EP0333816A4 - Kristalline aluminiumphosphat-zubereitungen. - Google Patents

Kristalline aluminiumphosphat-zubereitungen.

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Publication number
EP0333816A4
EP0333816A4 EP19880908535 EP88908535A EP0333816A4 EP 0333816 A4 EP0333816 A4 EP 0333816A4 EP 19880908535 EP19880908535 EP 19880908535 EP 88908535 A EP88908535 A EP 88908535A EP 0333816 A4 EP0333816 A4 EP 0333816A4
Authority
EP
European Patent Office
Prior art keywords
compositions
mole
directing agent
source
precursor mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19880908535
Other languages
English (en)
French (fr)
Other versions
EP0333816A1 (de
Inventor
Mark E Davis
Juan M Garces
Carlos H Saldarriga
De Correa Maria Del Con Montes
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/207,850 external-priority patent/US5374411A/en
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0333816A1 publication Critical patent/EP0333816A1/de
Publication of EP0333816A4 publication Critical patent/EP0333816A4/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/04—Aluminophosphates [APO compounds]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO

Definitions

  • the present invention relates to crystalline aluminumphosphate compositions and in particular to large pore crystalline aluminumphosphate compositions and to a method for their preparation.
  • zeolitic type which comprises crystalline aluminosilicate molecular sieves
  • other molecular sieves which are not of this crystalline alumino ⁇ silicate composition.
  • the naturally occurring and synthetic analogues of the zeolites include over a hundred compositions.
  • Zeolites are, by definition, tectosilicates, which means that their framework comprises tridimensional structures made of SiOi j and AIO ⁇ ' ⁇ tetrahedra which share vertices with oxygen atoms.
  • the zeolites can be characterized as having porous structures with openings of uniform dimensions; ion-exchange capacity; and the capacity to reversibly adsorb and desorb molecules within the cavities present in the crystals via the pore openings. These pore openings are defined by the linkage of 10 ⁇ tetrahedra, wherein T represents either silicon or aluminum atoms.
  • Zeolites are synthesized in general by j . hydrothermal methods from reactive components in closed systems. A large inventory of empirical data on synthesis compositions and conditions leading to the formation of given zeolites is available in the literature. Practice has shown that a wide variety of 10 zeolitic products can be obtained from the same starting composition, depending on the raw materials, mixing methods, and crystallization procedures employed.
  • the present invention further provides
  • AI2O3 and P2O5 orm an oxide lattice
  • R p j- represents a structure-directing agent
  • x>0 the structures being further defined as having an X-ray powder diffraction pattern characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially 30 as shown in Table 1.
  • the present invention also provides a method of preparing these crystalline aluminumphosphate- compositions from a precursor mixture whose chemical 35 composition expressed in terms of mole ratios is A1 2 0 3 : 1.0+0.2 P 2 0 5 : 10-100 H 2 0,
  • a structure- directing agent for each mole of AI2O3, comprising the steps of admixing an aluminum source, a phosphorus source, and water to form the precursor mixture, admixing the precursor mixture with the structure- directing agent to form a reaction mixture, and reacting the reaction mixture under conditions such 10 that a crystalline aluminumphosphate composition, characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially as shown in Table 1 , is formed.
  • the present invention further provides crystalline metal substituted aluminumphosphate compositions having three-dimensional microporous crystal framework structures comprising a structure-
  • AI2O3, ?2 ⁇ 5 and MC ⁇ z/2 form n oxide lattice;
  • R is a structure-directing agent;
  • M is a metal;
  • z is the oxidation state of M; and
  • M0 z / 2 is at least one metal oxide;
  • the chemical composition further comprising one or more charge-compensating species;
  • the present invention provides a method of preparing these crystalline metal substituted aluminumphosphate compositions from a precursor mixture whose chemical composition expressed in terms of mole ratios is
  • M is a metal
  • z is the oxidation state of M
  • 0 z 2 is at least one metal oxide
  • the chemical composition further comprising from one or more charge- compensating species and 0.02 to 4 moles of a structure-directing agent for each mole of AI2O ; comprising the steps of admixing an aluminum source, a phosphorus source, a metal oxide source, and water to form a precursor mixture, admixing the precursor mixture with the structure-directing agent to form a reaction mixture, and reacting the reaction mixture under conditions such that a crystalline metal substituted aluminumphosphate composition, characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially as shown in Table 1 , is formed.
  • FIG 1 shows argon adsorption isotherms for the aluminumphosphates of the present invention, denoted "VPI-5", and for Zeolite X(Na) , which is used therein for comparison.
  • Zeolite X(Na) is described in U.S. Patent 2,882,244.
  • Figure 2 shows the effective pore diameters in Angstroms for the aluminumphosphates of the present invention, denoted VPI-5, and for Zeolite X(Na) .
  • the compositions of one embodiment of the present invention are synthetic, crystalline aluminumphosphate materials, hereafter denoted as "VPI- 5", which are capable of reversibly adsorbing and desorbing large molecules, such as triisopropylbenzene, in intracrystalline pores. These materials are comprised of three-dimensional microporous crystal framework structures.
  • aluminumphosphate materials can be characterized in a number of ways.
  • the basic chemical composition of the molecular sieves as expressed in terms of mole ratios is
  • compositions having a crystalline structure defined by the X-ray powder diffraction pattern having d spacings substantially as given in Table 1.
  • substantially means that the d spacings given in Table 1 are within the allowance for experimental error, and thus allow for differences attributable to variances in equipment and technique.
  • the Table shows the characteristic d-spacings of VPI-5 between about three degrees two-theta and about 40 degrees two-theta as measured using copper K-alpha radiation.
  • "Characteristic” and “characterizing” as used herein refer to those d spacings representing all peaks having intensities relative to the largest peak greater than or equal to about 10. These peaks are shown as having intensities described as "vs" for very strong or "m” for medium.
  • the d spacings remain substantially the same after VPI-5 samples are heated to at least about 600°C. This heating can take place, for example, under vacuum, in air, or in air/steam mixtures.
  • the experimental X-ray diffraction patterns were obtained in an automated powder diffraction unit using copper K-alpha radiation.
  • R represents a structure-directing agent used in the synthesis of the large pore material
  • x denotes the mole ratio value of R to AI2O , wherein x>0. Since the structure-directing agent is a part of the preparation process, as discussed below, its amount in the composition will depend in part on whether it has been subjected to partial desorption or decomposition.
  • argon adsorption isotherms of the VPI-5 aluminum phosphate of this invention and Zeolite X(Na) , described in U.S. Patent 2,882,244, are shown. These results were determined in an 0MNIS0RP* 360 instrument (*0MNIS0RP is a trademark of Omicron Technology Corporation) at liquid argon temperature.
  • Figure 2 shows effective pore diameters for VPI-5 and the Zeolite of U.S. Patent 2,882,244.
  • the adsorption isotherms and the pore size distributions were derived using Horvath-Kawazoe analysis (G.
  • Zeolite X(Na) is representative of the faujasite structure with pore openings limited by 12-membered ring tetrahedra whose accepted dimension is around 0.8 nm. This dimension is in good agreement with the value shown in Figure 2. It is evident that VPI-5 has pores substantially larger than Zeolite X(Na).
  • the VPI-5 compositions exhibit a crystalline structure with a pore system such that some of the pore space is large enough to allow the entry of molecules of triisopropylbenzene. Additional pore space is available to smaller molecules.
  • the metal substituted aluminumphosphates were also characterized via X-ray diffraction.
  • the observed powder patterns show the same characterizing d spacings as those obtained for the unsubstituted VPI-5, as shown in Table 1.
  • These metal substituted aluminumphosphates show similar molar ratios of AI2O3 to P 05 « In general these compositions are defined by the following molar ratios:
  • M is a metal
  • z is the oxidation state of M
  • M0 z / 2 is at least one metal oxide.
  • the formula showing the molar ratios of the silicoaluminumphosphate compositions is:
  • the structure-directing agent is present in the same proportion for the metal substituted aluminumphosphates as for the unsubstituted aluminumphosphate composi ⁇ tions, and the same choices as to aluminum and phosphorus sources as well as structure directing agents will be applicable. Similarly, the structure- directing agent may or may not remain in the final silicoaluminumphosphate VPI-5 compositions, depending on whether desorption or decomposition has occurred.
  • the chemical composition further comprises one or more species that are charge-compensating for the metal- ' substituted aluminumphosphates species such that the T charges are balanced. These charge-compensating species can be selected from various cations or anions including, for example, sodium, potassium, hydroxides, chlorides, and so forth, as will be known to those skilled in the art.
  • the present invention also comprises a method of preparing the VPI-5 compositions described herein.
  • the specified mole ratios of the constituent reactants are significant in attaining a pc - final crystalline solid adhering to the above characterizing data.
  • the crystalline aluminumphosphates of this invention are prepared by admixing an aluminum source, a phosphorus source, a structure-directing agent, and water to form a reaction
  • the combining of the components can be done in a variety of ways, such that the described VPI-5 compositions are produced.
  • the aluminum source can be admixed with water, and the phosphorus source can be separately admixed with water.
  • the phosphorus source/water admixture can then preferably be added to the aluminum source/water admixture while stirring to ensure homogeneity. It is also possible to add the aluminum source to the phosphorous source/water admixture, or to add an aluminum source/water admixture to a phosphorus source/water admixture. Other mixing orders can also be employed.
  • the precursor mixture is preferable to age the precursor mixture sufficiently for its pH to stabilize. This aging can be done with or without stirring, but it is preferred that stirring is not done during the time required to allow pH stabilization. The aging is preferably done at room temperature for a period of from 1 to 5 hours.
  • the metal source can, for example, be preferably added to the aluminum source/phosphorous source/water precursor mixture after it has been aged as described above. It is also possible to add the metal source to an aluminum source/water admixture or to a phosphorus source/water admixture prior to combining the admixtures. It is alternatively also possible to add the metal source in stages at various points in the synthesis.
  • Starting materials for preparing the aluminumphosphate or metal-substituted aluminumphos- phate compositions of the present invention can be selected from a number of possible choices.
  • Possible sources of phosphorus include, for example, elemental phosphorus, orthophosphoric acid (H3PO4), phosphorus oxide, esters of phosphoric acid, and mixtures of these. Of these, orthophosphoric acid is preferred.
  • Preferred aluminum sources include hydrates of aluminum such as boehmite, pseudo-boehmite, gibbsite, bayerite, and mixtures of these. Elemental aluminum, aluminum alkoxides, aluminum oxides, and mixtures of these are among other possible sources.
  • the phosphorus source include, for example, elemental phosphorus, orthophosphoric acid (H3PO4), phosphorus oxide, esters of phosphoric acid, and mixtures of these. Of these, orthophosphoric acid is preferred.
  • Preferred aluminum sources include hydrates of aluminum such as boehmite, pseudo-boehmite
  • the silicon source 10 and the aluminum source, and in the case of the silicoaluminumphosphate VPI-5, also the silicon source should be such that they are capable of forming an oxide of the metal upon incorporation into the
  • Preferred silicon sources include fumed silica, aqueous colloidal silica, tetraethylorthosilicate, and other reactive silicas. Other silicon-containing compounds can also be used.
  • the acetate dihydrates or tetrahydrates of the metals e.g., cobalt acetate tetrahydrate, zinc acetate dihydrate, or magnesium acetate tetrahydrate, are preferred, but other metal-containing compounds are also possible sources.
  • the metal can also be supplied 5 as a complex ion, such q,s a metal oxalate, an ethylenediaminetetraacetic acid complex, or the like.
  • the next step in the synthesis is the addition of the structure directing agent. This is preferably
  • the structure directing agent combined with all of the other starting materials is called the ⁇ r reaction mixture. It is preferable to age this reaction mixture for 1 to 2 hours, again to allow for pH stabilization.
  • Various effective structure-directing agents j - are dipropylamine, diisopropylamine, tetrapropyl- ammonium hydroxide, tetrabutylammonium hydroxide, dipentylamine, tripentylamine, tributylamine, alkylammoniu and alkylphosphonium compounds in general, and mixtures of these. Of these,
  • the proportions of the reactants can be varied within given ranges. Basing proportions on an AI2O3 molar value of 1, the structure directing agent ("R") to Al 2 ⁇ 3 molar ratio can be preferably 0.02 to 4, more 0 preferably 0.2 to 2, and most preferably 1; the P2O5 to
  • AI2O3 molar ratio can be preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and most preferably 1; and the water to Al 2 ⁇ 3 molar ratio can be preferably 10 to 100, 5 more preferably 30 to 70, and most preferably 35 to 55.
  • the above ratios are still applied, and in addition the M0 z / 2 to AI2O3 molar ratio can be 0 preferably from 0.001 to 0.5 mole of metal oxide per mole of AI2O3.
  • the ratio to Al 2 ⁇ be 0.2 to 0.5 for 5 silicon dioxide, and most preferred that it be 0.3 to
  • the ratio to Al 2 ⁇ " 3 of most other metal oxides be 0.001 to 0.1, and most preferred 0.02.
  • a polar organic solvent for part of the water.
  • an alcohol such as hexanol, or a ketone or other polar solvent can be employed.
  • the reaction mixture is reacted under conditions such that a crystalline solid having the X-ray powder diffraction pattern by which VPI-5 compositions are defined is formed.
  • known methods of heating are preferably employed. Autoclaving in bombs lined with TEFLON* (*TEFL0N is a trademark of Du Pont de Nemours, Inc.) is one effective and convenient means of achieving this. Other types of reactors can alternatively be used.
  • the temperature preferably ranges 50°C to 200°C, and 100°C to 150°C is more preferable.
  • the reaction can preferably be carried out under pressure, for example, autogenous pressure, or at atmospheric pressure.
  • Time of reaction varies, in part depending on the temperature used. Insufficient heating may lead to amorphous products, and excessive heating may result in the formation of amorphous products or undesirable phases
  • a time of 2 hours to 50 hours in conjunction with a temperature of 100°C to 150°C is preferred, depending on the reactants and the composition of the reaction mixture.
  • the product is preferably subjected to conventional means of separation and recovery. Separation from the mother liquor is conveniently accomplished by filtration, but centrifugation, settling and decantation, and related methods can also be employed.
  • the subsequent recovery of the crystalline VPI-5 compositions can involve traditional washings with acid solutions such as HC1 or boric acid, organic solvents such as acetone or methanol, salt solutions such as magnesium acetate, or deionized water, as well as drying and/or .thermal treatment steps. These post-synthesis treatments may help to remove the structure directing agent if desired and may also impart certain physical and chemical properties to the final product.
  • the final crystalline aluminumphosphate compositions will exhibit catalytic, adsorbent ion exchange and/or molecular sieve properties, and may be suitable for catalysis of reactions of various organic compounds.
  • Example 1 is given to more fully show various embodiments of the present invention. They are set forth for illustrative purposes only and are not intended to be, nor should they be construed as being, limitative of the scope of the invention in any way.
  • Example 1 is given to more fully show various embodiments of the present invention. They are set forth for illustrative purposes only and are not intended to be, nor should they be construed as being, limitative of the scope of the invention in any way.
  • Example 1 is given to more fully show various embodiments of the present invention. They are set forth for illustrative purposes only and are not intended to be, nor should they be construed as being, limitative of the scope of the invention in any way.
  • the reaction mixture is heated at 145°C for 24 hours in a TEFLON*-lined stainless steel autoclave.
  • the product is removed, washed with water, and dried at room temperature overnight.
  • the resulting X-ray diffraction pattern is characterized by d spacings that are substantially as shown in Table 1.
  • the reaction mixtures are heated at 150°C for 18 hours in TEFLON* lined stainless steel reactors.
  • the white solids are recovered by slurrying the contents of each reactor with deionized water and allowing the solids to settle.
  • the solids are dried at room temperature in air overnight.
  • the X-ray diffraction pattern of the resulting crystalline materials show a pattern characterized by d spacings that are substantially those of VPI-5 as listed in Table 1.
  • aqueous orthophosphoric acid 85 percent concentration
  • a slurry is prepared by mixing about 5.3 g of aluminum oxide dihydrate with about 6.0 g of distilled water.
  • the acid solution is then added to the slurry while stirring at room temperature.
  • the resulting precursor mixture is stirred with a magnetic bar for about 20 minutes.
  • Another solution is prepared by combining about 18.3 g of aqueous 55 percent tetrabutylammonium hydroxide (TBA), and about 10.9 g of distilled water. This solution is then added to the precursor mixture while stirring. Stirring is then continued at room temperature in air for about 1.5 hours. At this point the mixture has the following molar ratio composition:
  • This reaction mixture is then transferred to five TEFLON* lined stainless steel autoclaves labeled, respectively, 1, 2, 3, 4, and 5, and heated under 5 autogenous pressure at 142°C for the times specified in Table 4.
  • the pH is measured as to each of the portions and found to be 7.0.
  • a white solid is recovered by separately slurrying the contents of each autoclave in deionized water, stirring for several minutes to allow the solid to settle, and discarding the supernatant liquid. This solid is then filtered and dried in an oven at 100°C and is characterized by Table 1.
  • reaction composition of all runs is DPrA: AI2O3 P2O5: 37 H 2 0, and is further characterized by Table 1
  • the reaction mixtures are heated in stainless steel TEFL0N*-lined autoclaves for periods of time, as shown in Table 8.
  • White solids are recovered by slurrying the contents of each reactor with deionized water and allowing the solids to settle, then washing with acetone.
  • the solids are dried at room temperature in air overnight and are characterized by Table 1.
  • orthophosphoric acid H3PO4 is dissolved in about 6.0 g of distilled water. Separately, about 5.3 g of aluminum oxide dihydrate is mixed with about 6.0 g of distilled water. The phosphorus-containing mixture is then added to the aluminum-containing mixture, and the resulting precursor mixture is homogenized by stirring with a magnetic bar for about 20 minutes.
  • reaction mixture has the 5 following molar ratio composition:
  • the solid products are then separated from the _, £ . mother liquor by filtration and recovered by slurrying the contents of each autoclave in about 100 ml of distilled water, stirring for several minutes, allowing the solid to settle by gravity, and then discarding the . supernatant liquid. Then the solid is filtered and 20 dried in air at J00°C for about 30 minutes.
  • ⁇ 5 products are white solids which are recovered by slurrying the contents of the reactor with deionized water and allowing the solids to settle. This dried at room temperature in air overnight.
  • a solution prepared with 8.9 g of orthophos ⁇ 0 phoric acid (85 percent H3PO2J) and 6.0 g of water is added to a slurry of 5.3 g of aluminum oxide dihydrate in 6.0 g of water. This precursor mixture is homogenized for several minutes.
  • a second solution is prepared by adding 18.3 g of aqueous 55 weight percent 5 tetrabutylammonium hydroxide (TBA) and 0.928 g of fumed silica to 10.9 g of water. This second solution is added with mixing and the resulting reaction mixture is homogenized for 90 minutes.
  • TSA tetrabutylammonium hydroxide
  • a solution is prepared with 8.9 g of 85 percent orthophosphoric a:cid and 6 g of water. This is added to a slurry of 5.3 g of aluminum oxide dihydrate in 6 g
  • reaction composition is as follows:
  • the gel is heated at 150°C for 41 hrs as described in previous examples.
  • the white solid is recovered by slurrying the contents of the reactor with deionized water and allowing the solids to settle.
  • the solid is dried at room temperature in air overnight and is 25 characterized by Table 1.
  • a solution prepared with 11.5 g of - 3Q orthophosphoric acid (85 percent ⁇ PO ⁇ ) and 9.8 g of water is stirred for 20 minutes.
  • the phosphoric acid solution is then added to the aluminum-containing 35' mixture with stirring.
  • About 0.93 g of fumed silica is then added.
  • the silicoaluminumphospha * te precursor mixture is homogenized for 2 hours, and during this time the pH of the mixture increases from 0.9 to 1.6, stabilizing at 1.6.
  • product is recovered by slurrying the contents of each autoclave in water, stirring for several minutes, allowing the solid to settle and discarding the supernatant liquid. The solid is then filtered and dried in an oven at 100°C and is characterized by Table 0 1.
  • VPI-5 compositions of the invention showing the unique X-ray diffraction pattern of Table 1 as described above, adsorption experiments were carried out on samples of VPI-5 previously heated to at least about 350°C for at least about one hour, and then cooled to room temperature under vacuum. The samples were then 0 exposed to atmospheres of given adsorbates until an equilibrium uptake was obtained. Equilibrium was defined as constant weight of the sample plus adsorbate for at least about 2 hours. The results of these experiments are summarized in Table 13, which includes 5 adsorption data for water, oxygen, nitrogen, cyclohexane, neopentane, and triisopropylbenzene.
  • That table shows adsorption data for VPI-5 prepared using two different structure directing 0 materials, dipropylamine and tetrabutylammonium hydroxide. It also shows adsorption data for three other reported materials, which are zeolite Y (described in U.S. Patent 3,216,789) and molecular c - sieves AlPO ⁇ -5 and AlPOi j -8 (as described in U.S. Patent 3,414,602). From the table it can be inferred that molecules having a kinetic diameter In the range of from about 3 Angstroms to about 14 Angstroms can be admitted into the VPI-5 intracrystalline free 0 micropores.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)
EP19880908535 1987-08-28 1988-08-24 Kristalline aluminiumphosphat-zubereitungen. Withdrawn EP0333816A4 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US9080187A 1987-08-28 1987-08-28
US90801 1987-08-28
US07/207,850 US5374411A (en) 1987-08-28 1988-06-15 Crystalline aluminumphosphate compositions
US207850 1988-06-15

Publications (2)

Publication Number Publication Date
EP0333816A1 EP0333816A1 (de) 1989-09-27
EP0333816A4 true EP0333816A4 (de) 1989-12-13

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EP19880908535 Withdrawn EP0333816A4 (de) 1987-08-28 1988-08-24 Kristalline aluminiumphosphat-zubereitungen.

Country Status (8)

Country Link
EP (1) EP0333816A4 (de)
JP (1) JPH03505720A (de)
CN (1) CN1018624B (de)
FI (1) FI89037C (de)
HU (1) HU208511B (de)
IL (1) IL87606A (de)
RO (1) RO104858B1 (de)
WO (1) WO1989001912A1 (de)

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AU2924089A (en) * 1987-12-21 1989-07-19 Mobil Oil Corporation Crystalline molecular sieve
NZ228425A (en) * 1988-04-08 1990-11-27 Mobil Oil Corp Method of synthesising a crystalline molecular sieve comprising oxides of aluminium and phosphorus, and other elements
JPH03503631A (ja) * 1988-04-08 1991-08-15 モービル・オイル・コーポレイション 結晶性分子ふるいの合成
US5013535A (en) * 1989-04-20 1991-05-07 Uop Stabilized aluminophosphate compositions and process for preparing same
DD299288A5 (de) * 1989-07-07 1992-04-09 ���������������@����@�������������@�K@����������K@��������@�K@���@�K@���@M�����]k�� Verfahren zur herstellung eines kristallinen molekularsiebes
US5208006A (en) * 1990-05-28 1993-05-04 Engelhard Corporation Large-pored molecular sieves containing at least one octahedral site comprising titanium and at least silicon as a tetrahedral site
US5124136A (en) * 1990-06-26 1992-06-23 Mobil Oil Corporation Synthesis of crystalline metalloluminophosphate composition
US5108727A (en) * 1990-06-26 1992-04-28 Mobil Oil Corporation Synthesis of crystalline aluminophosphate composition
DK0464249T3 (da) * 1990-07-05 1994-04-25 Leuna Werke Gmbh Fremgangsmåde til fremstilling af en storporet krystallinsk molekylsi
US5091073A (en) * 1990-07-13 1992-02-25 Mobil Oil Corp. Crystalline molecular sieve compositions mcm-37
US5104495A (en) * 1990-12-11 1992-04-14 Mobil Oil Corp. Crystalline (metallo) aluminophosphate composition MCM-40, its synthesis and usage in hydrocarbon conversion
US5094828A (en) * 1990-12-31 1992-03-10 Mobil Oil Corporation Synthesis of large-pore
FR2671790B1 (fr) * 1991-01-18 1993-04-16 Inst Francais Du Petrole Procede de preparation de composes aluminophosphates et derives substitues de type structural vfi invention de : jean-francois joly, herve cauffriez et jean-louis guth.
US5480556A (en) * 1991-07-01 1996-01-02 Ulan; Judith G. Trapping and sealing process
NL1001553C2 (nl) * 1995-11-02 1997-05-13 Akzo Nobel Nv Werkwijze voor de synthese van poreuze keramische materialen.
AU779140B2 (en) * 1999-11-18 2005-01-06 Exxon Chemical Patents Inc. Method for the synthesis of molecular sieves
US6685905B2 (en) 2001-12-21 2004-02-03 Exxonmobil Chemical Patents Inc. Silicoaluminophosphate molecular sieves
WO2013158509A1 (en) * 2012-04-16 2013-10-24 Bunge Amorphic Solutions Llc Antimicrobial chemical compositions

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US4310440A (en) * 1980-07-07 1982-01-12 Union Carbide Corporation Crystalline metallophosphate compositions
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
US4673559A (en) * 1983-12-19 1987-06-16 Mobil Oil Corporation Silicoaluminophosphate crystallization using hydrolysis

Also Published As

Publication number Publication date
IL87606A (en) 1992-06-21
HU208511B (en) 1993-11-29
HU885511D0 (en) 1990-02-28
IL87606A0 (en) 1989-01-31
CN1036376A (zh) 1989-10-18
CN1018624B (zh) 1992-10-14
FI891964A0 (fi) 1989-04-25
EP0333816A1 (de) 1989-09-27
JPH03505720A (ja) 1991-12-12
FI891964A (fi) 1989-04-25
FI89037C (fi) 1993-08-10
JPH0574523B2 (de) 1993-10-18
WO1989001912A1 (en) 1989-03-09
FI89037B (fi) 1993-04-30
RO104858B1 (en) 1993-04-01
HUT52003A (en) 1990-06-28

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