WO1991017954A1 - Procede de fabrication de zeolites a partir de sable recuit - Google Patents

Procede de fabrication de zeolites a partir de sable recuit Download PDF

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Publication number
WO1991017954A1
WO1991017954A1 PCT/EP1991/000862 EP9100862W WO9117954A1 WO 1991017954 A1 WO1991017954 A1 WO 1991017954A1 EP 9100862 W EP9100862 W EP 9100862W WO 9117954 A1 WO9117954 A1 WO 9117954A1
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WO
WIPO (PCT)
Prior art keywords
source
hydroxide solution
potassium
sodium
solution
Prior art date
Application number
PCT/EP1991/000862
Other languages
German (de)
English (en)
Inventor
Johannes W. Hachgenei
Hans Dolhaine
Arnold Heins
Peter Christophliemk
Rudolf Novotny
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1991017954A1 publication Critical patent/WO1991017954A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2815—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L)
    • C01B33/2823—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L) from aqueous solutions of an alkali metal aluminate and an alkali metal silicate excluding any other source of alumina or silica

Definitions

  • the invention relates to a process for the production of sodium or potassium aluminosilicates (zeolites) from tempered sand, an aluminum oxide source and a sodium oxide or potassium oxide source in aqueous alkaline systems, the production of the zeolites being carried out without pressure in a single reaction container can be.
  • zeolites sodium or potassium aluminosilicates
  • the crystal lattice of the zeolites is built up from SiO.4 and AlO4 tetrahedra, which are linked via oxygen bridges. This creates a spatial arrangement of cavities that are accessible via channels. These cavities can accommodate molecules of different sizes, which is also the reason for the name molecular sieves for zeolites (Rö pp Chemie-Lexikon, 8th edition, volume 6 (1988), p. 4690f).
  • Zeolites are widely used due to their adsorption behavior. Zeolite A with the ideal composition
  • Nai2 [(Al ⁇ 2) i2 (Si ⁇ 2) i2] • 27 H2O is used, for example, instead of phosphate as a builder in washing and cleaning agents.
  • zeolites for drying gases and organic solvents is also widespread. Zeolites are used in large quantities as catalysts in petrochemical processes, the pore diameter for the corresponding one Process is tailor-made (Römpp or the like; Ullmann's Encyclopedia of Technical Chemistry, Volume 24 (1982), pp. 120f, 575ff).
  • Naturally occurring zeolites usually do not have the purity required for the application. Zeolites can be produced from naturally occurring kaolin clays after the kaolin has been converted into metakaolin by heating.
  • the aluminum for the zeolite synthesis is obtained from sodium aluminate solutions
  • the silicon oxide is used as a water glass solution, finely divided silica or as a silica sol (Büchner et al. "Industrial Inorganic Chemistry", Verlag Chemie, 1984, p. 337).
  • These SiO 2 sources have to be produced via one or more wet chemical processes, some of which are very energy-intensive.
  • Water glass solutions are obtained via the melting process of quartz sand and soda and subsequent hydrothermal solution or the direct reaction of quartz with sodium hydroxide solution at elevated temperatures and pressures in an autoclave (Büchner et al., Op. Cit., P. 332).
  • Finely divided silica and silica brine are obtained in a further step from water glass solutions (Büchner et al., Op. Cit., Pp. 533f) and are therefore an expensive SiÜ2 source.
  • the type of zeolite formed depends on several factors. This includes the stoichiometry of the reaction batch, the choice of the reaction temperature or temperature consequences, the shear energy during stirring and the addition of further cations (Büchner et al., Op. Cit .; p. 338).
  • the object of the present invention is. a process for the preparation of zeolites of the general formula (I)
  • the object was achieved according to the invention by using tempered quartz sands as SiO 2 source, which have an increased reactivity towards alkali and solubility in aqueous alkali hydroxide solutions.
  • the invention accordingly relates to a process for the preparation of zeolitic sodium or potassium aluminosilicates of the general formula (I)
  • aqueous sodium or potassium aluminate solution is preferably used as the Al 2 O 3 source.
  • Sodium or potassium aluminosilicate suspensions can be produced without pressure from tempered quartz sands, a raw material for A12Ü3 and aqueous sodium hydroxide or potassium hydroxide solutions.
  • reactive SiO 2 phases are obtained which are composed, among other things, of cristobalite, tridymite and amorphous S O 2.
  • the subject of this patent application is a process for the production of reactive silicon dioxide phases, which is characterized in that quartz sand is mixed with an alkali metal compound or its aqueous solution, the alkali metal compound being selected from the group of compounds which, when heated into the Corresponding alkali metal oxides pass over that the molar ratio of S1O2 to alkali metal oxide is between 1: 0.0025 and 1: 0.1 and that this mixture is heated to a temperature between 1100 ° C. and 1700 ° C.
  • the preferred alkali metal compounds here are in particular lithium, sodium or potassium hydroxide and the carbonates, nitrates, sulfates, sulfites, oxalates or formates of these alkali metals Question.
  • the molar ratio of SiO 2 to alkali metal oxide is preferably between 1: 0.0035 and 1: 0.05.
  • the mixture is preferably heated to a temperature of at least 1300 ° C., the reaction time being 10 to 180 minutes.
  • the type of zeolite formed in the synthesis depends on many factors (e.g. falling temperature, falling concentration).
  • the composition of the product often differs from the stoichiometry of the starting solution or suspension. For these reasons, only the general reaction route can be given.
  • the boundary conditions, such as stoichiometry of the reaction batch and temperature control, must be determined in each individual case or taken from the literature, for example D.W. Breck, "Zeolite Molecular Sieves,” John Wiley & Sons, N.Y. 1974, or "Zeolite Synthesis", ACS Symposium Series 398, Ed. by M.L. Occelli, H.E. Robson, American Chemical Society, Washington D.C. 1989.
  • the tempered quartz sand is reacted with aqueous sodium hydroxide or potassium hydroxide solution until it dissolves completely.
  • this is preferably done with the largest possible amount of alkali metal hydroxide (total alkali metal oxide minus the alkali metal oxide that is introduced with the aluminate) and in a concentrated solution of the alkylimetal hydroxide.
  • the aqueous sodium hydroxide solution or potassium hydroxide solution used has a concentration of 40 to 55% by weight, in particular a concentration of 50% by weight of sodium hydroxide or Potassium hydroxide.
  • the highest reaction rate is also achieved if the digestion is carried out at an elevated temperature and preferably at the boiling point of the reaction mixture. Temperatures suitable for this are in the range from 80 to 150 ° C., the temperature range from 100 to 140 ° C. and in particular the particular boiling temperature of the reaction mixture being particularly preferred.
  • a particular advantage of the method lies precisely in the fact that the dissolution rate of the tempered quartz sands used is so high that the dissolution is carried out without pressure at elevated temperature and preferably at the boiling point of the sodium hydroxide solution or potassium hydroxide solution or the alkali metal silicate solution or suspension which forms can be, and therefore no complex pressure autoclave is necessary.
  • water can optionally be added in a second reaction step to adjust the temperature and concentration.
  • optimal conditions can be set for the precipitation of the desired zeolite.
  • the amount of water to be added is calculated from the amount required after the reaction batch minus the amount introduced by the alkali metal hydroxide solution and aluminum inate solution (aluminate lye).
  • the heat content of the alkali silicate solution can advantageously be used to precipitate the zeolite at elevated temperature. If the temperature control when the zeolite is precipitated, this can be cooled further or a part of the water added can be replaced by ice, in order, for example, to cool down to room temperature.
  • the process described can be carried out discontinuously as a one-pot process in a suitable boiler with corresponding units (such as stirrer, condenser, heating and cooling). Continuous operation, for example in a system of loop reactors, is also possible.
  • the process according to the invention allows the zeolites of the general formula (I), for example the zeolite types NaA, NaX and KF, to be prepared in a simple manner.
  • the tests were carried out in a glass three-necked round-bottom flask with paddle stirrer, ground thermometer and reflux condenser.
  • the reaction solution or suspension was heated by a patio heater.
  • cristobalite with grain sizes of 0.1 to 0.8 mm was used, which was obtained as follows:
  • the NaOH was dissolved in just enough water that the quartz sand was covered with the solution.
  • the reaction mixture was then dried slowly and the dry sand was mixed vigorously. The reaction mixture was then heated to 1400 ° C. for 60 minutes.
  • aluminum hydroxide solution or suspension can also be used as the Al2 ⁇ 3 source.
  • the X-ray diffraction diagram confirms the formation of zeolite potassium F (comparison Breck or above; p. 357).

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

Abstract

L'invention concerne un procédé de fabrication d'alumino-silicates de sodium ou de potassium zéolitiques, de formule générale M2 . Al2O3 . xSiO2 dans laquelle M = Na ou K et x = 1,8 à 12, et ayant une teneur en eau fonction du degré de séchage, à partir d'une source de SiO2, d'une source de Al2O3 et d'une source de Na2O ou K2O ou dans des systèmes alcalins aqueux, à température élevée, caractérisé en ce qu'on utilise comme source de SiO2, du sable recuit dissous dans une solution aqueuse d'hydroxyde de sodium ou d'hydroxyde de potassium, à température élevée.
PCT/EP1991/000862 1990-05-17 1991-05-08 Procede de fabrication de zeolites a partir de sable recuit WO1991017954A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4015850.0 1990-05-17
DE19904015850 DE4015850A1 (de) 1990-05-17 1990-05-17 Verfahren zur herstellung von zeolithen aus getempertem sand

Publications (1)

Publication Number Publication Date
WO1991017954A1 true WO1991017954A1 (fr) 1991-11-28

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PCT/EP1991/000862 WO1991017954A1 (fr) 1990-05-17 1991-05-08 Procede de fabrication de zeolites a partir de sable recuit

Country Status (3)

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AU (1) AU7799091A (fr)
DE (1) DE4015850A1 (fr)
WO (1) WO1991017954A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0889004A1 (fr) * 1997-07-01 1999-01-07 Clariant GmbH Procédé de préparation d'un silicate en couches synthétique de type hectorite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882243A (en) * 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
JPS59156911A (ja) * 1983-02-22 1984-09-06 Agency Of Ind Science & Technol 火山ガラスを主原料とするａ型ゼオライトの製造方法
EP0363197A2 (fr) * 1988-10-06 1990-04-11 Unilever Plc Préparation de silicate de sodium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882243A (en) * 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
JPS59156911A (ja) * 1983-02-22 1984-09-06 Agency Of Ind Science & Technol 火山ガラスを主原料とするａ型ゼオライトの製造方法
EP0363197A2 (fr) * 1988-10-06 1990-04-11 Unilever Plc Préparation de silicate de sodium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
World Patents Indexe Latest, Eintrittsnr. 84-259418, Woche 42, Derwent Publications LTD, (London, GB) & JP-A-59156911 (6. September 1984) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0889004A1 (fr) * 1997-07-01 1999-01-07 Clariant GmbH Procédé de préparation d'un silicate en couches synthétique de type hectorite

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DE4015850A1 (de) 1991-11-21
AU7799091A (en) 1991-12-10

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