WO1993014028A1 - Procede de fabrication de silicates de sodium-aluminium amorphes - Google Patents

Procede de fabrication de silicates de sodium-aluminium amorphes Download PDF

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Publication number
WO1993014028A1
WO1993014028A1 PCT/EP1993/000044 EP9300044W WO9314028A1 WO 1993014028 A1 WO1993014028 A1 WO 1993014028A1 EP 9300044 W EP9300044 W EP 9300044W WO 9314028 A1 WO9314028 A1 WO 9314028A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction components
ball mill
mill
agitator ball
precipitation
Prior art date
Application number
PCT/EP1993/000044
Other languages
German (de)
English (en)
Inventor
Günther Just
Bernd Larson
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
Priority to JP5512132A priority Critical patent/JPH07502966A/ja
Priority to EP93902169A priority patent/EP0623096A1/fr
Priority to KR1019940702512A priority patent/KR950700216A/ko
Publication of WO1993014028A1 publication Critical patent/WO1993014028A1/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
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • 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
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • 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

Definitions

  • the invention relates to a process for the continuous production of an aqueous alkaline suspension of finely divided, X-ray amorphous sodium aluminum silicates having the composition 0.9 to 1.1 Na 2 O: 1 Al 2 O 3: 1.8 to 3.6 Si O 2 by continuous mixing of an aqueous sodium aluminate solution with a aqueous sodium silicate solution in the presence of excess sodium hydroxide solution at elevated temperature.
  • the product obtained can be crystallized to form finely divided sodium aluminum silicates having a zeolitic structure, which u. a. characterized by particularly low grit fractions.
  • a further alkalinity, a higher silicate content or a stronger dilution of the precipitation mixture are not technically sensible.
  • a lower water content of the batch than the one specified above leads to particularly strong lump formation in the precipitation and to inconsistent products.
  • the silicate content of the precipitation product is largely determined by the SiO 2: Al 2 O 3 molar ratio in the precipitation.
  • zeolites having grit values in the range from 0.1 to 0.2% by weight have hitherto been obtained using conventional reaction and crystallization conditions.
  • the invention is therefore based on the object of providing a process of the type mentioned at the outset with a considerably higher space-time yield of the precipitation stage without problems with the flowability of the reaction mixture occurring.
  • the incrustations in the precipitation apparatus and the proportion of grit in the crystalline product obtained by a subsequent process step are said to be considerably reduced.
  • reaction components are continuously fed into an agitator ball mill suitable for wet comminution, the ball filling of which has a bulk volume of more than 50%, in particular 75 to 85% of the grinding chamber volume, and one average residence time of the reaction mixture in the mill is from 3 to 40 s, in particular from 5 to 15 s, at a temperature of 40 to 80 ° C., in particular from 50 to 70 ° C.
  • the process steps according to the invention result in average particle sizes of only about 5 ⁇ m in the suspension obtained with an unusually narrow distribution width.
  • the precipitation apparatus works self-cleaning in the process according to the invention. This reduces the formation of coarse grains due to incrustations. After crystallization, the proportion of grit in the crystalline product is only about 0.01% by weight.
  • the use of ball mills is known.
  • the finished product the crystalline zeolite in the form of a liquid slurry
  • the slurry containing the finished crystalline product is also ground in a ball mill after washing and drying in order to increase the fine fraction in the powder.
  • the finished product is first ground.
  • the use of a ball mill as a reaction apparatus is not known from this prior art.
  • Another process relates to the production of high-silica zeolites with a SiO 2 / Al 2 O 3 molar ratio greater than 10 (DD-PS 206 551).
  • These zeolites can only be prepared by other processes in the presence of organic cations, mostly ammonium or phosphonium ions or their precursors. Instead of using these cations, a ball mill is used in which the reaction components are stirred continuously for about 30 minutes. The grinding takes place at elevated temperature under increased pressure, so that complex special constructions of ball mills are required here.
  • conventional, only slightly modified standard ball mills suitable for wet grinding under normal pressure and only slightly modified can be used. The advantage achieved according to the invention of restricting the formation of incrustations so that longer downtimes of the precipitation apparatus are achieved is not mentioned in this document.
  • reaction components are preferably mixed under their own pressure.
  • an additional static pressure is not necessary.
  • reaction components are fed into the agitator ball mill via different inlets.
  • the mixing therefore takes place only in the grinding chamber. In this way, no incrustations can occur in the feed lines of the ball mill.
  • reaction components be mixed in a stirred ball mill having a grinding section and the sodium aluminate solution continuously at the beginning of the grinding section and the sodium silicate solution downstream between the beginning and the end of the grinding section via one or more inlets feeds the agitator ball mill.
  • the sodium silicate solution can be fed in in one stream or in a plurality of partial streams connected in series according to the known method according to EP 16 393 B1.
  • the latter measure increases the fluidity of the reaction mixture.
  • the reverse order is also possible and applicable.
  • a particular advantage of the process according to the invention lies in the possibility of using unfiltered reaction components.
  • the starting solutions had to be filtered, since undissolved fractions contained therein greatly increased the coarse fractions in the crystalline product. This also increased the incrustation. These problems no longer occur in the process according to the invention.
  • Another important advantage of the invention lies in the possibility of using starting solutions with higher concentrations than usual. This further increases the space-time yield in the precipitation process.
  • concentration of the starting solutions used is limited by the increasing viscosity.
  • the molar ratios of the reaction components are 1.5 to 12 a2 ⁇ : 1.0 Al2O3: 1.5 to 6.0 SiO2: 40 to 80 H2O.
  • the amorphous sodium aluminum silicates produced by the process according to the invention are preferably converted to zeolites in a second process step (crystallization). These are advantageously used as a heterogeneous inorganic builder in washing, rinsing and cleaning agents. If necessary, the finished product still has to be washed and dried after crystallization or subjected to other packaging.
  • FIG. 1 shows an agitator ball mill suitable for carrying out the method, in longitudinal section
  • Figures 2 and 3 grain size distributions of the amorphous precipitation.
  • a stirring shaft 3 equipped with stirring disks 2 is mounted in a fixed cylindrical grinding container 1, with the aid of which grinding balls in the grinding container 1 are moved rapidly in a rotating manner.
  • the grinding ball size is mainly 1 to 3 mm. Balls of the same size are mostly used. The degree of ball filling is up to 85%.
  • agitator ball mills with at least two inlet ports 4.5 were used.
  • One nozzle was used for the aluminate solution, namely nozzle 4.
  • the second nozzle 5 was used for the joint introduction of sodium silicate solution and sodium hydroxide solution.
  • several nozzles were fitted in the cylindrical part of the grinding container. The separation of the Grinding balls of the precipitating product flowing through take place at outlet 6 via a narrow gap or an inserted sieve.
  • the grain size distribution shown in FIG. 2 was measured on a sample from this test, which was quenched immediately after the precipitation in ice water in order to rule out a change.
  • a sample of this precipitation batch was crystallized by heating to 85 ° C. for 40 minutes, then filtered and washed out without alkali.
  • the calcium binding capacity was 164 mg CaO / g sodium aluminum silicate, the average particle size X50 2.8 ⁇ m and the grit value 0.03% by weight.
  • the particle size X50 indicates the diameter, which is less than 50% of all particles.
  • the grit value was determined as a wet sieve residue, modified according to Mocker (DIN 53580) on a 50 ⁇ sieve.
  • a crystallized sample processed as in Example 1 had a calcium binding capacity of 167 mg CaO / g sodium aluminum silicate, an average particle size X50 of 2.7 ⁇ m and a grit value of 0.08% by weight.
  • Example 1 An average residence time of about 6.0 seconds was observed.
  • the average particle size X50 of the suspension for suspension was 3.6 ⁇ m.
  • a sample crystallized and worked up as in Example 1 had a calcium binding capacity of 165 mg CaO / g sodium aluminum silicate, an average particle size X50 of 2.5 ⁇ m and a grit value of 0.01% by weight.

Landscapes

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

Abstract

Une suspension alcaline aqueuse de silicates de sodium-aluminium finement répartis, amorphes aux rayons X, de composition 0,9 à 1,1 Na2O : 1 Al2O3 : 1,8 à 3,6 SiO2 est fabriquée en mélangeant en continu une solution aqueuse d'aluminate de sodium avec une solution aqueuse de silicate de sodium, en présence d'un excès de lessive de soude, à température élevée. Les composants réactionnels sont introduits en continu dans un broyeur à boulets et malaxeur, convenant pour le broyage par voie humide, et dont les boulets occupent un volume apparent de plus de 50 % du volume de broyage, en réglant le temps moyen de séjour du mélange réactionnel dans le broyeur à 3 à 4 s, pour une température de 40 à 80 °C. On obtient un rendement de l'espace-temps très élevé, au stade de la précipitation, sans problème d'écoulement du mélange réactionnel. Les incrustations dans les appareils de précipitation sont nettement réduites.
PCT/EP1993/000044 1992-01-21 1993-01-12 Procede de fabrication de silicates de sodium-aluminium amorphes WO1993014028A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP5512132A JPH07502966A (ja) 1992-01-21 1993-01-12 無定形ケイ酸アルミニウムナトリウムの製法
EP93902169A EP0623096A1 (fr) 1992-01-21 1993-01-12 Procede de fabrication de silicates de sodium-aluminium amorphes
KR1019940702512A KR950700216A (ko) 1992-01-21 1993-01-12 무정형 규산알루미늄나트륨의 제조방법(Process for Producing Amorphous Sodium Aluminium Silicates)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4201455A DE4201455A1 (de) 1992-01-21 1992-01-21 Verfahren zum herstellen von amorphen natriumaluminiumsilikaten
DEP4201455.7 1992-01-21

Publications (1)

Publication Number Publication Date
WO1993014028A1 true WO1993014028A1 (fr) 1993-07-22

Family

ID=6449915

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000044 WO1993014028A1 (fr) 1992-01-21 1993-01-12 Procede de fabrication de silicates de sodium-aluminium amorphes

Country Status (5)

Country Link
EP (1) EP0623096A1 (fr)
JP (1) JPH07502966A (fr)
KR (1) KR950700216A (fr)
DE (1) DE4201455A1 (fr)
WO (1) WO1993014028A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6868002B2 (ja) * 2016-03-31 2021-05-12 日本碍子株式会社 ゼオライト粉末の製造方法
JP6609693B2 (ja) * 2016-03-31 2019-11-20 日本碍子株式会社 ゼオライト粉末の製造方法
CN111167569B (zh) * 2019-12-31 2021-08-17 曲靖华益兴新材料有限公司 直接球磨制备易分散铝粉颜料的方法和设备

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0016393A2 (fr) * 1979-03-15 1980-10-01 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de silicates amorphes d'aluminium et de sodium
DD206551A1 (de) * 1982-02-23 1984-02-01 Bitterfeld Chemie Verfahren zur herstellung von hochkieselsaeurehaltigen zeolithen v

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0016393A2 (fr) * 1979-03-15 1980-10-01 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de silicates amorphes d'aluminium et de sodium
DD206551A1 (de) * 1982-02-23 1984-02-01 Bitterfeld Chemie Verfahren zur herstellung von hochkieselsaeurehaltigen zeolithen v

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SWISS CHEM Bd. 4, Nr. 3A, 1982, ZUERICH,CH SEITEN 61,62,65,66,69,70,73,74 D.WOLF ET AL. *

Also Published As

Publication number Publication date
KR950700216A (ko) 1995-01-16
DE4201455A1 (de) 1993-07-22
JPH07502966A (ja) 1995-03-30
EP0623096A1 (fr) 1994-11-09

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