WO1998056718A1 - Aluminosilicate of utd-1 structure type - Google Patents

Aluminosilicate of utd-1 structure type Download PDF

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Publication number
WO1998056718A1
WO1998056718A1 PCT/EP1998/003704 EP9803704W WO9856718A1 WO 1998056718 A1 WO1998056718 A1 WO 1998056718A1 EP 9803704 W EP9803704 W EP 9803704W WO 9856718 A1 WO9856718 A1 WO 9856718A1
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WIPO (PCT)
Prior art keywords
aluminosilicate
range
silicon
aluminium
borosilicate
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PCT/EP1998/003704
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French (fr)
Inventor
Carolus Maria Van Ballegoy
Alexei Grigorievich Gabrielov
Theodorus Ludovicus Michael Maesen
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Shell Internationale Research Maatschappij B.V.
Shell Canada Limited
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Application filed by Shell Internationale Research Maatschappij B.V., Shell Canada Limited filed Critical Shell Internationale Research Maatschappij B.V.
Priority to AU84388/98A priority Critical patent/AU8438898A/en
Publication of WO1998056718A1 publication Critical patent/WO1998056718A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • 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
    • C01B39/12—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 replacing atoms being at least boron atoms
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers

Definitions

  • the present invention relates to a crystalline aluminosilicate and process for its preparation, a crystalline borosilicate intermediate and process for its preparation, a catalyst composition containing the aluminosilicate and process for converting a hydrocarbonaceous feedstock using the catalyst composition.
  • UTD-1 an all-silica large pore molecular sieve
  • UTD-2 an all-silica large pore molecular sieve
  • III bis (pentamethylcyclopentadienyl) cobalt (III) cation
  • H2O/S1O2 60
  • Na+/S ⁇ 2 0.1
  • the X-ray diffraction pattern of UTD-1, m its as synthesized form, has values as shown in Table 1 and, in its calcined form (500 °C for 4 hours), has values as shown in Table 2.
  • the amount of aluminium added is only small and does not exceed 0.05 %w such that the gel mixture has an Si/Al ratio of the order of 350 (it is not stated whether this is a bulk ratio or framework ratio) .
  • Both the all-silica and the aluminium-containing forms of UTD-1 are said to demonstrate catalytic activity for the conversion of methanol to hydrocarbons at 400 °C.
  • an aluminosilicate having in its calcined form a silicon to aluminium bulk molar ratio in the range from 10 to 50 and an X-ray diffraction pattern including values substantially as set forth in the table below :
  • the X-ray diffraction data specified in the above table and also hereinafter in the present specification were collected with a Phillips diffraction system, equipped with a proportional solid state detector, using copper K-alpha (K ⁇ ) radiation.
  • the diffraction data were recorded by step scanning at 0.025 degrees (°) of two theta (2 ⁇ ) , where theta ( ⁇ ) is the Bragg angle, and a counting time of 1 second for each step.
  • the interplanar spacings (d) were calculated in Angstrom units (A) , and the relative intensities of the lines (I/I 0 is one hundredth of the intensity of the strongest line above the background noise) were derived with the use of a profile fitting routine (or second derivative algorithm) .
  • the intensities of some lines have been found to be variable depending on the water content of the aluminosilicate. Without being bound to any particular theory, it is believed that the more hydrated the aluminosilicate, the more water that accumulates m the pores of the aluminosilicate thereby resulting in weaker lines m the X-ray diffraction pattern and hence lower relative intensities.
  • the term "silicon to aluminium bulk molar ratio" m the present specification should be understood to mean the Si/Al molar ratio as determined on the basis of the total or overall amount of silicon and aluminium (framework and non-framework) present in the crystalline aluminosilicate.
  • the calcined aluminosilicate according to the present invention has a silicon to aluminium bulk molar ratio in the range from 10 to 50, preferably from 10 to 49, more preferably from 10 to 45, still more preferably from 10 to 40 and especially from 10 to 30.
  • the present invention further provides a process for the preparation of an aluminosilicate according to the invention which comprises l) sub ecting a borosilicate having in ts as synthesized form a silicon to boron bulk molar ratio m the range from 20 to 50 and an X-ray diffraction pattern including values substantially as set forth in the table below d (Angstrom) Relative Intensity,
  • steps (i) and (iii) may be carried out in air at elevated temperature, e.g. at a temperature in the range of from 200 to 800 °C, preferably from 400 to 650 °C for a period, e.g., from 1 to 48, preferably from 1 to 5, hours.
  • the calcination treatment in step (i) is preferably followed by an acid wash treatment using a mineral acid such as hydrochloric or nitric acid before the calcined product is contacted in step (ii) with a source of aluminium ions (Al-X) in such a manner as to effect alumination of the product.
  • a mineral acid such as hydrochloric or nitric acid
  • Al-X aluminium ions
  • Step (ii) may conveniently be carried out in a manner analogous to the contacting procedure described in US patent specification No. 4,912,073.
  • the calcined product is contacted with an aqueous solution, preferably mildly acidic, of an aluminium salt such as a sulphate, nitrate, chloride, fluoride or acetate.
  • the contacting may be conducted at relatively low temperature, e.g., in the range of from 25 to 125 °C, preferably from 50 to 100 °C, for a total period of time of, e.g., from 1 to
  • the present invention also provides a borosilicate intermediate product having in its as synthesized form a silicon to boron bulk molar ratio in the range of from 20 to 50, suitably from 20 to 40, and an X-ray diffraction pattern including values substantially as set forth in the table below
  • the present invention still further provides a process for the preparation of the borosilicate intermediate product which comprises crystallizing a synthesis gel mixture comprising a source of silicon dioxide (Si ⁇ 2), a source of boron (B) , a template and water (H2O) , wherein the synthesis gel mixture has a composition, expressed in molar ratios, as follows:
  • H 0/S ⁇ m the range from 10 to 80
  • Si/B in the range from 1.5 to 20 Si/template m the range from 4 to 10.
  • the process will typically involve heating to temperatures of from 90 to 200 °C, preferably from 120 to 200 °C, more preferably from 160 to 180 °C, a synthesis gel mixture comprising a source of silicon dioxide (e.g. fumed silica, colloidal silica, silica gel, tetraethyl orthosilicate or a zeolite such as a zeolite beta) , a source of boron (e.g. boron oxide, B2O3; metaboric acid,
  • silicon dioxide e.g. fumed silica, colloidal silica, silica gel, tetraethyl orthosilicate or a zeolite such as a zeolite beta
  • boron e.g. boron oxide, B2O3; metaboric acid
  • H 2 0/S ⁇ in the range from 10 to 60
  • the crystals of borosilicate obtained may vary considerably m size, e.g. from ⁇ 1 - 15 ⁇ (micron) m their largest dimension.
  • the process preferably yields borosilicate of small crystal size whose largest dimension does not exceed 5 ⁇ , i.e. from ⁇ 1 - 5 ⁇ , preferably from 0.1 - 5 ⁇ , more preferably from 0.1 - 3 ⁇ and particularly from 0.1 - l.O ⁇ , which can be advantageously used to prepare aluminosilicate of small crystal size which is more catalytically active.
  • the aluminosilicate according to the invention therefore comprises crystals whose largest dimension preferably does not exceed 3 ⁇ , more preferably does not exceed l ⁇ .
  • the borosilicate crystal size may be controlled using techniques conventional in the art. More particularly, it has been found that smaller crystal sizes can be obtained by utilizing a silica source having a high surface area and/or adding seed crystals to the synthesis gel mixture.
  • the seed crystals may be added as a dry solid, as a suspension of the crystals in an appropriate liquid or as a preformed gel.
  • the templates mentioned above are extremely costly and it is therefore highly desirable to recover as much of the unreacted template as possible from the crystallized synthesis gel mixture for re-use.
  • the mixture is filtered to separate a filtrate containing unreacted template from the crystals of borosilicate which are subsequently washed.
  • the template may be recovered by passing the filtrate over a basic AMBERLITE (AMBERLITE is a trade mark) IRA-440C(OH) column, either as untreated mother liquor or after removal of unreacted silica by precipitation with hydrochloric acid.
  • aluminosilicate according to the invention may be combined with one or more other components conventional in the art to form a catalyst composition for use in refinery processes, e.g., catalytic cracking, hydrocracking, reforming and hydrodewaxing.
  • the present invention provides a catalyst composition comprising an aluminosilicate according to the invention and a binder.
  • binder it is convenient to use an amorphous or crystalline inorganic oxide or a mixture of two or more such oxides .
  • suitable inorganic oxide binders include alumina, silica, magnesia, titania, zirconia, silica-alumina, silica-zirconia, silica-boria and mixtures thereof.
  • the catalyst composition of the present invention preferably contains from 1 to 90 %w (per cent by weight) , more preferably from 1 to 80 %w, of the aluminosilicate and from 10 to 99 %w, more preferably from 20 to 99 %w, of binder, based on the total dry weight of aluminosilicate and binder.
  • the catalyst composition contains from 10 to 70 %w of the aluminosilicate and from 30 to 90 %w binder, in particular from 20 to 50 %w of the aluminosilicate and from 50 to 80 %w binder, based on the total dry weight of aluminosilicate and binder.
  • the present catalyst composition may further comprise at least one hydrogenation metal component.
  • hydrogenation metal components that may suitably be used include Group VI (e.g. molybdenum and tungsten) and Group VIII metals (e.g. cobalt, nickel, iridium, platinum and palladium) , their oxides and sulphides and combinations thereof.
  • the catalyst composition will preferably contain at least two hydrogenation metal components such as a molybdenum and/or tungsten component in combination with a cobalt and/or nickel component. Particularly preferred combinations are nickel/tungsten and nickel/molybdenum. Very advantageous results are obtained when the metal sulphides are used.
  • the catalyst composition may contain up to 50 parts by weight of hydrogenation metal component, calculated as metal per 100 parts by weight of total catalyst composition.
  • the catalyst composition may contain from 2 to 40, more preferably from 5 to 25 and especially from 10 to 20, parts by weight of Group VI metal (s) and/or from 0.05 to 10, more preferably from 0.5 to 8 and advantageously from 2 to 6, parts by weight of Group VIII metal (s), calculated as metal per 100 parts by weight of total catalyst composition.
  • the present catalyst composition may be prepared in accordance with techniques conventional in the art.
  • a convenient method for preparing a catalyst composition for use in cracking comprises mixing binder material with water to form a slurry or sol, adjusting the pH of the slurry or sol as appropriate and then adding powdered aluminosilicate as defined above together with additional water to obtain a slurry or sol with a desired solids concentration.
  • the slurry or sol is then spray-dried.
  • the spray-dried particles thus formed may be used directly or may be calcined prior to use.
  • One method for preparing a catalyst composition for use in hydrocracking comprises mulling an aluminosilicate as defined above and binder in the presence of water and optionally a peptizing agent, extruding the resulting mixture into pellets and calcining the pellets.
  • the pellets thus obtained are then impregnated with one or more solutions of Group VI and/or Group VIII metal salts and again calcined.
  • the aluminosilicate and binder may be co-mulled in the presence of one or more solutions of Group VI and/or Group VIII metal salts and optionally a peptizing agent, and the mixture so formed extruded into pellets. The pellets may then be calcined.
  • the present invention also provides a process for converting a hydrocarbonaceous feedstock into lower boiling materials which comprises contacting the feedstock at elevated temperature with a catalyst composition according to the invention.
  • the hydrocarbonaceous feedstocks useful in the present process can vary within a wide boiling range. They include lighter fractions such as kerosene fractions as well as heavier fractions such as gas oils, coker gas oils, vacuum gas oils, deasphalted oils, long and short residues, catalytically cracked cycle oils, thermally or catalytically cracked gas oils, and syncrudes, optionally originating from tar sands, shale oils, residue upgrading processes or biomass. Combinations of various hydrocarbon oils may also be employed.
  • the feedstock will generally comprise hydrocarbons having a boiling point of at least 330 °C . In a preferred embodiment of the invention, at least 50 %w of the feedstock has a boiling point above 370 °C .
  • the feedstock may have a nitrogen content of up to about 5000 ppmw (parts per million by weight) and a sulphur content of up to about 6 %w.
  • nitrogen contents can be in the range of from 250 to 2000 ppmw and sulphur contents can be in the range of from 0.2 to 5 %w.
  • a pretreatment for example, hydrode- nitrogenation, hydrodesulphurization or hydrode- metallization, methods for which are known in the art. If the process is carried out under catalytic cracking conditions (and therefore in the absence of added hydrogen) , the process is conveniently carried out in an upwardly or downwardly moving catalyst bed, e.g.
  • Thermofor Catalytic Cracking (TCC) or Fluidized Catalytic Cracking (FCC) processes.
  • the process conditions are preferably a reaction temperature within the range of from 400 to 900 °C, more preferably from 450 to 800 °C and especially from 500 to
  • a total pressure within the range of from 1 x 10 ⁇ to 1 x 10 6 Pa (1 to 10 bar), in particular from 1 x 10 5 to 7.5 x 10 ⁇ Pa (1 to 7.5 bar); a catalyst composition/- feedstock weight ratio (kg/kg) within the range from 5 to 150, especially 20 to 100; and a contact time between catalyst composition and feedstock of from 0.1 to 10 seconds, advantageously from 1 to 6 seconds.
  • the process according to the present invention is preferably carried out under catalytic hydrocracking conditions (and therefore in the presence of added hydrogen) .
  • reaction temperature is preferably in the range of from 250 to 500 °C, more preferably from 300 to 450 °C and especially from 350 to 450 °C .
  • the total pressure is preferably in the range of from 5 x 10 6 to 3 x 10 7 Pa (50 to 300 bar), more preferably from 7.5 x 10 6 to 2.5 x 10 7 Pa (75 to 250 bar) and even more preferably from 1 x 10 7 to 2 x 10 7 Pa (100 to 200 bar) .
  • the hydrogen partial pressure is preferably within the range of from 2.5 x 10 6 to 2.5 x 10 7 Pa (25 to
  • a space velocity is preferably in the range of from 0.05 to 10 kg feedstock per litre catalyst composition per hour (kg .1 " X . h- ⁇ ) is conveniently used. More preferably the space velocity is in the range of from 0.1 to 8, particularly from 0.1 to 5, kg.l _1 .h _1 .
  • total gas rates is preferably in the range of from 100 to 5000 Nl/kg are conveniently employed.
  • the total gas rate employed is in the range of from 250 to 2500 Nl/kg.
  • Example 1 (i) Preparation of a template
  • the template bis (pentamethylcyclopentadienyl) cobalt (III) hydroxide [Cp*2CoOH] , was prepared by dissolving bis (pentamethylcyclopentadienyl) cobalt (III) hexafluorophos-phate [Cp*2CoPFg] (200 g, commercially available from STREN) in a solution of 10% w water in acetone. This solution was then ion exchanged using an acidic DOWEX-50W (DOWEX-50W is a trade mark) cation resin exchanger (2 kg) to remove hexafluorophosphoric acid
  • TEOS tetraethyl orthosilicate
  • Si(OC2H5) tetraethyl orthosilicate
  • the solution was added to a 15.1 %w solution of Cp*2CoOH prepared as described in (i) above (12.81 g) together with 0.1 %w of wetted, ground, borosilicate seeds and stirred for half an hour to produce a synthesis gel mixture having the following molar composition:
  • TEFLON is a trade mark
  • Parr a TEFLON -lined pressure reactor
  • the reactor was heated at 175 °C under static conditions for seven days to yield, after filtration and water washing, a yellow crystalline product comprising 3-5 ⁇ , (micron) long crystals of a borosilicate (as determined using Scanning Electron Microscopy, SEM) having a Si/B bulk molar ratio of 38.0 (as determined using Inductively Coupled Plasma Atomic Emission Spectroscopy, ICPAES, after dissolution in an aqueous solution of a base) .
  • SEM Scanning Electron Microscopy
  • ICPAES Inductively Coupled Plasma Atomic Emission Spectroscopy
  • the X-ray diffraction pattern of the borosilicate product was found to contain lines at the d-spacings shown in Table 3 following, where the symbols w (weak), m (medium), s (strong) and vs (very strong) denote relative intensity values (I/I 0 x 100) in the ranges respectively of 1-20, 20-40, 40-60 and 60-100.
  • step (ii) a borosilicate was prepared as follows.
  • the synthesis mixture was then transferred to a TEFLON-lined pressure reactor (Parr) .
  • the reactor was heated at 175 °C under static conditions for two days to yield, after filtration and water washing, a yellow crystalline product comprising 0.8-1.0 ⁇ (micron) long crystals of a borosilicate (as determined using SEM) having a Si/B bulk molar ratio of 37.8 (as determined using ICPAES) .
  • the borosilicate product was found to have an X-ray diffraction pattern as shown in Table 3 above .
  • Example 3 The method of Example 2 was repeated except that the synthesis mixture was heated at 175 °C, with stirring, in a pressure reactor for two days to yield, after filtration and water washing, a yellow crystalline product comprising 0.8-1.0 ⁇ (micron) long crystals of a borosilicate (as determined using SEM) having a Si/B bulk molar ratio of 37.8 (as determined using ICPAES).
  • the borosilicate product was found to have an X-ray diffraction pattern as shown in Table 3 above.
  • Example 1 The method of Example 1 was repeated except that in step (ii) a borosilicate was prepared as below and no seeds were used.
  • Boron-zeolite beta (B-BEA) Si/B bulk molar ratio of B-BEA
  • the synthesis mixture was then transferred to a TEFLON-lined pressure reactor (Parr) .
  • the reactor was heated at 175 °C under static conditions for two days to yield, after filtration and water washing, a yellow crystalline product comprising 0.2-0.5 ⁇ (micron) long crystals of a borosilicate (as determined using SEM) having a Si/B bulk molar ratio of 39.2 (as determined using ICPAES) .
  • the borosilicate product was found to have an X-ray diffraction pattern as shown in Table 3 above .
  • a borosilicate was prepared as follows. A solution was formed by dissolving boric acid (0.67 g) in the 15.1 %w solution of CP2C0OH (33.21 g) . To this solution was added BINDZIL (BINDZIL is a trade mark) I5NH3/5OO silica sol (ex Akzo Nobel, 28.67 g) and thereafter water was removed to obtain a synthesis gel mixture having the following molar composition: 100Si ⁇ 2 : I5H3BO3 : 20Cp* 2 CoOH : 3000H 2 O
  • the synthesis mixture containing 0.1 %w of wetted, ground, borosilicate seeds, was then transferred to a TEFLON-lined pressure reactor (Parr) .
  • the reactor was heated at 175 °C under static conditions for two days to yield, after filtration and water washing, a yellow crystalline product comprising 0.8-1.0 ⁇ (micron) long crystals of a borosilicate (as determined using SEM) having a Si/B bulk molar ratio of 32.2 (as determined using ICPAES) .
  • the borosilicate product was found to have an X-ray diffraction pattern as shown in Table 3 above . Examples 6 to 10
  • borosilicates were prepared by methods analogous to Examples 1 to 5, details of which are given in Table 4 together with details of the borosilicates prepared in Examples 1 to 5.
  • 'TEOS' denotes tetraethyl orthosilicate
  • 'B-BEA' denotes boron-zeolite beta
  • 'sol' denotes BINDZIL silica sol.
  • the silicate obtained in (i) above was contacted with a 1M aqueous solution of aluminium nitrate (20 ml/g of silicate) at 90 °C for a certain period of time (6 hrs or 3 x 6 hrs) and then washed thoroughly with distilled water.
  • the solid was then reslurried in water (20 ml/g), to which small amounts of an aqueous ammonia solution (5 %w ammonia) were added to adjust the pH to between 7 and 8.
  • the solid was then filtered, washed with distilled water and finally calcined at 450 °C in air for one hour to yield a product comprising ⁇ l ⁇ (micron) long crystals of an aluminosilicate.
  • the bulk ratio of silicon to aluminium was determined by X-ray fluorescence, whilst the framework ratio of silicon to aluminium and the acidity were determined by monitoring temperature programmed desorption of isopropylamine (IPAm) from the aluminosilicate by thermogravimetric analysis (IPAm TPD-TGA) in a manner analogous to the methods of W.E. Farneth et al . , Chem. Rev. 95 (1995) 615; A.I. Biaglow et al., J. Catalysis, 144 (1993) 193; and A.I. Biaglow et al . , J. Catalysis, 151 (1995) 373.
  • IPAm TPD-TGA thermogravimetric analysis
  • the sample of aluminosilicate was initially heated in a pretreatment step to a temperature of 500 °C in flowing helium to remove water and other previously adsorbed volatile species that may have been present.
  • the sample was then cooled to 100 °C, still in the presence of helium, and then isopropylamine (molecular weight 59) was introduced, entrained in helium.
  • isopropylamine molecular weight 59
  • IPAm/gram aluminosilicate could be calculated according to the following equation
  • Example 8 The borosilicate obtained in Example 8 was treated as described in Example 11. After a 6 hour contact with the aluminium nitrate solution, it yielded a UTD-1 zeolite with Si/Al framework ratio of 32 mol/mol and a Si/Al bulk ratio of 15 mol/mol.

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Abstract

The invention provides a crystalline aluminosilicate and process for its preparation, a crystalline borosilicate intermediate and process for its preparation, a catalyst composition containing the aluminosilicate and process for converting a hydrocarbonaceous feedstock using the catalyst composition, the aluminosilicate having in its calcined form a silicon to aluminium bulk molar ratio in the range from 10 to 50 and an X-ray diffraction pattern including values substantially as set forth in the table (a).

Description

ALUMINOSILICATE OF UTD-1 STRUCTURE TYPE
The present invention relates to a crystalline aluminosilicate and process for its preparation, a crystalline borosilicate intermediate and process for its preparation, a catalyst composition containing the aluminosilicate and process for converting a hydrocarbonaceous feedstock using the catalyst composition.
US patent specifications Nos. 5,489,424 and 5,603,914 describe the preparation of five structurally different molecular sieves designated UTD-1, UTD-2, UTD-3, UTD-5 and UTD-6 using certain cobalt ion complexes as templates or structure-directing agents. UTD-1, an all-silica large pore molecular sieve, is prepared using bis (pentamethylcyclopentadienyl) cobalt (III) cation [Cp*2c°X as template, from a gel containing water, sodium hydroxide, silica and the template in the following molar ratios: H2O/S1O2 = 60, Na+/Sιθ2 = 0.1,
OH-/S1O2 = 0.2 and Cp* Co+/Sι02 = 0.1.
The X-ray diffraction pattern of UTD-1, m its as synthesized form, has values as shown in Table 1 and, in its calcined form (500 °C for 4 hours), has values as shown in Table 2.
Table 1 (UTD-1 as synthesized)
d (Angstrom) Relative Intensity,
I/I0 x 100
14.686 48
11.742 44
6.058 53
4.891 50
4.553 50
4.193 100
4.031 57
3.668 41
3.611 34
Table 2 (UTD-1 as calcined)
d (Angstrom) Relative Intensity,
I/I0 x 100
14.609 100
11.509 64
6.094 10
4.882 13
4.478 23
4.211 45
4.049 10
3.659 17
3.560 14
In the article entitled "Synthesis and Characterization of UTD-1: A Novel Zeolite Molecular Sieve" by Balkus et al . , Synthesis of Microporous Materials: Zeolites, Clays, Nanocomposites, H. Kessler and M. Ocelli (Eds.), Marcel Dekker, New York (1996) 77, there is a description of the preparation of samples of UTD-1 containing added aluminium. The UTD-1 is prepared as described in US patent specifications Nos. 5,489,424 and 5,603,914 except that one to ten drops of sodium aluminate solution are added to the synthesis (gel) mixture. The amount of aluminium added is only small and does not exceed 0.05 %w such that the gel mixture has an Si/Al ratio of the order of 350 (it is not stated whether this is a bulk ratio or framework ratio) . Both the all-silica and the aluminium-containing forms of UTD-1 are said to demonstrate catalytic activity for the conversion of methanol to hydrocarbons at 400 °C.
In another article by Balkus et al . entitled "The Synthesis and Characterization of UTD-1: The first large pore zeolite based on a 14-membered ring system", Studies in Surface Science and Catalysis, 105, (1997), 415, it is stated that, in addition to aluminium, also boron, titanium, vanadium and zinc can be incorporated into the structure of UTD-1 during synthesis. Furthermore, it is indicated that by removing the boron from B-UTD-1 using acid treatment and replacing with aluminium, Si/Al ratios closer to 50 are more accessible (whether these are bulk ratios or framework ratios is not specified) , although how this would be achieved in practice is not explained. It has now surprisingly been found possible to incorporate aluminium into the structure of UTD-1 at higher concentration than has previously been achieved in the prior art to obtain a crystalline aluminosilicate having very useful catalytic properties.
In accordance with the present invention, there is therefore provided an aluminosilicate having in its calcined form a silicon to aluminium bulk molar ratio in the range from 10 to 50 and an X-ray diffraction pattern including values substantially as set forth in the table below :
d (Angstrom) Relative Intensity,
I/I0 x 100
14.51 ± 0.29 w-vs
11.43 ± 0.23 w-s 9.45 ± 0.19 w
6.10 ± 0.12 w
4.88 ± 0.10 w
4.47 ± 0.09 w-m
4.21 ± 0.08 vs
3.96 ± 0.08 vs
The X-ray diffraction data specified in the above table and also hereinafter in the present specification were collected with a Phillips diffraction system, equipped with a proportional solid state detector, using copper K-alpha (Kα) radiation. The diffraction data were recorded by step scanning at 0.025 degrees (°) of two theta (2θ) , where theta (θ) is the Bragg angle, and a counting time of 1 second for each step. The interplanar spacings (d) were calculated in Angstrom units (A) , and the relative intensities of the lines (I/I0 is one hundredth of the intensity of the strongest line above the background noise) were derived with the use of a profile fitting routine (or second derivative algorithm) . No corrections were made for Lorenz and polarization effects. The relative intensities are given in terms of the symbols w (weak) , m (medium) , s (strong) and vs (very strong) which correspond respectively to I/IQ χ 100 values in the approximate ranges of 1-20, 20-40, 40-60 and 60-100.
In the X-ray diffraction pattern of the present aluminosilicate, the intensities of some lines (relative to the line at 4.21 ± 0.08 A), e.g. those at 14.51 ± 0.29 A and 11.43 ± 0.23 A, have been found to be variable depending on the water content of the aluminosilicate. Without being bound to any particular theory, it is believed that the more hydrated the aluminosilicate, the more water that accumulates m the pores of the aluminosilicate thereby resulting in weaker lines m the X-ray diffraction pattern and hence lower relative intensities. Conversely, the drier the aluminosilicate, the less water there is in the pores of the aluminosilicate thereby resulting in stronger lines in the X-ray diffraction pattern and hence higher relative intensities . Unless otherwise indicated, the term "silicon to aluminium bulk molar ratio" m the present specification should be understood to mean the Si/Al molar ratio as determined on the basis of the total or overall amount of silicon and aluminium (framework and non-framework) present in the crystalline aluminosilicate. The term
"silicon to boron bulk molar ratio" should be construed accordingly.
The calcined aluminosilicate according to the present invention has a silicon to aluminium bulk molar ratio in the range from 10 to 50, preferably from 10 to 49, more preferably from 10 to 45, still more preferably from 10 to 40 and especially from 10 to 30.
The present invention further provides a process for the preparation of an aluminosilicate according to the invention which comprises l) sub ecting a borosilicate having in ts as synthesized form a silicon to boron bulk molar ratio m the range from 20 to 50 and an X-ray diffraction pattern including values substantially as set forth in the table below d (Angstrom) Relative Intensity,
I/I0 x 100
14.71 ± 0.59 w-s
11.61 ± 0.35 w-s
7.28 ± 0.15 w-m
6.00 ± 0.12 w-m 4.88 ± 0.10 w-m 4.53 ± 0.09 m 4.17 ± 0.08 vs
4.01 ± 0.08 s
to a calcination treatment to obtain a calcined product,
(ii) contacting the calcined product with a source of aluminium ions (Al-X) in such a manner as to effect alumination of the product, and (iii) subjecting the aluminated product to a calcination treatment.
The calcination treatments of steps (i) and (iii) may be carried out in air at elevated temperature, e.g. at a temperature in the range of from 200 to 800 °C, preferably from 400 to 650 °C for a period, e.g., from 1 to 48, preferably from 1 to 5, hours.
The calcination treatment in step (i) is preferably followed by an acid wash treatment using a mineral acid such as hydrochloric or nitric acid before the calcined product is contacted in step (ii) with a source of aluminium ions (Al-X) in such a manner as to effect alumination of the product.
Step (ii) may conveniently be carried out in a manner analogous to the contacting procedure described in US patent specification No. 4,912,073. Thus, the calcined product is contacted with an aqueous solution, preferably mildly acidic, of an aluminium salt such as a sulphate, nitrate, chloride, fluoride or acetate. The contacting may be conducted at relatively low temperature, e.g., in the range of from 25 to 125 °C, preferably from 50 to 100 °C, for a total period of time of, e.g., from 1 to
40 hours, preferably from 5 to 20 hours. In general, it is preferred if the aluminated product obtained from the contacting step is washed with water before it is calcined according to step (iii) . The present invention also provides a borosilicate intermediate product having in its as synthesized form a silicon to boron bulk molar ratio in the range of from 20 to 50, suitably from 20 to 40, and an X-ray diffraction pattern including values substantially as set forth in the table below
d (Angstrom) Relative Intensity,
I/I0 x 100
14.71 ± 0.59 w-s
11.61 ± 0.35 w-s
7.28 ± 0.15 w-m
6.00 ± 0.12 w-m 4.88 ± 0.10 w-m 4.53 ± 0.09 m 4.17 ± 0.08 vs
4.01 ± 0.08 s 3.63 ± 0.07 m-s
The present invention still further provides a process for the preparation of the borosilicate intermediate product which comprises crystallizing a synthesis gel mixture comprising a source of silicon dioxide (Siθ2), a source of boron (B) , a template and water (H2O) , wherein the synthesis gel mixture has a composition, expressed in molar ratios, as follows:
H 0/Sι m the range from 10 to 80
Si/B in the range from 1.5 to 20 Si/template m the range from 4 to 10. The process will typically involve heating to temperatures of from 90 to 200 °C, preferably from 120 to 200 °C, more preferably from 160 to 180 °C, a synthesis gel mixture comprising a source of silicon dioxide (e.g. fumed silica, colloidal silica, silica gel, tetraethyl orthosilicate or a zeolite such as a zeolite beta) , a source of boron (e.g. boron oxide, B2O3; metaboric acid,
HBO2; boric acid, H3BO3; tetraboric acid, H3B4O7; fluoroboric acid, HBF4; or an alkali metal borate such as potassium or caesium borate) , a template for promoting the formation of a UTD-1 type structure (e.g. bis (tetramethylcyclopentadienyl) cobalt (III) ion or bis (pentamethylcyclopentadienyl) cobalt (III) ion), and water, the amounts of the reagents in the gel mixture, expressed m molar ratios, being preferably as follows:
H20/Sι in the range from 10 to 60
Si/B in the range from 2 to 10 Si/template in the range from 4 to 6. The crystals of borosilicate obtained may vary considerably m size, e.g. from <1 - 15μ (micron) m their largest dimension. However, the process preferably yields borosilicate of small crystal size whose largest dimension does not exceed 5μ, i.e. from <1 - 5μ, preferably from 0.1 - 5μ, more preferably from 0.1 - 3μ and particularly from 0.1 - l.Oμ, which can be advantageously used to prepare aluminosilicate of small crystal size which is more catalytically active. The aluminosilicate according to the invention therefore comprises crystals whose largest dimension preferably does not exceed 3μ, more preferably does not exceed lμ.
The borosilicate crystal size may be controlled using techniques conventional in the art. More particularly, it has been found that smaller crystal sizes can be obtained by utilizing a silica source having a high surface area and/or adding seed crystals to the synthesis gel mixture. The seed crystals may be added as a dry solid, as a suspension of the crystals in an appropriate liquid or as a preformed gel.
The templates mentioned above are extremely costly and it is therefore highly desirable to recover as much of the unreacted template as possible from the crystallized synthesis gel mixture for re-use. Thus, once crystallization is complete, the mixture is filtered to separate a filtrate containing unreacted template from the crystals of borosilicate which are subsequently washed. The template may be recovered by passing the filtrate over a basic AMBERLITE (AMBERLITE is a trade mark) IRA-440C(OH) column, either as untreated mother liquor or after removal of unreacted silica by precipitation with hydrochloric acid.
The aluminosilicate according to the invention may be combined with one or more other components conventional in the art to form a catalyst composition for use in refinery processes, e.g., catalytic cracking, hydrocracking, reforming and hydrodewaxing.
Accordingly, the present invention provides a catalyst composition comprising an aluminosilicate according to the invention and a binder.
As binder, it is convenient to use an amorphous or crystalline inorganic oxide or a mixture of two or more such oxides . Examples of suitable inorganic oxide binders include alumina, silica, magnesia, titania, zirconia, silica-alumina, silica-zirconia, silica-boria and mixtures thereof.
The catalyst composition of the present invention preferably contains from 1 to 90 %w (per cent by weight) , more preferably from 1 to 80 %w, of the aluminosilicate and from 10 to 99 %w, more preferably from 20 to 99 %w, of binder, based on the total dry weight of aluminosilicate and binder.
More preferably, the catalyst composition contains from 10 to 70 %w of the aluminosilicate and from 30 to 90 %w binder, in particular from 20 to 50 %w of the aluminosilicate and from 50 to 80 %w binder, based on the total dry weight of aluminosilicate and binder.
Depending on the application of the present catalyst composition (e.g. in hydrocracking) , it may further comprise at least one hydrogenation metal component. Examples of hydrogenation metal components that may suitably be used include Group VI (e.g. molybdenum and tungsten) and Group VIII metals (e.g. cobalt, nickel, iridium, platinum and palladium) , their oxides and sulphides and combinations thereof. The catalyst composition will preferably contain at least two hydrogenation metal components such as a molybdenum and/or tungsten component in combination with a cobalt and/or nickel component. Particularly preferred combinations are nickel/tungsten and nickel/molybdenum. Very advantageous results are obtained when the metal sulphides are used.
The catalyst composition may contain up to 50 parts by weight of hydrogenation metal component, calculated as metal per 100 parts by weight of total catalyst composition. For example, the catalyst composition may contain from 2 to 40, more preferably from 5 to 25 and especially from 10 to 20, parts by weight of Group VI metal (s) and/or from 0.05 to 10, more preferably from 0.5 to 8 and advantageously from 2 to 6, parts by weight of Group VIII metal (s), calculated as metal per 100 parts by weight of total catalyst composition.
The present catalyst composition may be prepared in accordance with techniques conventional in the art. A convenient method for preparing a catalyst composition for use in cracking comprises mixing binder material with water to form a slurry or sol, adjusting the pH of the slurry or sol as appropriate and then adding powdered aluminosilicate as defined above together with additional water to obtain a slurry or sol with a desired solids concentration. The slurry or sol is then spray-dried. The spray-dried particles thus formed may be used directly or may be calcined prior to use.
One method for preparing a catalyst composition for use in hydrocracking comprises mulling an aluminosilicate as defined above and binder in the presence of water and optionally a peptizing agent, extruding the resulting mixture into pellets and calcining the pellets. The pellets thus obtained are then impregnated with one or more solutions of Group VI and/or Group VIII metal salts and again calcined.
Alternatively, the aluminosilicate and binder may be co-mulled in the presence of one or more solutions of Group VI and/or Group VIII metal salts and optionally a peptizing agent, and the mixture so formed extruded into pellets. The pellets may then be calcined.
The present invention also provides a process for converting a hydrocarbonaceous feedstock into lower boiling materials which comprises contacting the feedstock at elevated temperature with a catalyst composition according to the invention.
The hydrocarbonaceous feedstocks useful in the present process can vary within a wide boiling range. They include lighter fractions such as kerosene fractions as well as heavier fractions such as gas oils, coker gas oils, vacuum gas oils, deasphalted oils, long and short residues, catalytically cracked cycle oils, thermally or catalytically cracked gas oils, and syncrudes, optionally originating from tar sands, shale oils, residue upgrading processes or biomass. Combinations of various hydrocarbon oils may also be employed. The feedstock will generally comprise hydrocarbons having a boiling point of at least 330 °C . In a preferred embodiment of the invention, at least 50 %w of the feedstock has a boiling point above 370 °C . The feedstock may have a nitrogen content of up to about 5000 ppmw (parts per million by weight) and a sulphur content of up to about 6 %w. Typically, nitrogen contents can be in the range of from 250 to 2000 ppmw and sulphur contents can be in the range of from 0.2 to 5 %w. It is possible and may sometimes be desirable to subject part or all of the feedstock to a pretreatment, for example, hydrode- nitrogenation, hydrodesulphurization or hydrode- metallization, methods for which are known in the art. If the process is carried out under catalytic cracking conditions (and therefore in the absence of added hydrogen) , the process is conveniently carried out in an upwardly or downwardly moving catalyst bed, e.g. in the manner of conventional Thermofor Catalytic Cracking (TCC) or Fluidized Catalytic Cracking (FCC) processes. The process conditions are preferably a reaction temperature within the range of from 400 to 900 °C, more preferably from 450 to 800 °C and especially from 500 to
650 °C; a total pressure within the range of from 1 x 10^ to 1 x 106 Pa (1 to 10 bar), in particular from 1 x 105 to 7.5 x 10^ Pa (1 to 7.5 bar); a catalyst composition/- feedstock weight ratio (kg/kg) within the range from 5 to 150, especially 20 to 100; and a contact time between catalyst composition and feedstock of from 0.1 to 10 seconds, advantageously from 1 to 6 seconds.
However, the process according to the present invention is preferably carried out under catalytic hydrocracking conditions (and therefore in the presence of added hydrogen) .
Thus, the reaction temperature is preferably in the range of from 250 to 500 °C, more preferably from 300 to 450 °C and especially from 350 to 450 °C .
The total pressure is preferably in the range of from 5 x 106 to 3 x 107 Pa (50 to 300 bar), more preferably from 7.5 x 106 to 2.5 x 107 Pa (75 to 250 bar) and even more preferably from 1 x 107 to 2 x 107 Pa (100 to 200 bar) .
The hydrogen partial pressure is preferably within the range of from 2.5 x 106 to 2.5 x 107 Pa (25 to
250 bar) , more preferably from 5 x 106 to 2 x 107 Pa (50 to 200 bar) and still more preferably from 6 x 10^ to
1.8 x 107 Pa (60 to 180 bar).
A space velocity is preferably in the range of from 0.05 to 10 kg feedstock per litre catalyst composition per hour (kg .1"X . h-^) is conveniently used. More preferably the space velocity is in the range of from 0.1 to 8, particularly from 0.1 to 5, kg.l_1.h_1.
Furthermore, total gas rates (gas/feed ratios) is preferably in the range of from 100 to 5000 Nl/kg are conveniently employed. Preferably, the total gas rate employed is in the range of from 250 to 2500 Nl/kg.
The present invention will now be illustrated by the following Examples. The crystal length, when quoted, represents the largest dimension of the crystal. Example 1 (i) Preparation of a template
The template, bis (pentamethylcyclopentadienyl) cobalt (III) hydroxide [Cp*2CoOH] , was prepared by dissolving bis (pentamethylcyclopentadienyl) cobalt (III) hexafluorophos-phate [Cp*2CoPFg] (200 g, commercially available from STREN) in a solution of 10% w water in acetone. This solution was then ion exchanged using an acidic DOWEX-50W (DOWEX-50W is a trade mark) cation resin exchanger (2 kg) to remove hexafluorophosphoric acid
(HPFg) . The resin exchanger was thereafter eluted with
3M hydrochloric acid (120 1) to remove the bis (pentamethylcyclo-pentadienyl) cobalt (III) cation
[Cp*2Co+_ • Evaporation of the eluant under reduced pressure yielded relatively pure bis (pentamethylcyclopentadienyl) cobalt (III) chloride [Cp*2CoCl] as a solid. The solid was then dissolved in as little water as possible to give a 0.2M solution and ion-exchanged on a basic Amberlite IRA-420C(OH) anion resin exchanger to form, after concentration, a 15.1 %w solution of Cp*2CoOH.
(ii) Preparation of a borosilicate
To a solution of boric acid (H3BO3, 0.26 g) in water
(19 ml) was added tetraethyl orthosilicate (TEOS, Si(OC2H5) ) (6.67 g) . After hydrolysis of the TEOS, the solution was added to a 15.1 %w solution of Cp*2CoOH prepared as described in (i) above (12.81 g) together with 0.1 %w of wetted, ground, borosilicate seeds and stirred for half an hour to produce a synthesis gel mixture having the following molar composition:
100SiO2 : I5H3BO3 : 20Cp*2CoOH : 5600H2O : 4OOC2H5OH
The synthesis mixture was then transferred to a TEFLON (TEFLON is a trade mark) -lined pressure reactor (Parr) . The reactor was heated at 175 °C under static conditions for seven days to yield, after filtration and water washing, a yellow crystalline product comprising 3-5μ, (micron) long crystals of a borosilicate (as determined using Scanning Electron Microscopy, SEM) having a Si/B bulk molar ratio of 38.0 (as determined using Inductively Coupled Plasma Atomic Emission Spectroscopy, ICPAES, after dissolution in an aqueous solution of a base) . The X-ray diffraction pattern of the borosilicate product was found to contain lines at the d-spacings shown in Table 3 following, where the symbols w (weak), m (medium), s (strong) and vs (very strong) denote relative intensity values (I/I0 x 100) in the ranges respectively of 1-20, 20-40, 40-60 and 60-100.
Table 3 (Borosilicate)
d (Angstrom) Relative Intensity,
I/I0 x 100
14.71 ± 0.59 w-s
11.61 ± 0.35 w-s
7.28 ± 0.15 w-m
6.00 ± 0.12 w-m 4.88 ± 0.10 w-m 4.53 ± 0.09 m 4.17 ± 0.08 vs
4.01 ± 0.08 s 3.63 ± 0.07 m-s
Example 2
The method of Example 1 was repeated except that in step (ii) a borosilicate was prepared as follows.
Firstly, a solution of boric acid (0.67 g) in a small amount of water was added to a 15.1 %w solution of Cp*2Co0H (33.21 g) . The mixture (A) thus formed was concentrated by evaporation of water until it weighed 16.22 g. Secondly, fumed silica (8 g, commercially available from Aldrich or Degussa) was mixed with water (19.4 g) to form a homogeneous slurry (B) .
Mixture A (16.22 g) and 0.1 %w of wetted, ground, borosilicate seeds were thereafter added to a portion of slurry B (14.72 g) with stirring to yield a homogeneous gel-like synthesis mixture having the following molar composition: 100SiO2 : I5H3BO3 : 20Cp*2CoOH . 1600H2O
The synthesis mixture was then transferred to a TEFLON-lined pressure reactor (Parr) . The reactor was heated at 175 °C under static conditions for two days to yield, after filtration and water washing, a yellow crystalline product comprising 0.8-1.0μ (micron) long crystals of a borosilicate (as determined using SEM) having a Si/B bulk molar ratio of 37.8 (as determined using ICPAES) . The borosilicate product was found to have an X-ray diffraction pattern as shown in Table 3 above . Example 3 The method of Example 2 was repeated except that the synthesis mixture was heated at 175 °C, with stirring, in a pressure reactor for two days to yield, after filtration and water washing, a yellow crystalline product comprising 0.8-1.0μ (micron) long crystals of a borosilicate (as determined using SEM) having a Si/B bulk molar ratio of 37.8 (as determined using ICPAES). The borosilicate product was found to have an X-ray diffraction pattern as shown in Table 3 above. Example 4
The method of Example 1 was repeated except that in step (ii) a borosilicate was prepared as below and no seeds were used. Boron-zeolite beta (B-BEA) (Si/B bulk molar ratio of
60) was thoroughly crushed and then slowly heated up at a rate of 5 °C/min in a nitrogen atmosphere to 600 °C and maintained at this temperature for two hours before being cooled to room temperature (20 °C) in a desiccator. The thus calcined B-BEA (0.9 g) was then added slowly and carefully over a period of five minutes to a vigorously stirred mixture of an aqueous solution of Cp*2c°0H (15.1 %w, 7.23 g) , deionized water (4.65 g) and boric acid (0.17 g) . Stirring was continued for a further hour, resulting in a synthesis gel mixture having the following molar composition: 100Siθ2 : 2OH3BO3 : 21.2Cp*2CoOH : 4000H O
The synthesis mixture was then transferred to a TEFLON-lined pressure reactor (Parr) . The reactor was heated at 175 °C under static conditions for two days to yield, after filtration and water washing, a yellow crystalline product comprising 0.2-0.5μ (micron) long crystals of a borosilicate (as determined using SEM) having a Si/B bulk molar ratio of 39.2 (as determined using ICPAES) . The borosilicate product was found to have an X-ray diffraction pattern as shown in Table 3 above . Example 5
The method of Example 1 was repeated except that in step (ii) a borosilicate was prepared as follows. A solution was formed by dissolving boric acid (0.67 g) in the 15.1 %w solution of CP2C0OH (33.21 g) . To this solution was added BINDZIL (BINDZIL is a trade mark) I5NH3/5OO silica sol (ex Akzo Nobel, 28.67 g) and thereafter water was removed to obtain a synthesis gel mixture having the following molar composition: 100Siθ2 : I5H3BO3 : 20Cp*2CoOH : 3000H2O
The synthesis mixture, containing 0.1 %w of wetted, ground, borosilicate seeds, was then transferred to a TEFLON-lined pressure reactor (Parr) . The reactor was heated at 175 °C under static conditions for two days to yield, after filtration and water washing, a yellow crystalline product comprising 0.8-1.0μ (micron) long crystals of a borosilicate (as determined using SEM) having a Si/B bulk molar ratio of 32.2 (as determined using ICPAES) . The borosilicate product was found to have an X-ray diffraction pattern as shown in Table 3 above . Examples 6 to 10
Further borosilicates were prepared by methods analogous to Examples 1 to 5, details of which are given in Table 4 together with details of the borosilicates prepared in Examples 1 to 5. In Table 4, 'TEOS' denotes tetraethyl orthosilicate, 'B-BEA' denotes boron-zeolite beta, and 'sol' denotes BINDZIL silica sol.
Table 4
Siθ2 H3BO3 Cp*2Co0H H2° Silica Synthesis Crystal Bulk molar Example (mole) (mole) (mole) (mole source time (days) length (μ) ratio Si/B No.
Figure imgf000021_0001
100 6 14 5600 TEOS 7 12-15 46.3 6 100 15 20 5600 TEOS 7 3-5 38.0 1 100 25 22 3600 TEOS 7 2 31.9 7 100 40 20 3600 TEOS 10 0.5-0.7 33.1 100 15 20 1600 Fumed 2 0.8-1.0 37.8 silica
100 15 20 1600 fumed 0.8-1.0 37.8 silica
100 20 21.2 4000 B-BEA 2 0.2-0.5 39.2 4 V0 100 40 21.2 4000 B-BEA 4 0.2-0.5 37.7 9 100 15 20 3000 Sol 2 0.5-0.7 32.2 5 100 45 30 3000 Sol 1.5 0.8-1.0 22.1 10
Figure imgf000021_0002
Example 11
(i) Preparation of a silicate
The borosilicate obtained in Example 1 above was calcined in air at 500 °C to decompose the template, Cp*2^oOH, into cobalt oxides. This was followed by twice leaching the calcined material with 12M hydrochloric acid (10 ml/g) at ambient temperature (20 °C) to effect substantially complete removal of cobalt and boron, thereby to yield a silicate material. (ii) Preparation of an aluminosilicate
The silicate obtained in (i) above was contacted with a 1M aqueous solution of aluminium nitrate (20 ml/g of silicate) at 90 °C for a certain period of time (6 hrs or 3 x 6 hrs) and then washed thoroughly with distilled water. The solid was then reslurried in water (20 ml/g), to which small amounts of an aqueous ammonia solution (5 %w ammonia) were added to adjust the pH to between 7 and 8. The solid was then filtered, washed with distilled water and finally calcined at 450 °C in air for one hour to yield a product comprising < lμ (micron) long crystals of an aluminosilicate. The X-ray diffraction pattern of each aluminosilicate product was found to have lines at the d-spacings indicated in Table 5 following, in which the symbols w (weak), m (medium), s (strong) and vs (very strong) denote relative intensity values (I/I0 x
100) in the ranges respectively of 1-20, 20-40, 40-60 and 60-100.
The bulk ratio of silicon to aluminium was determined by X-ray fluorescence, whilst the framework ratio of silicon to aluminium and the acidity were determined by monitoring temperature programmed desorption of isopropylamine (IPAm) from the aluminosilicate by thermogravimetric analysis (IPAm TPD-TGA) in a manner analogous to the methods of W.E. Farneth et al . , Chem. Rev. 95 (1995) 615; A.I. Biaglow et al., J. Catalysis, 144 (1993) 193; and A.I. Biaglow et al . , J. Catalysis, 151 (1995) 373.
Thus, the sample of aluminosilicate was initially heated in a pretreatment step to a temperature of 500 °C in flowing helium to remove water and other previously adsorbed volatile species that may have been present. After the pretreatment step, the sample was then cooled to 100 °C, still in the presence of helium, and then isopropylamine (molecular weight 59) was introduced, entrained in helium. Once the sample had reached a constant or near constant weight, the gas flow was switched back to pure helium and the sample began to lose weight as molecules of physisorbed isopropylamine began to desorb. When the sample had again reached a constant or near constant weight, a linear temperature ramp was initiated at a rate of 10 °C per minute. Thereafter, two separate weight losses were observed: a low temperature weight loss attributable to isopropylamine desorption from weak acid sites on the aluminosilicate, and a higher temperature weight loss attributable to isopropylamine desorption from stronger acid sites on the aluminosilicate. By measuring the higher temperature weight loss, the acidity (mostly Brensted acidity) of the aluminosilicate, expressed in units of millimole
IPAm/gram aluminosilicate, could be calculated according to the following equation
acidity (mmole/g) = weight loss (mg) x 1000
59 x sample weight (mg)
Once the acidity was known, the framework ratio of silicon to aluminium could then be calculated. The results are shown in Table 6 below. Table 5 (Aluminosilicate!
d (Angstrom) Relative Intensity, I/I0 x 100
14.51 ± 0.29 w-vs 11.43 ± 0.23 w-s 9.45 ± 0.19 w 6.10 ± 0.12 w 4.88 ± 0.10 w 4.47 ± 0.09 w-m 4.21 ± 0.08 vs 3.96 ± 0.08 m
Table 6
Figure imgf000024_0001
Example 12
The borosilicate obtained in Example 8 was treated as described in Example 11. After a 6 hour contact with the aluminium nitrate solution, it yielded a UTD-1 zeolite with Si/Al framework ratio of 32 mol/mol and a Si/Al bulk ratio of 15 mol/mol.

Claims

C L I M S
1. An aluminosilicate having in its calcined form a silicon to aluminium bulk molar ratio in the range of from 10 to 50 and an X-ray diffraction pattern including values substantially as set forth in the table below:
d (Angstrom) Relative Intensity,
I/I0 x 100
14.51 ± 0.29 w-vs
11.43 ± 0.23 w-s
9.45 ± 0.19 w
6.10 ± 0.12 w
4.88 ± 0.10 w
4.47 ± 0.09 w-m
4.21 ± 0.08 vs
3.96 ± 0.08 m
2. The aluminosilicate as claimed in claim 1, wherein the silicon to aluminium bulk molar ratio is in the range of from 10 to 40. 3. The aluminosilicate as claimed in claim 2, wherein the silicon to aluminium bulk molar ratio is in the of range from 10 to 30.
4. The aluminosilicate as claimed in any one of claims
1 to 3, comprising crystals whose largest dimension does not exceed 3 micron.
5. The aluminosilicate as claimed in claim 4, comprising crystals whose largest dimension does not exceed 1 micron.
6. A process for the preparation of an aluminosilicate as defined in claim 1, which comprises (i) subjecting a borosilicate having in its as synthesized form a silicon to boron bulk molar ratio in the range of from 20 to 50 and an X-ray diffraction pattern
d (Angstrom) Relative Intensity,
I/I0 x 100
14.71 ± 0.59 w-s
11.61 ± 0.35 w-s
7.28 ± 0.15 w-m
6.00 ± 0.12 w-m 4.88 ± 0.10 w-m 4.53 ± 0.09 m 4.17 ± 0.08 vs
4.01 ± 0.08 s 3.63 ± 0.07 m-s
to a calcination treatment to obtain a calcined product, (ii) contacting the calcined product with a source of aluminium ions (Al^+) under conditions effective to aluminate the calcined product thereby producing an aluminated product, and
(iii) subjecting the aluminated product to a calcination treatment .
7. A process as claimed in claim 6, wherein the calcined product is contacted with an aqueous solution of an aluminium salt.
8. A process as claimed in claim 7, wherein the aluminium salt is a sulphate, nitrate, chloride, fluoride or acetate.
9. A borosilicate having in its as synthesized form a silicon to boron bulk molar ratio in the range of from 20 to 50 and an X-ray diffraction pattern including values substantially as set forth in the table below
d (Angstrom) Relative Intensity, I/I0 x 100
14.71 ± 0.59 w-s
11.61 ± 0.35 w-s
7.28 ± 0.15 w-m
6.00 ± 0.12 w-m 4.88 ± 0.10 w-m 4.53 ± 0.09 m 4.17 ± 0.08 vs
4.01 ± 0.08 s 3.63 ± 0.07 m-s
10. A process for the preparation of a borosilicate as defined in claim 9, which comprises crystallizing a synthesis gel mixture comprising a source of silicon dioxide (Siθ2), a source of boron (B) , a template, and water (H2O) , wherein the synthesis gel mixture has a composition, expressed in molar ratios, as follows:
H20/Si in the range from 10 to 80
Si/B in the range from 1.5 to 20 Si/template in the range from 4 to 10.
11. A process as claimed in claim 10, wherein the template is bis (tetramethylcyclopentadienyl) cobalt (III) ion or bis (penta-methylcyclopentadienyl) cobalt (III) ion.
12. A process as claimed in claim 10 or claim 11, wherein the boron source is a (fluoro) boric acid, boron oxide or an alkali metal borate.
13. A catalyst composition comprising an aluminosilicate of claim 1 and a binder.
14. A catalyst composition as claimed in claim 13, which further comprises at least one hydrogenation metal component .
15. A process for converting a hydrocarbonaceous feedstock into lower boiling materials which comprises contacting the feedstock at elevated temperature with a catalyst composition as claimed in claim 13.
PCT/EP1998/003704 1997-06-12 1998-06-10 Aluminosilicate of utd-1 structure type WO1998056718A1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5489424A (en) * 1994-08-24 1996-02-06 Board Of Regents, The University Of Texas System Synthesis of novel molecular sieves using a metal complex as a template

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5489424A (en) * 1994-08-24 1996-02-06 Board Of Regents, The University Of Texas System Synthesis of novel molecular sieves using a metal complex as a template

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BALKUS KENNETH J. ET AL, STUDIES IN SURFACE SCIENCE AND CATALYSIS, vol. 105, 1997, pages 415 - 421, XP002081043 *

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