WO1993014029A1 - Verfahren zum herstellen feinteiliger kristalliner natriumaluminiumsilikate - Google Patents
Verfahren zum herstellen feinteiliger kristalliner natriumaluminiumsilikate Download PDFInfo
- Publication number
- WO1993014029A1 WO1993014029A1 PCT/EP1993/000045 EP9300045W WO9314029A1 WO 1993014029 A1 WO1993014029 A1 WO 1993014029A1 EP 9300045 W EP9300045 W EP 9300045W WO 9314029 A1 WO9314029 A1 WO 9314029A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- crystallization
- containers
- sodium aluminum
- continuously
- suspension
- Prior art date
Links
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
- C11D3/128—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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
Definitions
- the invention relates to a process for producing finely divided crystalline sodium aluminum silicates of the composition 0.9 to 1.1 Na ⁇ : 1 Al 2 O 3: 1.8 to 3.6 SiO 2 by crystallizing an aqueous suspension of X-ray amorphous sodium aluminum silicate at elevated temperature.
- a precipitate of amorphous sodium aluminum silicate is instantaneously formed in all batch and concentration ranges of the reaction partners which are customary in technology.
- amorphous silicates that are used, but rather their crystalline, preferably zeolitic, secondary products. They are widely used, for example, as cation exchangers, especially for softening water, as catalyst supports in chemical processes, as drying, separating or sorbents for solvents and gases, and as heterogeneous inorganic builders in detergents and cleaning agents.
- crystalline, finely divided zeolite 4A as a phosphate substitute in a high quality form.
- the following requirements must be met.
- a calcium binding capacity of about 170 mg CaO / g sodium aluminum silicate (active substance) and an average particle size of about 2 to 3 ⁇ m with a narrow-band grain spectrum is required.
- the proportion of particles with a grain size above 50 ⁇ m, hereinafter referred to as "grit" should not be more than 0.1% by weight.
- the invention is therefore based on the object of providing a method for producing finely divided crystalline sodium aluminum silicates of the composition mentioned at the beginning, the crystallization stage being carried out continuously and the abovementioned quality requirements being able to be met reliably and reproducibly.
- X-ray amorphous sodium aluminum silicates are used for crystallization, which can be obtained by, in particular continuous, mixing of an aqueous sodium aluminate solution with an aqueous sodium silicate solution in the presence of excess sodium hydroxide solution at elevated temperature, this precipitation batch being obtained at the Mixing of the reaction components or later, but before crystallization, has been passed through 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, with an average residence time in the mill of 3 up 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 crystallization is then carried out continuously. It is possible to work at crystallization temperatures and times as well as other process parameters which are in the ranges customary for the crystallization of zeolite A.
- the invention is not restricted to the known
- a variety of continuous manufacturing processes for zeolite A are known, e.g. B. from Swiss Chem. 4 (1982) pp. 61-74, but the known continuous synthesis routes do not allow the simultaneous fulfillment of all of the above-mentioned quality requirements, e.g. B. Prerequisites for use in formulations of detergents and cleaning agents are.
- X-ray amorphous sodium aluminum silicates are used for the crystallization, an agitator ball mill being used under the conditions mentioned during the precipitation or in a grinding step following any precipitation process.
- the agitator ball mill is not used, or at least not only for grinding the already precipitated sodium aluminum silicates, but, contrary to its original use, as a precipitation apparatus.
- mean particle sizes of only about 5 ⁇ m are obtained in the suspension of amorphous particles obtained with an unusually narrow distribution width.
- the grit content in the crystalline product is only about 0.01% by weight.
- Another process relates to the production of high-silica zeolites with a larger SiO 2 / Al 2 O 3 molar ratio 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.
- standard ball mills which are customary according to the invention and which are suitable for wet grinding under normal pressure and are only slightly modified can be used.
- an aqueous, alkaline suspension is used for the crystallization.
- the suspension obtained by precipitation in a stirred ball mill in accordance with the earlier application DE-A 4201455 is used directly with X-ray amorphous sodium aluminum silicates without further aftertreatment.
- the excess of alkali accelerates the crystallization through increased nucleation and enables a relatively short crystallization time.
- Precipitation and crystallization are preferably carried out continuously and immediately in succession. However, a process management that is separate in terms of time and space is also possible.
- the suspension flows through reaction apparatus such as stirred columns, tubular reactors, stirred tanks or the like, with a more or less strong backmixing occurring.
- reaction apparatus such as stirred columns, tubular reactors, stirred tanks or the like
- the crystallization can be carried out in a manner known per se and in apparatus known per se, provided that only the X-ray amorphous sodium aluminum silicates produced by the above-mentioned process using an agitator ball mill are used in order to obtain crystalline products without any significant loss in quality.
- containers filled with the X-ray amorphous sodium aluminum silicate suspension are transported on a route while maintaining the elevated temperature.
- the containers can be transported through a continuous furnace and / or the crystallization can be carried out in heated containers.
- Bucket elevators can also be used as containers or the containers can be transported on a conveyor belt.
- a particularly important advantage of the invention lies in the fact that when the suspension prepared in a stirred ball mill according to the invention is used under the conditions specified above, it is not necessary to stir the reaction mixture during crystallization or to have shear forces acting on it in any other way. If, in contrast to the invention, individual containers are filled with precipitation suspensions prepared according to the prior art by means of stirred columns and allowed to crystallize under the usual conditions, grit values of 1% by weight are obtained if the mixture was not stirred during the crystallization . The grit values are below 0.1% by weight only when stirred.
- the possibility according to the invention of carrying out the crystallization without the action of shear forces and nevertheless fulfilling all quality requirements for the product opens up a route to the technically particularly simple configuration of the continuous crystallization.
- the high expenditure on equipment for continuously conveyed and simultaneously stirred containers can therefore be avoided according to the invention. It is reproducibly possible to crystallize precipitate suspensions originating from stirred ball mills in unstirred systems in such a way that grit values are obtained which were obtained with those from stirred systems practically match.
- the suspension obtained in particular continuously, be filtered after crystallization.
- the crystalline zeolites obtained in the process according to the invention are advantageously used as a heterogeneous inorganic builder in washing, rinsing and cleaning agents. If necessary, the finished product must still be washed and dried after crystallization or be subjected to other packaging.
- FIG. 1 shows an agitator ball mill suitable for carrying out the method in longitudinal section.
- a stirring shaft 3 equipped with stirring disks 2 was mounted in a stationary cylindrical grinding container 1, with the aid of which grinding balls in the grinding container 1 were moved rapidly in a rotating manner.
- the grinding ball size was mainly 1 to 3 mm. Spheres of the same size were mostly used. The degree of ball filling was up to 85%.
- Agitator ball mills with at least two inlet ports 4, 5 were used to produce the precipitation suspensions used according to the invention.
- One nozzle was used for the aluminate solution, mainly nozzle 4.
- the second nozzle 5 was used for the joint introduction of sodium silicate solution and sodium hydroxide solution.
- several nozzles were installed in the cylindrical part of the grinding container. The grinding balls were separated from the precipitating product flowing through at outlet 6 via a narrow gap or an inserted sieve.
- Example 1 Preparation of a precipitation suspension
- An amorphous sodium aluminum silicate suspension which had been prepared by continuously reacting sodium aluminate, sodium silicate and sodium hydroxide solution in a stirred ball mill in accordance with Example 1 and the earlier application P 4201 455, was collected in a stirred container with an average residence time of 30 minutes (forming time) . From this suspension was continuously pumped into unstirred chambers which, after being completely filled, were introduced into a continuous furnace in which a temperature of 80 ° C. was maintained. After 30 minutes, the chamber on the other side left the oven, was completely emptied and could then be refilled. The crystal suspension was then continuously filtered and washed.
- the calcium binding capacity was 168 mg CaO / g sodium aluminum silicate, the average particle size X50 2.6 ⁇ m and the grit value 0.02% 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 ⁇ m sieve.
- amorphous sodium aluminate silicate suspension was removed from a stirred column and otherwise subjected to the same crystallization process as described in Example 1.
- the resulting zeolite A which was worked up as in Example 2, had a calcium binding capacity of 167 mg CaO / g sodium aluminum likate, an average particle size X50 of 2.8 ⁇ m and a grit value of 0.95% 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93902170A EP0623097A1 (de) | 1992-01-21 | 1993-01-12 | Verfahren zum herstellen feinteiliger kristalliner natriumaluminiumsilikate |
KR1019940702511A KR950700217A (ko) | 1992-01-21 | 1993-01-12 | 미립 결정질 규산 알루미늄 나트륨의 제조방법(process for producing finely-divided crystalline sodiun aluminium silicates) |
JP5512133A JPH07502967A (ja) | 1992-01-21 | 1993-01-12 | 微細化された結晶性ケイ酸アルミニウムナトリウムの製法 |
Applications Claiming Priority (4)
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 | ||
DE19924210366 DE4210366A1 (de) | 1992-03-30 | 1992-03-30 | Verfahren zum Herstellen feinteiliger kristalliner Natriumaluminiumsilikate |
DEP4210366.5 | 1992-03-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993014029A1 true WO1993014029A1 (de) | 1993-07-22 |
Family
ID=25911114
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1993/000045 WO1993014029A1 (de) | 1992-01-21 | 1993-01-12 | Verfahren zum herstellen feinteiliger kristalliner natriumaluminiumsilikate |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0623097A1 (de) |
JP (1) | JPH07502967A (de) |
KR (1) | KR950700217A (de) |
WO (1) | WO1993014029A1 (de) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0016393A2 (de) * | 1979-03-15 | 1980-10-01 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung von amorphen Natriumaluminiumsilikaten |
DD206551A1 (de) * | 1982-02-23 | 1984-02-01 | Bitterfeld Chemie | Verfahren zur herstellung von hochkieselsaeurehaltigen zeolithen v |
-
1993
- 1993-01-12 KR KR1019940702511A patent/KR950700217A/ko not_active Application Discontinuation
- 1993-01-12 EP EP93902170A patent/EP0623097A1/de not_active Withdrawn
- 1993-01-12 WO PCT/EP1993/000045 patent/WO1993014029A1/de not_active Application Discontinuation
- 1993-01-12 JP JP5512133A patent/JPH07502967A/ja active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0016393A2 (de) * | 1979-03-15 | 1980-10-01 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung von amorphen Natriumaluminiumsilikaten |
DD206551A1 (de) * | 1982-02-23 | 1984-02-01 | Bitterfeld Chemie | Verfahren zur herstellung von hochkieselsaeurehaltigen zeolithen v |
Non-Patent Citations (1)
Title |
---|
SWISS CHEM Bd. 4, Nr. 3A, 1982, ZUERICH,CH seiten 61,62,65,66,69,70,73,74 D.WOLF ET AL. in der Anmeldung erwähnt * |
Also Published As
Publication number | Publication date |
---|---|
EP0623097A1 (de) | 1994-11-09 |
KR950700217A (ko) | 1995-01-16 |
JPH07502967A (ja) | 1995-03-30 |
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