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WO1996014267A1 - Synthese directe de disilicates cristallins a partir d'une solution de silicate de sodium - Google Patents

Synthese directe de disilicates cristallins a partir d'une solution de silicate de sodium Download PDF

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Publication number
WO1996014267A1
WO1996014267A1 PCT/EP1995/004159 EP9504159W WO9614267A1 WO 1996014267 A1 WO1996014267 A1 WO 1996014267A1 EP 9504159 W EP9504159 W EP 9504159W WO 9614267 A1 WO9614267 A1 WO 9614267A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkali metal
sodium
crystalline
water
silicate
Prior art date
Application number
PCT/EP1995/004159
Other languages
German (de)
English (en)
Inventor
Helmut Blum
Wolfgang Breuer
Hans Dolhaine
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1996014267A1 publication Critical patent/WO1996014267A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type

Definitions

  • the invention describes a process for the production of water-soluble crystalline alkali metal disilicates by introducing a water glass solution into a gas stream heated to 580 to 800 ° C.
  • the products can be used as powder substances and as anti-corrosion agents in washing and cleaning agents.
  • Figure 2 of this work shows in the left half that after the annealing of previously melted water glass at 500 ° C there is little oc phase in addition to a lot of gamma phase, while at 550 ° C about the same proportions of ⁇ and ⁇ phases 600 ° C about 1/3 as much ⁇ - as ß-phase and above 650 ° C in excess ⁇ -phase.
  • a material which mainly consists of the “modification” and contains small amounts of a delta modification.
  • the delta modification is characterized by its X-ray diffraction diagram in DE-A-34 17649.
  • the X-ray diffraction patterns e of the ⁇ , ⁇ and gamma modifications are also given. They are also contained in the JCPDS file familiar to the crystallographer.
  • the X-ray characterization can also be found in EP-B-164514, which also gives the numbers of the corresponding entries in the JCPDS file.
  • DE-A-34 17649 does not explicitly set itself the task of producing the delta modification of the layered disilicate, but is limited from the above-mentioned literature reference in glass technology. Report that the delta modification could not be obtained by the process there.
  • a production process is claimed in which an aqueous solution of an amorphous sodium silicate with a modulus between 1.9 and 3.5 with the addition of 0.01 to 30 parts by weight of the crystalline sodium silicate to be produced is dewatered and the dehydrated reaction mixture as long at a temperature between 450 ° C and the melting point until the sodium silicate has crystallized. It is emphasized that it is essential that crystal seeds of the desired sodium silicate are added to the amorphous alkali metal silicate before it is heated to the crystallization temperature.
  • EP-A-293640 the production of the delta modification is aimed at, but in the main claim a process for the production of crystalline sodium silicates with a layer structure and a module of 1.9 to 3.5 is more generally claimed.
  • the process is characterized in that a) a water glass solution with a solids content of 20 to 65 wt .-% spray dried such that the exhaust gas from the spray drying has a temperature of at least 140 ° C, b) the spray-dried product in a moving solid layer at temperatures of 500 to 800 ° C for tempering for a period of 1 to 60 minutes in the presence of at least 10% by weight of a return material.
  • amorphous sodium silicate is first dissolved in water and then converted into a water-containing, powdery form by evaporation of the water, for example by spray drying, which is then carried out at a temperature above 450 ° C anneals.
  • These processes are therefore two-stage and require isolation and transport of the powdery amorphous intermediate.
  • WO91 / 08171 describes a process for the hydro-thermal production of crystalline sodium disilicate, in which an aqueous silicate solution with a solids content of between 50 and 75% by weight is heated in a pressure vessel at a temperature of at least 235 ° C. under autogenous pressure is, the crystalline layered sodium disilicate precipitates and is separated from the mother liquor.
  • the ⁇ modification is obtained.
  • the object of the invention is to provide a process for the direct pressure-free production of crystalline alkali metal disilicates from an aqueous solution of alkali silicates (water glass) without isolating an amorphous intermediate product.
  • sodium or potassium silicates or mixtures thereof can be used as alkali metal silicates.
  • Sodium silicates are preferred for economic reasons.
  • potassium silicates have the advantage of increased solubility, so that potassium silicates will be preferred in cases where particularly good solubility is important.
  • a compromise in terms of cost and solubility is represented by sodium silicates doped with potassium, in which, for example, the sodium is replaced by potassium to such an extent that the product has a K 2 O content of up to 5% by weight. If crystalline sodium disilicate is prepared by the process according to the invention, products are obtained whose X-ray diffraction pattern corresponds to the delta phase without the addition of crystal nuclei being necessary.
  • crystalline sodium disilicate when used in the sense of this invention, it means products which have the X-ray diagrams typical of crystalline sodium disilicate with a layer structure, as are given, for example, in the literature cited at the beginning. In practice it is possible that these products do not have the exact composition Na2Si2 ⁇ 5, but differ from this strictly stoichiometric composition. In particular, it is possible for some of the sodium ions to be replaced by hydrogen ions, so that the products analytically have a lower sodium content or an increased silicon content.
  • the solids content of the alkali metal silicate solution to be used is limited at the bottom by economic criteria such as space-time yield and energy requirement for water evaporation and at the top by technical criteria such as the pumpability of the solution.
  • the solids content given above from 20 to 65% by weight represents a technically sensible concentration range. For economic reasons it is preferred to use solutions with a solids content above about 40% by weight.
  • the heated gas stream used for the direct synthesis of the crystalline alkali metal disilicates consists of is in principle insignificant, unless it reacts with the alkali metal silicate solution in such a way that the formation of the desired products is prevented or inhibited.
  • heated nitrogen can be used.
  • heated air is preferred, and the heating can also be carried out by direct combustion of fossil fuels.
  • a gas mixture is also suitable for the synthesis, which is formed when air is combusted with carbon-containing fuels.
  • the carbon dioxide content of the fuel gas, together with the desired product, results in a subordinate amount of amorphous silica, which, however, does not interfere with the intended use of the product in detergents and cleaning agents.
  • the process can be operated batchwise or continuously, with continuous operation being preferred for economic reasons.
  • the process is preferably controlled so that the product is whirled up by the heating gas stream and held in a fluidized bed.
  • the drying / crystallization times mentioned between 10 and 30 minutes are to be understood in such a way that the average residence time of the product in the gas stream heated to 580 to 800 ° C. is within this period. It is harmless that the dwell time of a certain product portion falls below or exceeds this time interval.
  • the process can be carried out by spraying an alkali metal silicate solution into a chamber through which the heated gas flows and in which there is still no solid.
  • the gas flow rate based on the chamber cross-section in such a way that it is not sufficient to form a fluidized bed
  • the product is in the form of a foamy mass which loosely fills the chamber, which can be easily removed from the crystallization chamber and assembled by breaking or grinding.
  • the fluidized bed increasingly forms due to the evaporation of the water from the alkali metal silicate solution.
  • the process can also be carried out in such a way that a fluidized bed composed of a foreign material is initially introduced before the alkali metal silicate solution is introduced.
  • this foreign material be readily water-soluble.
  • this foreign material has at least the function of a disintegrant, but if possible has a builder function itself, in order not to contaminate the product with inert material.
  • a disintegrant for example, sodium sulfate comes into consideration.
  • the crystalline alkali metal silicates are combined with other builder substances, preferably selected from alkali metal carbonate or bicarbonate, alkali metal oligo- or polyphosphate and alkali metal citrate, glycinate and / or polycarboxylate, preferably as sodium - and / or potassium salts, or of amorphous or crystalline alkali metal silicates with a modulus ⁇ 1.6 or> 2.4, for example Sodium metasilicate (module ⁇ 1) or amorphous sodium silicate with module 3.3, the proportion of the other builder substances and / or adjusting agents based on the dry matter content of the alkali metal silicate components being between 5 and 120% by weight.
  • other builder substances preferably selected from alkali metal carbonate or bicarbonate, alkali metal oligo- or polyphosphate and alkali metal citrate, glycinate and / or polycarboxylate, preferably as sodium - and / or potassium salts, or of amorphous
  • Pentasodium triphosphate and / or soda are particularly preferred. If sodium carbonate is used, its water-free form is preferred. This process makes it possible to produce builder compounds in one process step which consist of crystalline alkali metal disilicate and a further builder component.
  • the quantitative ratios of silicate to soda with which optimum properties with regard to primary and secondary washing capacity are observed depend, among other things, on the water hardness present and on the other constituents of the washing liquor. It is generally known from the prior art to use silicate-soda compounds in which the soda content is between 5 and 120% by weight of the alkali metal silicate components. Compounds are described in particular in the prior art in which the soda content on the one hand is between 7.5 and 25% by weight with respect to the alkali metal silicate components and on the other hand between 55 and 95% by weight with respect to the alkali metal silicate components. Analogously to this, these quantitative ranges are also preferred for the production process according to the invention of the compounds with crystalline alkali metal silicates.
  • a glass tube 50 cm long and about 5 cm in diameter was used, which was closed at one end with a frit.
  • the glass tube was placed frit vertically in a tube furnace, which made it possible to Heat the pipe to the desired temperature up to 800 ° C.
  • a Stic material flow of 12 l / minute which was heated to the temperatures given in the table, was passed into the lower end of the tube.
  • the tube furnace was set to the same temperature in each case.
  • sodium water glass solution with a modulus of 2 and a solids content of between 50 and 60% by weight was added dropwise from a dropping funnel. The times given in the table describe the time intervals between the beginning of the dropping and the end thereof.
  • the tube contained a foam-like mass of the product, which could be removed after loosening with a rod.
  • the table contains more information about the selected temperatures and crystallization times as well as about the crystallinity of the products obtained.
  • the experiments showed that for the direct synthesis according to the invention of crystalline alkali metal disilicates from water glass solution, temperatures of the heated gas stream in the range between 580 and 800 ° C. and crystallization times in the range between about 10 and about 30 minutes are required. Of course, longer times are possible, but do not bring any further advantage.
  • a fluidized bed reactor is preferably chosen, into which the water glass solution can be introduced through nozzles and in which the product is swirled by the heated gas fed in.
  • the heating gas has a temperature in the range between 580 and 800 ° C.
  • either the appropriate foreign substance can be added to the water glass solution or the foreign substance in powder form Submit in the fluidized bed or meter in parallel so that it is enveloped and granulated by the alkali metal disilicate which is injected and crystallizes at the selected temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé de fabrication de disilicates de métaux alcalins cristallins, caractérisé en ce que l'on introduit une solution de silicate de métaux alcalins, présentant un module (rapport molaire SiO2 : M2O, M = métal alcalin) de l'ordre de 1,8 à 2,5 et des teneurs en matières solides de l'ordre de 20 à 65 % en poids, dans un flux de gaz chauffé à 580-800 °C, où le produit séjourne entre 10 et 30 minutes. D'autres substances servant d'adjuvant ou d'explosif peuvent également être présentes, de sorte que l'on obtient des composés de ces substances avec des disilicates cristallins.
PCT/EP1995/004159 1994-11-02 1995-10-24 Synthese directe de disilicates cristallins a partir d'une solution de silicate de sodium WO1996014267A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4439083.1 1994-11-02
DE19944439083 DE4439083A1 (de) 1994-11-02 1994-11-02 Direktsynthese kristalliner Disilicate aus Wasserglaslösung

Publications (1)

Publication Number Publication Date
WO1996014267A1 true WO1996014267A1 (fr) 1996-05-17

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Application Number Title Priority Date Filing Date
PCT/EP1995/004159 WO1996014267A1 (fr) 1994-11-02 1995-10-24 Synthese directe de disilicates cristallins a partir d'une solution de silicate de sodium

Country Status (2)

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DE (1) DE4439083A1 (fr)
WO (1) WO1996014267A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19943237A1 (de) * 1999-09-11 2001-05-17 Clariant Gmbh Cogranulate aus Alkalischichtsilikaten und Sprengmitteln
DE19943550A1 (de) * 1999-09-11 2001-03-15 Clariant Gmbh Hochalkalisches kristallines Natriumsilikat

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2104081A5 (en) * 1970-08-08 1972-04-14 Knapsack Ag Granules contg sodium tripolyphosphate prepn - for use as rinsing agent for crockery
JPH04238809A (ja) * 1991-01-10 1992-08-26 Nippon Chem Ind Co Ltd 結晶性層状珪酸ナトリウムの製造方法
WO1993011214A1 (fr) * 1991-12-03 1993-06-10 Basf Aktiengesellschaft Produits de lavage et detergents
EP0548599A1 (fr) * 1991-12-21 1993-06-30 Hoechst Aktiengesellschaft Procédé de préparation de disilicates de sodium cristallins
EP0550077A1 (fr) * 1992-01-03 1993-07-07 The Procter & Gamble Company Composition de blanchiment granulaire pour le lavage du linge
EP0667391A2 (fr) * 1994-02-15 1995-08-16 Degussa Aktiengesellschaft Mélanges homogènes contenant silicate alcalin et carbonate alcalin

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2104081A5 (en) * 1970-08-08 1972-04-14 Knapsack Ag Granules contg sodium tripolyphosphate prepn - for use as rinsing agent for crockery
JPH04238809A (ja) * 1991-01-10 1992-08-26 Nippon Chem Ind Co Ltd 結晶性層状珪酸ナトリウムの製造方法
WO1993011214A1 (fr) * 1991-12-03 1993-06-10 Basf Aktiengesellschaft Produits de lavage et detergents
EP0548599A1 (fr) * 1991-12-21 1993-06-30 Hoechst Aktiengesellschaft Procédé de préparation de disilicates de sodium cristallins
EP0550077A1 (fr) * 1992-01-03 1993-07-07 The Procter & Gamble Company Composition de blanchiment granulaire pour le lavage du linge
EP0667391A2 (fr) * 1994-02-15 1995-08-16 Degussa Aktiengesellschaft Mélanges homogènes contenant silicate alcalin et carbonate alcalin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9241, Derwent World Patents Index; Class D25, AN 92-335303 *

Also Published As

Publication number Publication date
DE4439083A1 (de) 1996-05-09

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