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WO1996034827A1 - Zeolithe a structure mel contenant du titane en phase pure - Google Patents

Zeolithe a structure mel contenant du titane en phase pure Download PDF

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Publication number
WO1996034827A1
WO1996034827A1 PCT/US1996/005216 US9605216W WO9634827A1 WO 1996034827 A1 WO1996034827 A1 WO 1996034827A1 US 9605216 W US9605216 W US 9605216W WO 9634827 A1 WO9634827 A1 WO 9634827A1
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WO
WIPO (PCT)
Prior art keywords
titanium
zeolite
crystalline
compound
calcination
Prior art date
Application number
PCT/US1996/005216
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English (en)
Inventor
Yumi Nakagawa
Chris Dartt
Original Assignee
Chevron U.S.A. Inc.
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 Chevron U.S.A. Inc. filed Critical Chevron U.S.A. Inc.
Priority to AU54852/96A priority Critical patent/AU5485296A/en
Publication of WO1996034827A1 publication Critical patent/WO1996034827A1/fr

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Classifications

    • 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
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • 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
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a titanium-containing 10 zeolite having a framework structure designated MEL in pure phase form (referred to herein as "SSZ-46 n ) , to a process
  • Titanium-containing zeolite ZSM-11 which contains the MEL
  • TSA tetrabutylammonium hydroxide
  • this pure phase zeolite (SSZ-46) is useful as a catalyst in oxidation reactions.
  • the present invention provides a titanium-containing crystalline composition, as-synthesized and in the anhydrous state, whose general formula, in terms of mole ratios, is:
  • Q is an organic templating agent comprising at least one 3,5-d ⁇ methylp ⁇ per ⁇ d ⁇ n ⁇ um compound
  • Y is silicon, germanium, or mixtures thereof.
  • titanium-containing refers to the fact that the zeolites of this invention contain titanium atoms in their framework structure.
  • the titanium-containing zeolite SSZ-46 having no intergrowth within its crystalline structure of any crystalline structure other than the MEL structure.
  • the SSZ-46 of this invention has no intergrowth of ZSM-5 (or its titanium-containing analog, TS-1) crystalline structure.
  • the present invention further provides the zeolite SSZ-46 having no intergrowth within its crystalline structure of any crystalline structure other than the MEL structure and having the X-ray diffraction pattern of Table I or Table II below. " 1 In accordance with the present invention, there is also provided a process for preparing titanium-containing
  • 0 u 4 comprises:
  • the present invention also provides the above-described 21 process for preparing titanium-containing zeolites wherein 22 the organic templating agent comprises a mixture of a 3,5- 23 dimethylpiperidinium compound and a tetraalkylammonium 24 compound. 25 26 Further provided in accordance with this invention are the 27 above-described processes for preparing titanium-containing 28 zeolites wherein the zeolite so prepared is in pure phase 29 form (i.e., is SSZ-46) .
  • the present invention further provides a process for 32 oxidation of hydrocarbons comprising contacting said 33 hydrocarbon with hydrogen peroxide in the presence of a catalytically effective amount of a crystalline, titanium- containing molecular sieve for a time and at a temperature effective to oxidize said hydrocarbon, wherein the crystalline titanium-containing molecular sieve is a zeolite whose general formula is, after calcination,
  • the present invention also provides a process for epoxidation of an olefin comprising contacting said olefin with hydrogen peroxide in the presence of a catalytically effective amount of a crystalline, titanium-containing molecular sieve for a time and at a temperature effective to epoxidize said olefin, wherein the crystalline titanium- containing molecular sieve is a zeolite whose general formula is, after calcination,
  • a process for oxidizing cyclohexane comprising contacting said cyclohexane with hydrogen peroxide in the presence of a catalytically effective amount of a crystalline, titanium- containing molecular sieve for a time and at a temperature effective to- oxidize said cyclohexane, wherein the crystalline titanium-containing molecular sieve is a zeolite whose general formula is, after calcination, Ti0 2 : wSi0 2
  • the present invention is based on the discovery that titanium-containing zeolites containing the MEL crystal structure can be made using an organic templating agent comprising at least one 3,5-dimethylpiperidinium compound. It is especially surprising that, by using these 3,5-dimethylpiperidinium compounds as the templating agent, the titanium-containing zeolite can be prepared in essentially pure phase form. Heretofore, it has been difficult to prepare titanium- containing the MEL crystal structure (such as TS-2) using conventional templating agents without also crystallizing the closely related zeolite ZSM-5.
  • the templating agents useful in the present process are water-soluble 3,5-d ⁇ methylp ⁇ per ⁇ d ⁇ n ⁇ um compounds which are capable of acting as a templating agent to form titanium- containing zeolites containing the MEL crystal structure. They have a molecular structure of the general form:
  • R 1 and R 2 independently represent an alkyl group, either branched or unbranched, substituted or unsubstituted, containing from 1 to about 7 carbon atoms.
  • R 1 and R 2 together may comprise a cyclic alkyl ring system, which, including the positively charged nitrogen atom, contains from 4 to 7 atoms, said ring system being unsubstituted or substituted with branched or unbranched alkyl groups having, e.g., one to three carbon atoms.
  • X" is an anion which is not detrimental to the formation of the titanium-containing zeolite, such as those described below.
  • Preferred 3,5-DMP compounds are 3,5-dimethyl-N,N- diethylpiperidinium compounds; 3,5-dimethyl-N-methyl-N- ethylpiperidinium compounds; and spiro 3,5- dimethylpiperidinium compounds such as 1-azonia-3,5,7- trimethy1-spiro[5.4] decane compounds.
  • the anion for the salt may be essentially any anion such as halide or hydroxide which is not detrimental to the formation of the zeolite.
  • halide refers to the halogen anions, particularly fluorine, chlorine, bromine, iodine, and combinations thereof.
  • representative anions include hydroxide, acetate, sulfate, carboxylate, tetrafluoroborate, and halides such as fluoride, chloride, bromide, and iodide. Hydroxide and iodide are particularly preferred as anions.
  • the organic templating agent comprises a mixture comprising a 3,5-DMP compound and a tetraalkylammonium ("TAA") compound
  • TAA tetraalkylammonium
  • the TAA facilitates nucleation and quickly forms very small crystals (though not necessarily of SSZ-46) .
  • the 3,5-DMP templating agent then forms the pure phase SSZ-46 around the nuclei formed by the TAA.
  • use of the combination of TAA and 3,5-DMP compounds can produce smaller crystallites than when either templating agent is used alone under corresponding conditions.
  • Suitable TAA compounds include, but are not limited to, tetrabutylammonium and tetrapropylammonium compounds.
  • the TAA compound is a tetrabutylammonium compound.
  • the anion for the TAA compounds may be selected from those described above for the 3,5-DMP compounds.
  • TAA compound(s) When mixtures of 3,5-DMP and TAA compounds are used, they are generally used in a mole ratio of TAA compound(s) to 3,5-DMP compound(s) of from about 1:2 to about 1:500. Preferably, this mole ratio is from about 1:50 to about 1:200.
  • a surprising advantage of using a mixture of 3,5-DMP and TAA compounds as the organic templating agent is that crystallization occurs much faster than when a 3,5-DMP compound is used alone. Thus, when only a 3,5-DMP compound is used as the organic template, crystallization of the titanium-containing zeolite typically takes about 30 days.
  • the process of the present invention comprises forming a reaction mixture containing sources of titanium oxide; sources an oxide of silicon, germanium or mixtures thereof
  • reaction mixture having a composition in terms of mole ratios within the following ranges:
  • the reaction mixture may be prepared using standard zeolite preparation techniques.
  • Typical sources of silicon oxide include silica hydrogel, tetraalkyl orthosilicates, and fumed silica.
  • Typical sources of titanium include ° tetraalkylorthotitanates. In addition, coprecipitates
  • 07 zeolites of this invention should not contain alkali metal
  • titanium-containing zeolites of this invention should be free of aluminum in order to perform optimally as oxidation catalysts. It is, however, possible that traces of aluminum
  • 17 may be i.ntroduced i.nto the zeolite from, e.g., a si.li.ca
  • the crystallization period is typically
  • period is from about five days to about 20 days.
  • the reaction 07 mixture can be stirred during crystallization.
  • the solid product is 10 separated from the reaction mixture by standard mechanical 11 separation techniques, such as filtration.
  • the crystals are 12 water-washed and then dried, e.g., at 90°C to 150°C for from 13 8 to 24 hours, to obtain the as-synthesized zeolite 14 crystals.
  • the drying step can be performed at atmospheric 15 or subatmospheric pressures.
  • 16 17 During the hydrothermal crystallization step, the crystals 18 can be allowed to nucleate spontaneously from the reaction
  • reaction mixture can also be seeded with
  • the titanium-containing zeolite product made by the process of this invention has an as-synthesized composition comprising, in terms of mole ratios in the anhydrous state, the following:
  • the titanium-containing zeolite product was identified by its X-ray diffraction (XRD) pattern.
  • XRD X-ray diffraction
  • the X-ray powder diffraction patterns were determined by standard techniques.
  • the radiation was the K-alpha/doublet of copper.
  • the peak heights I and the positions, as a function of 20 where ⁇ is the Bragg angle, were read from the relative intensities, 100 x I/I 0 where I 0 is the intensity of the strongest line or peak, and d, the interplanar spacing in Angstroms corresponding to the recorded lines, can be calculated.
  • the X-ray diffraction pattern of Table I is representative of as-synthesized SSZ-46 made in accordance with this invention. Minor variations in the diffraction pattern can result from variations in the silica-to-titania mole ratio of the particular sample due to changes in lattice constants. In addition, sufficiently small crystals will affect the shape and intensity of peaks, leading to significant peak broadening. TABLE I
  • the X-ray patterns provided are based on a relative g intensity scale in which the strongest line in the X-ray Q pattern is assigned a value of 100: W(weak) is less than - 20; M(medium) is between 20 and 40; S(strong) is between 40 2 and 60; VS (very strong) is greater than 60.
  • Table IA shows a typical X-ray diffraction pattern for as-synthesized SSZ-46 zeolite made in accordance with this invention.
  • the intensity (I) of the peaks or lines is expressed as the intensity relative to the strongest peak or line in the pattern, i.e., I/I 0 x 100 where I 0 is the intensity of the strongest peak or line.
  • Table IIA shows the X-ray diffraction pattern of calcined SSZ-46 made in accordance with this invention, including the intensities of the peaks or lines.
  • the SSZ-46 of this invention is in pure phase form.
  • the phrase "pure phase form” refers to the fact that the SSZ-46 of this invention is composed of crystals having only the MEL crystal structure, i.e., the crystals contain no other crystal structure as an intergrowth with the MEL structure. It is believed that, heretofore, although “pure” titanium-containing zeolites containing the MEL crystal structure (i.e., TS-2) may have been reported as having been prepared, these materials have actually contained some amount of an intergrowth of another crystal structure, typically ZSM-5.
  • TS-2 titanium-containing zeolites containing the MEL crystal structure
  • One of the principal advantages of this invention is that it provides SSZ-46 without these intergrowths of other crystal structures.
  • Oxidation Reactions 2 3 The SSZ-46 prepared by the process of this invention is 4 useful as a catalyst in the oxidation of hydrocarbons. 05 Examples of such reactions include, but are not limited to, 06 the epoxidation of olefins, oxidation of alkanes, and the 07 oxidation of cyclohexane. 08 09 The amount of SSZ-46 catalyst employed is not critical, but 10 should be sufficient so as to substantially accomplish the
  • the amount of catalyst will be from
  • the catalyst may be utilized in powder, pellet,
  • silica-titania silica-thoria, silica-magnesia, silica- 34 zirconia, silica-beryllia, and ternary compositions of silica with other refractory oxides.
  • clays such as montmorillonites, kaolins, bentonites, halloysites, dickites, nacrites and anaxites.
  • the proportion of SSZ-46 to binder may range from about 99:1 to about 1:99, but preferably is from about 5:95 to about 80:20, all expressed on a weight basis.
  • the oxidizing agent employed in the oxidation processes of this invention is a hydrogen peroxide source such as hydrogen peroxide (H 2 0 2 ) or a hydrogen peroxide precursor (i.e., a compound which under the oxidation reaction conditions is capable of generating or liberating hydrogen peroxide) .
  • a hydrogen peroxide source such as hydrogen peroxide (H 2 0 2 ) or a hydrogen peroxide precursor (i.e., a compound which under the oxidation reaction conditions is capable of generating or liberating hydrogen peroxide) .
  • the amount of hydrogen peroxide relative to the amount of hydrocarbon substrate is not critical, but must be sufficient to cause oxidation of at least some of the hydrocarbon.
  • the molar ratio of hydrogen peroxide to hydrocarbon is from about 100:1 to about 1:100, preferably 10:1 to about 1:10.
  • additional hydrogen peroxide may be required.
  • one equivalent of hydrogen peroxide is required to oxidize one equivalent of a mono-unsaturated substrate, but it may be desirable to employ an excess of one reactant to optimize selectivity to the epoxide.
  • the use of a small to moderate excess (e.g., 5 to 50%) of olefin relative to hydrogen peroxide may be advantageous for certain substrates.
  • a solvent may additionally be present during the oxidation reaction in order to dissolve the reactants other 1 than the SSZ-46, to provide better temperature control, or to favorably influence the oxidation rates and 3 selectivities.
  • the solvent if present, may comprise from 1 4 to 99 weight percent of the total oxidation reaction mixture 5 and is preferably selected such that it is a liquid at the ° oxidation reaction temperature.
  • Organic compounds having 7 boiling points at atmospheric pressure of from about 25°C to 8 about 300°C are generally preferred for use.
  • Excess 9 hydrocarbon may serve as a solvent or diluent.
  • Illustrative 0 examples of other suitable solvents include, but are not 1 limited to, ketones (e.g., acetone, methyl ethyl ketone, 2 *2 acetophenone) , ethers (e.g., tetrahydrofuran, butyl ether), 3 nitriles (e.g., acetonitrile) , aliphatic and aromatic 4 hydrocarbons, halogenated hydrocarbons, and alcohols (e.g., 5 methanol, ethanol, isopropyl alcohol, t-butyl alcohol, 6 alpha-methyl benzyl alcohol, cyclohexanol) . More than one 7 type of solvent may be utilized.
  • ketones e.g., acetone, methyl ethyl ketone, 2 *2 acetophenone
  • ethers e.g., tetrahydrofuran, butyl ether
  • 3 nitriles e.g
  • the reaction temperature is not critical, but should be 1 sufficient to accomplish substantial conversion of the 2 substrate hydrocarbon within a reasonably short period of 3 time. It is generally advantageous to carry out the 4 reaction to achieve as high a hydrogen peroxide conversion 5 as possible, preferably at least about 50%, more preferably 6 at least about 90%, most preferably at least about 95%, 7 consistent with reasonable selectivities.
  • the optimum 8 reaction temperature will be influenced by catalyst 9 activity, hydrocarbon reactivity, reactant concentrations, 0 and type of solvent employed, among other factors, but 1 typically will be in a range of from about 0°C to about 2 150°C (more preferably from about 25°C to about 120°C) .
  • reaction or residence times from about one minute to about 4 48 hours (more desirably from about ten minutes to about eight hours) will typically be appropriate, depending upon the above-identified variables.
  • subatmospheric pressures can be employed, the reaction is preferably performed at atmospheric or at elevated pressure (typically, between one and 100 atmospheres) , especially when the boiling point of the hydrocarbon substrate is below the oxidation reaction temperature.
  • elevated pressure typically, between one and 100 atmospheres
  • Most (over 50%) of the hydrocarbon substrate should preferably be present in the liquid phase.
  • the oxidation process of this invention may be carried out in a batch, continuous, or semi-continuous manner using any appropriate type of reaction vessel or apparatus such as a fixed bed, transport bed, fluidized bed, stirred slurry, or CSTR reactor.
  • the reactants may be combined all at once or sequentially.
  • the hydrogen peroxide or hydrogen peroxide precursor may be added incrementally to the reacti.on zone.
  • the hydrogen peroxide could also be generated in situ within the same reactor zone where oxidation is taking place.
  • the oxidized product may be separated and recovered from the reaction mixture using any appropriate technique such as fractional distillation, extractive distillation, liquid-liquid extraction, crystallization, or the like.
  • the olefin 05 substrate epoxidized in the process of this invention may be 06 any organic compound having at least one ethylenically
  • the olefin may contain aryl groups (e.g., phenyl, 10 naphthyl) .
  • the olefin is aliphatic in character and contains from 2 to about 30 carbon atoms.
  • the use of 1 122 light (low-boiling) C 2 to C 10 mono-olefins is especially
  • the double bond may be in a
  • Suitable substrates include unsaturated
  • fatty acids or fatty acid derivatives such as esters or
  • 26 olefins may also be epoxidized, although the epoxides of
  • the olefin may contain substituents other than hydrocarbon
  • Exemplary olefins suitable for use in the process of this invention include ethylene, propylene, the butenes (i.e., 1,2-butene, 2,3-butene, isobutylene) , butadiene, the pentenes, isoprene, 1-hexene, 3-hexene, 1-heptene, 1-octene, diisobutylene, 1-nonene, 1-tetradecene, pentamyrcene, camphene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, the trimers and tetramers of propylene, styrene (and other vinyl aromatic substrates) , polybutadienes, polyiso
  • Olefins which are especially useful for epoxidation are the C 2 -C 30 olefins having the general structure
  • R 3 R 4 C CR 5 R 6 wherein R 3 , R 4 , R 5 and R 6 are the same or different and are selected from the group consisting of hydrogen and C ⁇ -C ' 2 20 alkyl.
  • Mixtures of olefins may be epoxidized and the resulting mixtures of epoxides either employed in the mixed form or separated into the different component epoxides.
  • amorphous silica (CabOSil M-5) was added slowly under
  • the crystalline product of this reaction was determined by X-ray diffraction (XRD) to be a titanium-containing zeolite having the MEL crystal structure in pure phase form, i.e., SSZ-46, having the following characteristic X-ray diffraction lines:
  • the crystalline product was analyzed by XRD and found to be SSZ-46 having the following characteristic X-ray diffraction lines:
  • a small amount of seed crystals (0.04 gram of pure phase ZSM-11 made with Template A) was added to the resulting clear colorless solution, which was then transferred into Teflon-lined autoclaves and tumbled at 160°C under autogenous pressure for four weeks.
  • the resulting crystalline product was recovered by centrifugation and readied for catalysis by calcination in air at 595°C for five hours.
  • the crystalline product was determined by XRD to be SSZ-46 having the following characteristic X-ray diffraction lines:
  • Example 3 The procedure described in Example 3 was used, except that the reaction mixture contained 13.19 grams TEOS, 0.15 gram TEOT, and 25.53 grams of an 11.36 wt% aqueous solution of Template A. This resulted in the following molar composition: -30-
  • Si : Ti : Template A : H 2 0 1 : 0.01 : 0.25 : 40
  • the resulting clear, colorless solution was placed in Teflon-lined autoclaves and a small amount of seed crystals (0.075 gram of a pure phase ZSM-11 made using Template A) was added to speed crystallization.
  • the autoclaves were tumbled at 175°C under autogenous pressure for 12 days.
  • the resulting crystalline product was recovered by filtration and readied for catalysis by calcination in air at 595°C for 5 hours.
  • the crystalline product was determined by XRD to be SSZ-46.
  • the crystalline product was determined by XRD to be SSZ-46.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

On prépare des zéolithes contenant du titane renfermant la structure cristalline MEL à l'aide d'un agent formant gabarit organique comprenant des composés de 3,5-diméthylpipéridinium. Lesdits zéolithes peuvent être fabriqués sous une forme en phase pure et sont utiles comme catalyseurs pour l'oxydation d'hydrocarbures.
PCT/US1996/005216 1995-05-04 1996-04-16 Zeolithe a structure mel contenant du titane en phase pure WO1996034827A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU54852/96A AU5485296A (en) 1995-05-04 1996-04-16 Pure phase titanium, containing zeolite having mel structure

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Application Number Priority Date Filing Date Title
US43446695A 1995-05-04 1995-05-04
US08/434,466 1995-05-04

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997020769A1 (fr) * 1995-12-01 1997-06-12 Chevron U.S.A. Inc. Zeolite ssz-44
WO1998029339A1 (fr) * 1996-12-31 1998-07-09 Chevron U.S.A. Inc. Procede pour preparer des zeolites au moyen de cations de piperidine substitues
WO1998047816A1 (fr) * 1997-04-21 1998-10-29 Exxon Chemical Patents, Inc. Tamis moleculaire
US5958370A (en) * 1997-12-11 1999-09-28 Chevron U.S.A. Inc. Zeolite SSZ-39
US5965104A (en) * 1996-12-31 1999-10-12 Chevron U.S.A. Inc. Zeolite SSZ-43
US6042807A (en) * 1997-04-02 2000-03-28 Arco Chemical Technology, L.P. Tellurium-containing molecular sieves
FR2784672A1 (fr) * 1998-10-19 2000-04-21 Rhodia Chimie Sa Procede de preparation d'une silicalite de titane de type mel, produit obtenu et ses applications en catalyse
WO2000076989A3 (fr) * 1999-06-11 2001-07-12 Basf Ag Procede pour faire reagir des composes organiques avec du peroxyde d'hydrogene
WO2003031423A1 (fr) * 2001-10-09 2003-04-17 Arco Chemical Technology, L.P. Procede d'epoxydation directe utilisant une zeolithe au titane pretraitee
FR2858334A1 (fr) * 2003-07-30 2005-02-04 Inst Francais Du Petrole Solide cristallise im-11 de type structural lta et son procede de preparation
CN102757306A (zh) * 2011-04-29 2012-10-31 岳阳昌德化工实业有限公司 一种环己酮的制备方法
CN102757304A (zh) * 2011-04-29 2012-10-31 岳阳昌德化工实业有限公司 一种环己烷氧化的方法
CN102766026A (zh) * 2011-05-05 2012-11-07 岳阳昌德化工实业有限公司 一种环己烷氧化制环己醇的方法
CN103012133A (zh) * 2011-09-28 2013-04-03 中国石油化工股份有限公司 一种催化氧化苯乙酮的方法
CN103204775A (zh) * 2012-01-13 2013-07-17 中国石油化工股份有限公司 一种苯乙酮的氧化方法
WO2013162040A1 (fr) * 2012-04-27 2013-10-31 Semiconductor Energy Laboratory Co., Ltd. Sel d'ammonium quaternaire cyclique, solvant non aqueux, électrolyte non aqueux et dispositif de stockage d'énergie
JP2018008978A (ja) * 2012-04-27 2018-01-18 株式会社半導体エネルギー研究所 非水溶媒、蓄電装置

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