EP0179875A1 - Titanium-silicate compositions - Google Patents
Titanium-silicate compositionsInfo
- Publication number
- EP0179875A1 EP0179875A1 EP85902353A EP85902353A EP0179875A1 EP 0179875 A1 EP0179875 A1 EP 0179875A1 EP 85902353 A EP85902353 A EP 85902353A EP 85902353 A EP85902353 A EP 85902353A EP 0179875 A1 EP0179875 A1 EP 0179875A1
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- EP
- European Patent Office
- Prior art keywords
- tiso
- process according
- titanium
- hydrocarbon conversion
- molecular sieves
- 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.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
- C07C5/412—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
- C07C5/2213—Catalytic processes not covered by C07C5/23 - C07C5/31 with metal oxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
Definitions
- the present invention relates to a new class of molecular sieve compositions containing titanium and silicon in the form of framework tetrahedral oxide units. These compositions are prepared hydrothermally from reaction mixtures containing reactive sources of titanium, silicon and oxygen and preferably at least one organic templating agent.
- Pattern A Pat.tern B: Pattern C:
- the titano-silicates of U.S. Patent No. 3,329,481 are prepared using as a "critical reagent" (column 3, line 17 et. seq.) an alkali metal peroxo-Groups IV-B metallate (M 4 XO 6 ) or hydraded forms thereof.
- the difficulty in obtaining compositions containing titanuim is evidenced by the disclosure of U.S. Patent No. 4,358,397 which discloses modified aluminosilicates.
- the aluminosilicates are modified by treating an aluminosilicate with a compound derived from one or more elements of titanium, zirconuim or hafnium.
- compositions are said to contain a minor proportion of an oxide of such elements. It is clear that in the disclosed compositions that the oxides of titanuim, zirconium and hafnium are present as deposited oxides and are present in a minor proportion.
- oxides of titanuim, zirconium and hafnium are present as deposited oxides and are present in a minor proportion.
- FIG. 1 SEM (Scanning Electron Micrograph of the product of European Application No. 82109451.3.
- the instant invention relates to new molecular sieve compositions having three- dimensional microporous crystalline framework structures of TiO 2 and SiO 2 tetrahedral oxide units.
- These new molecular sieves have a unit empirical formula on an anhydrous basis of: mR: (Ti x Si y )O 2 where "R” denominates an organic templating agent present in the intracrystalline pore system; "m” represents the moles of "R” present per mole of
- Ti x Si y (Ti x Si y )O 2 and has a value of from zero to about 0.3; and "x”. and “y” represent the mole fractions of titanium and silicon, respectively, present as framework tetrahedral oxide units. The values of "x” and “y” are generally greater than 0.01 and less than 0.99.
- x+y 1 and are such that: (1) “y” is less than 0.9615 and "x” is greater than 0.0385 when characterized by the x-ray pattern of Table III; (2) “x” and “y” are greater than 0.01 and less than 0.99 when characterized by the x-ray pattern of Table VII; or (3) “y”' is greater than 0.7776 and less than 0.9615 or less than 0.05 and "x” is greater than 0.0385 and less than 0.2224 and greater than 0.5.
- TiSO titanium silicate compositions will be generally referred to herein by the acronym "TiSO” to designate the instant molecular sieves having a framework structure of TiO 2 and SiO 2 tetrahedral oxide units.
- TiSO-i The individual class members or species will be identified by denominating the various structural species which make up the TiSO family by assigning a number to the species and. accordingly, are identified as "TiSO-i" where the number "i" is an integer. This designation is an arbitrary one and is not intented to denote structural relations to another material(s) which may also be characterized by a numbering system.
- the present invention relates to titanium silicate molecular sieves having three-dimensional microporous crystal framework structures of TiO 2 and SiO 2 tetrahedral units which have a unit empirical formula on an anhydrous basis of: mR : (Ti ⁇ Si y )O 2 (1) wherein "R” represents at least one organic templating agent present in the intracrystalline pore system; “m” represents the moles of "R” present per mole of (Ti x Si y )O 2 and has a value of between zero and about 0.3.
- unit empirical formula is used herein according to its common meaning to designate the simplest formula which gives the relative number of moles of titanium and silicon which form TiO 2 and SiO 2 tetrahedral units of the titanium silicate molecular sieves of the instant invention and which form the molecular framework of the TiSO composition(s).
- the unit empirical formula is given in terms of titanium and silicon and oxygen as shown in Formula (1). above, and does not include other compounds, cations or anions which may be present as a result of the preparation or the existence of other impurities or materials in the bulk composition not containing the aforementioned tetrahedral unit.
- the amount of template R is reported as part of the composition when the as-synthesized unit empirical formula is given, and water may also be reported unless such is defined as the anhydrous form.
- coefficient "m” for template “R” is reported as a value that is normalized by dividing the number of moles of organic by the total moles of titanium and silicon.
- the unit empirical formula for a given TiSO can be calculated using the chemical analysis data for that TiSO.
- the over all composition of the as-synthesized TiSO is calculated using the chemical analysis data and expressed in terms of molar oxide ratios on an anhydrous basis.
- the unit empirical formula for a TiSO may be given on an "as-synthesized” basis or may be given after an "as-synthesized” TiSO composition has been subjected to some post treatment process, e.g., calcination.
- a preferred subclass of the TiSO compositions of formula 1 is when "m" has a value of 0.01 to about 0.3.
- the term "as-synthesized” herein shall be used to refer to the TiSO composition(s) formed as a result of the hydrothermal crystallization but before the TiSO composition has been subjected to post treatment to remove any volatile components present therein.
- the actual value of "m” for a post-treated TiSO will depend on several factors (including: the particular TiSO, template, severity of the post-treatment in terms of its ability to remove the template from the TiSO. the proposed application of the TiSO composition, and etc.) and the value for "m” can be within the range of values as defined for the as-synthesized TiSO compositions although such is generally less than the as-synthesized TiSO unless such post-treatment process adds template to the TiSO so treated.
- a TiSO composition which is in the calcined or other post-treatment form generally has an empirical formula represented by Formula (1), except that the value of "m” is generally less than about 0.02 and preferably less than 0.01. Under sufficiently severe post-treatment conditions, e.g. roasting in air at high temperature for long periods (over 1 hr.), the value of "m” may be zero (0) or, in any event, the template, R, is undetectable by normal analytical procedures.
- the TiSO molecular sieves of the instant invention are generally synthesized by hydrothermal crystallization from a reaction mixture comprising reactive sources of titanium, silicon, oxygen and preferably one or more organic templating agents.
- alkali metal(s) may be present in the reaction mixture.
- the reaction mixture is generally placed in a pressure vessel, preferably lined .with an inert plastic material, such as polytetrafluoroethylene. and heated, preferably under the autogenous pressure, at an effective temperature between about 50°C and about 250°C, until crystals of the molecular sieve product are obtained, usually for an effective period of from several hours to several weeks and typically an effective period of from about 2 hours to about 2 weeks.
- the TiSO may be isolated and washed with water and dried in air.
- the as-synthesized TiSO generally contains within its intracrystalline pore system at least one form of any template employed in its formation.
- the template is an organic molecular species, but it is possible, steric considerations permitting, that at least some of the template is present as a charge-balancing cation.
- the template is too large to move freely through the intracrystalline pore system of the formed TiSO and may be removed by a post-treatment process, such as by calcining the TiSO at temperatures of between about 200°C and to about 700oC so as to thermally degrade the template or by employing some other post-treatment process for removal of at least part of the template from the TiSO.
- a post-treatment process such as by calcining the TiSO at temperatures of between about 200°C and to about 700oC so as to thermally degrade the template or by employing some other post-treatment process for removal of at least part of the template from the TiSO.
- the pores of the TiSO are sufficiently large to permit transport of the template, and, accordingly, complete or partial removal thereof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites.
- the TiSO compositions are preferably formed from a reaction mixture containing reactive sources of TiO 2 and SiO 2 and an organic templating agent, said reaction mixture comprising a composition expressed in terms of molar oxide ratios of: aR 2 O:(Ti ⁇ Si y )O 2 :b H 2 O wherein "R” is an organic templating agent; "a” is an effective amount of “R” said effective amount being that amount which form said TiSO compositions and preferably being from greater than zero to about 50 and more preferably between about 0.5 and about 10; "b” is an effective amount of water and has a value of from zero to about 400.
- x and y represent the mole fractions, respectively of titanium and silicon in the (Ti x Si y )O 2 constituent and each have a value of at least 0.001 and are preferably at least 0.01.
- the reaction mixture from which these TiSOs are formed generally contain one or more organic templating agents (templates) which can be most any of those heretofore proposed for use in the synthesis of aluminosilicates and aluminophosphates.
- the template preferably contains at least one element of Group VA of the Periodic Table, particularly nitrogen, phosphorus, arsenic and/or antimony, mote preferably nitrogen or phosphorus and most preferably nitrogen and are of the formula R 4 X + wherein X is selected from the group consisting of nitrogen, phosphorus, arsenic and/or antimony and R may be hydrogen, alkyl, aryl.
- araalkyl, or alkylaryl group is preferably aryl or alkyl containing between 1 and 8 carbon atoms. although more than eight carbon atoms may be present in "R" of group of the template.
- Nitrogen-containing templates are preferred, including amines and quaternary ammonium compounds, the latter being represented generally by the formula R' 4 N + wherein each R' is an alkyl. aryl, alkylaryl. or araalkyl group; wherein R' preferably contains from 1 to 8 carbon atoms or higher when R' is alkyl and greater than 6 carbon atoms when R' is otherwise, as hereinbefore discussed.
- Polymeric quaternary ammonium salts such as [(C 14 H 32 N 2 ) (OH) 2 ] x wherein "x" has a value of at least 2 may also be employed.
- the mono-, di- and tri-amines, including mixed amines, may also be employed as templates either alone or in combination with a quaternary ammonium compound, quarternary phosphonium compound or another template.
- the exact relationship of various templates when concurrently employed is not clearly understood. Mixtures of two or more templating agents can produce either mixtures of TiSOs or in the instance where one template is more strongly directing than another template the more strongly directing template may control the course of the hydrothermal crystallization with the other template serving primarily to establish the pH conditions of the reaction mixture.
- Representative templates include: tetramethylammonium; tetraethylammonium; tetrapropylammonium; tetrabutylammonium ions; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylaraine; N,N-diethylethanolamine; dicyclohexylamine; N,N-dimethylethanolamine; 1,4-diazabicyclo (2,2,2) octane; N-methyldiethanolamine, N-raethylethanolamine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; di-n-butylamine, neopentylamine; di
- an alkoxide is the reactive titanium and/or silicon source
- the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not as yet been determined whether this alcohol participates in the synthesis process as a templating agent, or in some other function and, accordingly, is not reported as a template in the unit formula of the TiSOs, although such may be acting as templates.
- Alkali metal cations when present in the reaction mixture may facilitate the crystallization of certain TiSOs although the exact function of such cations in crystallization, if any, is not presently known.
- Alkali cations present in the reaction mixture generally appear in the formed TiSO compositions, either as occluded (extraneous) cations and/or as structural cations balancing net negative charges at various sites in the crystal lattice. It should be understood that although the unit formula for the TiSOs does not specifically recite the presence of alkali cations they are not excluded in the same sense that hydrogen cations and/or hydroxyl groups are not specifically provided for in the traditional formulae for zeolitic aluminosilicates. Most any reactive titanium source may be employed herein.
- the preferred reactive titanium sources include titanium alkoxides, water-soluble titanates. titanium chelates, titanate esters and titanium salts and the like.
- any reactive source of silicon can be employed herein.
- the preferred reactive, sources of silicon are silica, either as a silica sol or as fumed silica, a reactive solid amorphous precipitated silica, silica gel, alkoxides of silicon, silicic acid or alkali metal silicate and mixtures thereof.
- the X-ray patterns carried out herein and all other X-ray patterns appearing herein were obtained using either: (1) standard x-ray powder diffraction techniques; or (2) by use of using copper K-alpha radiation with computer based techniques using Siemens D-500 X-ray powder diffractometers, Siemens Type K-805 X-ray sources, available from Siemens Corporation, Cherry Hill. New Jersey, with appropriate computer interface.
- the radiation source is a high-intensity, copper target.
- the diffraction pattern from the copper K-alpha radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder.
- the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about ⁇ 0.4° on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art.
- TEAOH tetraethylammonium hydroxide
- TPAOH tetrapropylammonium hydroxide
- Methods A. B and C are as follows:
- LUDOX-LS and one-third of the water were blended to form a homogeneous mixture.
- the sodium hydroxide was dissolved in two-thirds of the water and mixed with the above mixture to form a homogeneous mixture.
- Titanium isopropoxide was blended into this mixture followed by the addition of the organic templating agent (tetrapropylammonium hydroxide). This mixture was then blended until a homogeneous mixture was observed.
- Method B is similar to Method A except that LUDOX-LS was blended with eighty percent of the water and the sodium hydroxide was blended with 20 percent of the water.
- LUDOX-AS ammonium hydroxide and water are blended to form a homogeneous mixture. Titanium isopropoxide is added to this mixture and blended to form a homogeneous mixture. Tetrabutylammonium hydroxide was added and the mixture again blended until a homogeneous mixture was observed.
- Table I sets forth the preparation of TiSO-45 and TiSO-48 wherein the various reagents are set forth by denominating the moles of each as follows: cR: dTiO 2 : eSiO 2 : fNaOH: gH 2 O where c, d, e. f and g represent the number of moles of organic templating agent R, TiO 2 , SiO 2 , NaOH and H 2 O, respectively.
- EXAMPLE 19 The TiSO-45 product from example 10 was calcined in air at 600oC for 1 hour and its .adsorption capacity determined. The adsorption capacities were measured using a standard McBain-Bakr gravimetric adsorption apparatus on samples activated in a vacuum at 350°C. The data for TiSO-45 were as follows:
- EDAX energy dispersive analysis by X-ray microprobe analysis was carried out on clean crystals (polished with diamond powder and carbon coated) on the TiSO product prepared in example 10.
- the EDAX microprobe analysis showed titanium present as an integral part of the crystal particle of the TiSO compositions.
- the relative amounts of SiO 2 , TiO 2 and Na 2 O expressed as a weight percent was as follows:
- EXAMPLE 21 a TiSO-45. as prepared in example 10, was subjected to x-ray analysis. TiSO-45 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth in Table II below:
- a calcined (air, 600oC. 1 hour) sample of the product of Example 10 and an calcined and acid washed (air, 600°C. 1 hour. IN HCl) were tested for catalytic cracking.
- the test procedure employed was the catalytic cracking of premixed two (2) mole % n-butane in helium stream in a 1/2" O.D. quartz tube reactor over up to about 5 grams (20-40 mesh) of the TiSO samples to be tested.
- the sample was activated in situ for 60 minutes at 500°C under 200 cm 3 /min dry helium purge.
- Example 1 of European Patent Application No. 82109451.3 was repeated with the starting reaction mixture having a composition based on molar ratios of:
- the two samples were then analyzed by SEM (scanning electron microscope) and EDAX (energy dispersive analysis by X-ray) microprobe.
- SEM scanning electron microscope
- EDAX energy dispersive analysis by X-ray microprobe.
- the SEM probe of the two samples showed four morphologies to be present and such are shown in FIG. 1.
- the four morphologies of the two samples prepared in accordance with the European application and the EDAX microprobe analysis for each morphology was as follows:
- Needles or fine rods had an EDAX microprobe of: Average of Spot Probes Ti 0.05
- Tables X and XI shows an X-ray pattern typical of a ZSM-5 type product and can be attributed to the smooth, integrown hexagonal particles which contained no titanium.
- Two samples were calcined with a separate portion of each sample being calcined in air 540oC for sixteen hours. These calcination conditions correspond to those employed in European Application No. 82109451.3.
- the X-ray patterns of the calcined products were as follows:
- the X-ray diffraction patterns of the calcined samples show a ZSM-5 type pattern with only slight differences from the as-synthesized.
- chemical analysis (bulk) of a portion of the calcined samples 1 and 2 are carried out the following is obtained:
- the TiSO compositions of this invention have unique surface characteristics making them useful as molecular sieves and as catalyst or as bases for catalysts in a variety of separation, hydrocarbon conversion and oxidative combustionprocesses.
- the TiSO composition can be impregnated or otherwise associated with catalytically active metals by the numerous methods known in the art and used, for example, in fabricating catalysts compositions containing alumina or aluminosilicate materials.
- TiSO's may be employed for separating molecular species in admixture with molecular species of a different degree of polarity or having different kinetic diameters by contacting such mixtures with a TiSO(s) having pore diameters large enough to adsorb at least one but not all molecular species of the mixture based on the polarity of the adsorbed molecular species and/or its kinetic diameter.
- TiSOs are employed for such separation processes the TiSOs are at least partially activated whereby some molecular species selectively enter the intracrystalline pore system thereof.
- the hydrocarbon conversion reactions catalyzed by TiSO compositions include; cracking, hydrocracking; alkylation of both the aromatic and isoparaffin types; isomerization (including xylene isomerization); polymerization; reforming; hydrogenation; dehydrogenation; transalkylation; dealkylation; and hydration.
- a TiSO containing catalyst compositions contains a hydrogenation promoter
- a hydrogenation promoter may be platinum, palladium, tungsten, nickel or molybdenum and may be used to treat various petroleum stocks including heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks. These stocks can be hydrocracked at temperatures in the range of between about 400°F and about 825°F using molar ratios of hydrogen to hydrocarbon in the range of between about 2 and about 80. pressures between about 10 and about 3500 p.s.i.g., and a liquid hourly space velocity (LHSV) of between about 0.1 and about 20. preferably between about 1.0 and about 10.
- LHSV liquid hourly space velocity
- TiSO containing catalyst compositions may also be employed in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures between about 700oF and about 1000°F.
- hydrogen pressures of between about 100 and about 500 p.s.i.g., LHSV values in the range between about 0.1 and about 10 and hydrogen to hydrocarbon molar ratios in the range between about 1 and about 20, preferably between about 4 and about 12.
- TiSO containing catalysts which contain hydrogenation promoters are also useful in hydroisomerization processes wherein the feedstock(s). such as normal paraffins, is converted to saturated branched-chain isomers.
- Hydroisomerization processes are typically carried out at a temperature between about 200°F and about 600°F. preferably between about 300°F and about 550oF with an LHSV value between about 0.2 and about 1.0.
- Hydrogen is typically supplied to the reactor in admixture with the hydrocarbon feedstock in molar proportions of hydrogen to the feedstock of between about 1 and about 5.
- TiSO-containing compositions similar to those employed for hydrocracking and hydroisomerization may also be employed at between about 650°F and about 1000oF.
- the paraffin feedstock comprises normal paraffins having a. carbon number range of C 7 -C 20 .
- the contact time between the feedstock and the TiSO containing catalyst is generally relatively short to avoid undersirable side reactions such as olefin polymerization and paraffin cracking. LHSV values in the range between about 0.1 and about 10, preferably between about 1.0 and about 6.0 are suitable.
- the low alkali metal content (often not measurable by current analytical techniques) of the instant TiSO compositions make them particularly well suited for use in the conversion of alkylaromatic compounds, particularly for use in the catalytic disproportionation of toluene, xylene. trimethylbenzenes. tetramethylbenzenes and the like. In such disproportionation processes it has been observed that isomerization and transalkylation can also occur.
- the TiSO-containing catalysts for such processes will typically include Group VIII noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and chromium which are preferably included in such, catalyst compositions in amounts between about 3 and about 15 weight-% of the overall catalyst composition.
- Extraneous hydrogen can, but need not be present in the reaction zone which is maintained at a temperature between about 400 and about 750°F, pressures in the range between about 100 and about 2000 p.s.i.g. and LHSV values in the range between about 0.1 and about 15.
- TiSO containing catalysts may be employed in catalytic cracking processes wherein such are preferably employed with feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residues etc. with gasoline being the principal desired product.
- Temperature conditions are typically between about 850 and about 1100oF.
- LHSV values between about 0.5 and about 10 pressure conditions are between about 0 p.s.i.g. and about 50 p.s.i.g.
- TiSO containing catalysts may be employed for dehydrocyclization.
- reactions which employ paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like.
- Dehydrocyclization processes are typically carried out using reaction conditions similar to those employed for catalytic cracking. For such processes it is preferred to use a Group VIII non-noble metal cation such as cobalt and nickel in conjunction with the TiSO composition.
- TiSO containing catalysts may be employed in catalytic dealkylation where paraffinic side chains are cleaved from aromatic nuclei without substantially hydrogenating the ring structure at relatively high temperatures in the range between about 800°F and about 1000°F at moderate hydrogen pressures between about 300 and about 1000 p.s.i.g. with other conditions being similar to those described above for catalytic hydrocracking.
- TiSO containing catalysts for catalytic dealkylation are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.
- TiSO containing catalysts may be used in catalytic hydrofining wherein the primary objective is to provide for the selective hydrodecomposition of organic sulfur and/or nitrogen compounds without substantially affecting hydrocarbon molecules present therewith. For this purpose it is preferred to employ the same general conditions described above for catalytic hydrocracking.
- the catalysts are the same typically of the same general nature as described in connection with dehydrocyclization operations.
- Feedstocks commonly employed for catalytic hydroforming include: gasoline fractions; kerosenes; jet fuel fractions; diesel fractions; light and heavy gas oils; deasphalted crude oil residua; and the like.
- the feedstock may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of nitrogen.
- TiSO containing catalysts may be employed for isomerization processes under conditions similar to those described above for reforming although isomerization processes tend to require somewhat more acidic catalysts than those employed in reforming processes.
- Olefins are preferably isomerized at temperatures between about 500°F and about 900°F. while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures between about 700°F and about 1000°F.
- Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptane and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cylcohexane, meta-xylene and/or ortho-xylene to para-xylene.
- the preferred cation form is a combination of a TiSO with polyvalent metal compounds (such as sulfides) of metals of Group II-A.
- Group II-B and rare earth metals For alkylation and dealkylation processes TiSO compositions having pores of at least 5A are preferred.
- the temperature is usually at least 350°F and ranges up to a temperature at which substantial cracking of the feedstock or conversion products occurs, generally up to about 700°F.
- the temperature is preferably at least 450°F and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the liquid state.
- the temperature can be as low as 250°F but is preferably at least 350°F. In alkylation of benzene, toluene and xylene.
- the preferred alkylation agents are olefins such as ethylene and propylene.
- the TiSO compositions of this invention may be employed in conventional molecular sieving processes as heretofore have been carried out usingaluminosilicate, aluminophosphate or other commonly employed molecular sieves.
- TiSO compositions are preferably activated prior to their use in a molecular sieve process to remove any molecular species which may be present in the intracrystalline pore system as a result of synthesis or otherwise. For the TiSO compositions this is sometimes accomplished by thermally destroying the organic species present in an as-synthesized TiSO since such organic species may be too large to be desorbed by conventional means.
- the TiSO compositions of this invention are also useful as adsorbents and are capable of separating mixtures of molecular species both on the basis of molecular size (kinetic diameters) and based on the degree of polarity of the molecular species.
- the TiSO is chosen in view of the dimensions of its pores such that at least the smallest molecular specie of the mixture can enter the intracrystalline void space while at least the largest specie is excluded.
- degree of polarity it is generally the case that the more hydrophilic TiSO will preferentially adsorb the more polar molecular species of a mixture having different degrees of polarity even though. both molecular species can communicate with the pore system of the TiSO.
Abstract
Des tamis moléculaires de titane-silicate sont utilisés en tant que tamis moléculaires et en tant que compositions de catalyse dans la conversion d'hydrocarbures et dans d'autres processus. Les tamis moléculaires ont une formule empirique unitaire sur une base anhydre de mR: (TixSiy)O2, dans laquelle "R" représente au moins un agent organique de calibrage; "m" représente les moles de "R" présentes par mole de (TixSiy)O2; et "x" et "y" représentent les fractions de moles de titane et de silicium, respectivement, présentes en tant qu'oxydes tétraédriques.Titanium silicate molecular sieves are used as molecular sieves and as catalyst compositions in the conversion of hydrocarbons and in other processes. The molecular sieves have a unit empirical formula on an anhydrous basis of mR: (TixSiy) O2, in which "R" represents at least one organic sizing agent; "m" represents the moles of "R" present per mole of (TixSiy) O2; and "x" and "y" represent the mole fractions of titanium and silicon, respectively, present as tetrahedral oxides.
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US60423584A | 1984-04-26 | 1984-04-26 | |
US604235 | 1984-04-26 |
Publications (1)
Publication Number | Publication Date |
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EP0179875A1 true EP0179875A1 (en) | 1986-05-07 |
Family
ID=24418770
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP85902353A Withdrawn EP0179875A1 (en) | 1984-04-26 | 1985-04-26 | Titanium-silicate compositions |
Country Status (6)
Country | Link |
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EP (1) | EP0179875A1 (en) |
JP (1) | JPS61501981A (en) |
AU (1) | AU580780B2 (en) |
BR (1) | BR8506684A (en) |
CA (1) | CA1254189A (en) |
WO (1) | WO1985004853A1 (en) |
Families Citing this family (15)
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 |
FR2629443B1 (en) * | 1988-03-30 | 1990-12-07 | Rhone Poulenc Chimie | ZEOLITES OF MFI STRUCTURE BASED ON SILICA AND TITANIUM OXIDE, CATALYSTS CONTAINING SAME AND PROCESS FOR PRODUCING THE SAME |
DE3880369T2 (en) * | 1987-05-22 | 1993-08-05 | Rhone Poulenc Chimie | ZEOLITE WITH MFI STRUCTURE BASED ON SILICONE AND TITANIUM OXIDE AND METHOD FOR THE SYNTHESIS THEREOF. |
US4853202A (en) * | 1987-09-08 | 1989-08-01 | Engelhard Corporation | Large-pored crystalline titanium molecular sieve zeolites |
IT1222868B (en) * | 1987-10-12 | 1990-09-12 | Montedipe Spa | METHOD FOR THE PREPARATION OF TITANIUM SILICALITES |
FR2622574B1 (en) * | 1987-10-29 | 1990-02-23 | Rhone Poulenc Chimie | PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS |
EP0372132B1 (en) * | 1988-12-06 | 1993-01-13 | Engelhard Corporation | Small-pored crystalline titanium molecular sieve zeolites |
US5015453A (en) * | 1989-04-28 | 1991-05-14 | W. R. Grace & Co.-Conn. | Crystalline group IVA metal-containing molecular sieve compositions |
DE4138155A1 (en) * | 1991-11-21 | 1993-05-27 | Basf Ag | METHOD FOR PRODUCING ESSENTIALLY ALKALIFIED TITANICILICATE CRYSTALS WITH ZEOLITE STRUCTURE |
DE4322022A1 (en) * | 1993-07-02 | 1995-01-12 | Basf Ag | Crystalline oxides of titanium |
DE69426017T2 (en) * | 1993-12-20 | 2001-05-17 | Nippon Catalytic Chem Ind | Process for the preparation of aryl esters |
AU4108896A (en) * | 1994-11-18 | 1996-06-17 | Advanced Manufacturing Center At Cleveland State University, The | Air separation process |
EP1129992A1 (en) * | 2000-03-02 | 2001-09-05 | Degussa AG | Process for the preparation of a titanium-containing zeolite |
EP1129991A1 (en) * | 2000-03-02 | 2001-09-05 | Degussa AG | Process for the preparation of a titanium-containing zeolite |
CN114365953B (en) * | 2021-12-27 | 2023-07-28 | 浙江福腾宝家居用品有限公司 | Pot cover and cooking utensil |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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IT1096596B (en) * | 1978-06-22 | 1985-08-26 | Snam Progetti | SYNTHETIC SILICA-BASED MATERIAL |
GR66589B (en) * | 1978-06-22 | 1981-03-30 | Snam Progetti | |
IT1127311B (en) * | 1979-12-21 | 1986-05-21 | Anic Spa | SYNTHETIC, CRYSTALLINE, POROUS MATERIAL CONSTITUTED BY SILICON AND TITANIUM OXIDES, METHOD FOR ITS PREPARATION AND ITS USES |
EP0132550A1 (en) * | 1983-06-27 | 1985-02-13 | Norton Company | Novel zeolite and process for preparation |
-
1985
- 1985-04-26 EP EP85902353A patent/EP0179875A1/en not_active Withdrawn
- 1985-04-26 JP JP60501933A patent/JPS61501981A/en active Pending
- 1985-04-26 BR BR8506684A patent/BR8506684A/en unknown
- 1985-04-26 AU AU42931/85A patent/AU580780B2/en not_active Ceased
- 1985-04-26 CA CA000480178A patent/CA1254189A/en not_active Expired
- 1985-04-26 WO PCT/US1985/000750 patent/WO1985004853A1/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO8504853A1 * |
Also Published As
Publication number | Publication date |
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AU580780B2 (en) | 1989-02-02 |
CA1254189A (en) | 1989-05-16 |
BR8506684A (en) | 1986-04-15 |
WO1985004853A1 (en) | 1985-11-07 |
JPS61501981A (en) | 1986-09-11 |
AU4293185A (en) | 1985-11-15 |
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