will be up to about 5 weight percent.
  • Silicate precipitation can be coprecipitation in the presence of soluble sources of other framework elements including gallium, indium, boron, iron and chromium.
  • the soluble source of these other framework components can be, for example, nitrates.
  • the coprecipitation product would be amorphous, for example an amorphous gallosilicate, borosilicate or ferrosilicate.
  • Continuous precipitation of the amorphous silica precursor may comprise introducing the solution of silica source and the precipitating reagent to a reaction zone while maintaining a molar ratio of silica source to precipitating reagent substantially constant.
  • the precipitating reagent and the silica source are introduced simultaneously into the reaction zone.
  • the continuous precipitation of silica precursor effects two results. Firstly, silica gel formation is at least substantially eliminated and secondly, precipitated silica precursor particle size exceeds that at which silica gel formation is possible.
  • the precipitated silica precursor comprises agglomerated solids in the shape of microspheres. Suspensions of these particles exhibit low viscosities at high solids loading in the subsequent synthesis reaction mixture of the present invention, even at solids loading equal to or greater than about 20-40%.
  • the particle size of the precipitated silica precursor ranges between 1-500 microns, but the average size is 50-100 microns.
  • the temperature of the precipitation mixture can range from 80°F to 300°F (27°C to 150°C).
  • the time of contact of the solution of silica source and the precipitating reagent can range from 10 minutes to several hours at pH maintained from 6 to 11.
  • the silica precursor is processed by isolating it, for example by filtration, and removing soluble contaminants therefrom by washing and/or ion exchange. This stage can be considered a solids consolidation step.
  • the Kenyaite-type silicate prepared by the present method has a chemical composition in terms of mole ratios of oxides and in the anhydrous state, as-synthesized, as follows:
  • the silicate product of the invention is valuable as a catalyst component, e.g., low activity support, for various chemical conversion processes.
  • Such process mechanisms include (1) formation or rupture of carbon-carbon bonds, such as cracking, isomerization, polymerization, alkylation and olefin dismutation; (2) formation or rupture of carbon-hydrogen bonds, such as hydrogenation, dehydrogenation, hydrogen transfer and hydrogenolysis; (3) conversion of oxygenates to other oxygenates or hydrocarbons as well as other reactions involving heteroatom-containing organic compounds; (4) oxidation of alkanes, alkenes and aromatic hydrocarbons; and (5) the reactions of unsaturated hydrocarbons with carbon oxides.
  • the layered silicate product of the present invention can be modified to increase its interlayer spacing by introducing material between the layers.
  • chalcogenide, and preferably oxide, pillars can be intercalated between the layers to provide a thermally stable, highly porous structure useful as a catalyst or a catalyst support.
  • the preferred method for producing such a chalcogenide pillared product is described in detail in US Patent No. 4600503 and EP-A-205711.
  • the method involves physically separating the layers by introducing an organic cationic species, typically an organoammonium compound and preferably a C*-, or larger alkylammonium cation, at anionic sites between the layers and then introducing between the separated layers of the resultant "propped" species, an electrically neutral compound, such as an alkoxide, capable of conversion, preferably by hydrolysis, to the required chalcogenide pillars.
  • an electrically neutral compound such as an alkoxide
  • the hydrolyzable, electrically neutral compound is tetraraethylorthosilicate, tetrapropylorthosilicate or, more preferably, tetraethylorthosilicate.
  • Example 1-6 Six separate efforts were made to synthesize Kenyaite-type layered silicate directly under hydrotherraal conditions from reaction mixtures containing an organic agent.
  • the organic R added to Example 1 was trimethylhexamethylene diamine. Tetrapropylammonium bromide was the organic R added to the reaction mixtures of Examples 2, 5 and 6.
  • Tripropylamine was the organic R added to the Example 3 reaction mixture, and n-propylamine was added to the mixture of Example 4.
  • the silica source in Example 1 was Q-brand sodium silicate
  • reaction mixtures were stirred at 400 rpm for the reaction duration and maintained at 160°C.
  • Each example yielded pure 100% crystalline Kenyaite-type layered silicate.
  • Figure 1 is a reproduction of an X-ray diffraction scan of as-synthesized product from Example 3.
  • the X-ray diffraction pattern of the Example 3 product is set forth in Table 3.
  • the synthetic kenyaite-type product hereof is pillared by the following procedure.
  • the pH of the solution is kept at 2 for 24 hours with addition of acid as needed.
  • the mixture is then filtered, water-washed and vacuum-dried.
  • the dry sample is then treated with a dimethylsulfoxide(DMSO)/n-octylamine mixture at the weight ratio of 1:2:1 (sample:DMS0:amine) at ambient temperature for 24 hours.
  • the sample is then filtered and dried in air at ambient temperature.
  • the sample is finally suspended in tetraethylorthosilicate (TEOS), 5g TEOS/ lg solid, for 24 hours. After this treatment, the sample is filtered, dried and air calcined at 540°F for 3 hours.
  • TEOS tetraethylorthosilicate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
EP90904165A 1990-02-06 1990-02-06 Synthese von schichtsilikatmaterial von kenyait-typ und verbrücken des materials Withdrawn EP0466709A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1990/000406 WO1991012204A1 (en) 1990-02-06 1990-02-06 Synthesis of kenyaite-type layered silicate material and pillaring of said material

Publications (1)

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EP0466709A1 true EP0466709A1 (de) 1992-01-22

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EP90904165A Withdrawn EP0466709A1 (de) 1990-02-06 1990-02-06 Synthese von schichtsilikatmaterial von kenyait-typ und verbrücken des materials

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EP (1) EP0466709A1 (de)
JP (1) JPH04504557A (de)
KR (1) KR920702852A (de)
WO (1) WO1991012204A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2011224043B2 (en) * 2004-12-10 2014-04-17 Archer-Daniels-Midland Company Conversion of 2,5-(hydroxymethyl) furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69225311T2 (de) * 1991-01-11 1998-08-20 Mobil Oil Corp., Fairfax, Va. Schichtenförmige oxide sowie geschwollene und saeulenartige formen dieser materialien
CA2098395A1 (en) * 1991-01-11 1992-07-12 Charles Theodore Kresge Method of preparing a pillared layered oxide material
NL9202277A (nl) * 1992-12-29 1994-07-18 Pelt & Hooykaas Werkwijze ter bereiding van een gelaagd, klei-achtig materiaal alsmede een werkwijze voor het immobiliseerbaar maken van afvalmateriaal.
FR2865725B1 (fr) * 2004-01-29 2006-03-17 Inst Francais Du Petrole Methode de synthese de solides lamellaires a partir d'un structurant organique de type amino-alcool
FR2909905B1 (fr) * 2006-12-15 2009-02-06 Inst Francais Du Petrole Procede de preparation de magdiite ou kenyaite a partir d'un structurant orgnanique comp0rtant deux fonctions alcools terminales.
FR2909991B1 (fr) 2006-12-15 2009-02-06 Inst Francais Du Petrole Procede de preparation de magadiite a partir d'un structurant organique de type diammonium quaternaire.
FR2918049B1 (fr) 2007-06-28 2009-10-16 Inst Francais Du Petrole Procede de preparation de magadiite a partir du structurant n,n,n',n',-tetramethyl-n,n'-dibenzylhexanediammonium.
EP3467052B1 (de) * 2017-10-06 2022-04-13 Evonik Operations GmbH Wässrige dispersion enthaltend siliziumdioxid und trimethyl 1,6-hexamethylendiamin

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD220586A1 (de) * 1984-01-09 1985-04-03 Univ Halle Wittenberg Verfahren zur herstellung von kenyait
US4689207A (en) * 1985-03-06 1987-08-25 Chevron Research Company Process for the preparation of crystalline microporous organosilicates using magadiite as a silica source
DE3669490D1 (de) * 1985-06-13 1990-04-19 Hoechst Ag Verfahren zur herstellung von kristallinen alkalischichtsilikaten.
AU587075B2 (en) * 1985-11-12 1989-08-03 Mobil Oil Corporation Layered silicates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9112204A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2011224043B2 (en) * 2004-12-10 2014-04-17 Archer-Daniels-Midland Company Conversion of 2,5-(hydroxymethyl) furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor

Also Published As

Publication number Publication date
JPH04504557A (ja) 1992-08-13
KR920702852A (ko) 1992-10-28
WO1991012204A1 (en) 1991-08-22

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