EP2438010A1 - Zéolithe 4a présentant de nouvelles propriétés morphologiques, et synthèse et utilisation de celle-ci - Google Patents

Zéolithe 4a présentant de nouvelles propriétés morphologiques, et synthèse et utilisation de celle-ci

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Publication number
EP2438010A1
EP2438010A1 EP10725495A EP10725495A EP2438010A1 EP 2438010 A1 EP2438010 A1 EP 2438010A1 EP 10725495 A EP10725495 A EP 10725495A EP 10725495 A EP10725495 A EP 10725495A EP 2438010 A1 EP2438010 A1 EP 2438010A1
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European Patent Office
Prior art keywords
zeolite
fla
particles
sample
synthesis
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EP10725495A
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German (de)
English (en)
Inventor
Boris Subotic
Cleo Kosanovic
Sanja Bosnar
Tatjana Antonic Jelic
Josip Bronic
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Barchem LLC
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Barchem LLC
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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
    • C01B39/14—Type A
    • C01B39/16—Type A from aqueous solutions of an alkali metal aluminate and an alkali metal silicate excluding any other source of alumina or silica but seeds
    • 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

Definitions

  • the present invention relates to a zeolite 4A with new morphological properties, its synthesis and use.
  • the present invention solves technical problem of improved zeolite 4A with new morphological properties, more precisely, which is characterized by spheroidal-shape, ,,face-less" particles (zeolite FLA) .
  • the latter exhibits improved adsorption properties due to high external surface roughness and thus, significantly enhanced external specific surface area (SSA) as well as increased rate of ionic exchange. Thanks to this property, the product provides an improved alternative to existing, commercially available zeolite A as detergent builder, absorbents and carrier for active substances.
  • the invention also discloses a synthesis of zeolite FLA, as well as its potential uses.
  • Zeolites are a clas s o f aluminosilicates of general formula :
  • M metal cation (like Na + )
  • molar ratio of silicon to aluminum, y:x is between 1:1 to >100:l
  • number of crystalline water m is from 0 to >100.
  • zeolite 4A of general formula (usually expressed as molar ratio of corresponding metal oxide, aluminum oxide and silicon dioxide) :
  • Zeolite 4A binds calcium (Ca 2+ ) and magnesium (Mg 2+ ) ions from ordinary tap water making it soft, releasing equivalent amounts of sodium (Na + ) cations, and thus promotes overall washing process.
  • Synthesis of zeolites is generally based on crystallization from aluminosilicate hydrogels (hydrothermal synthesis) .
  • the latter are obtained by mixing of sodium silicate and sodium aluminosilicate solutions.
  • the synthesis of zeolites is influenced by a numerous parameters such as: molar ratio of reactants Na 2 O: Al 2 O 3 : SiO 2 : H 2 O, time and temperature of crystallization, intensity and kind of stirring of intermediate aluminosilicate gel, presence or absence and concentration of additional cations, alkalinity, and many others [T. Antonic, B. Subotic, N.
  • Stubicar Influence of gel properties on the crystallization of zeolites: Part 1: Influence of alkalinity during gel preparation on the kinetics of nucleation of zeolite A, Zeolites 18 (1997) 291-300; V. Grba, Z. Soljic: Low silica synthetic faujasite X and synthetic zeolite A formation from sodium-aluminosilicate gels, Bull. Groupe Franc. Argiles XXVII 167-175; RU 2003 122223 A; 0. Andac, M. Tather, A. Sirkecioglu, I. Ece, A. Erdem-Senatalar : Effect of ultrasound on zeolite A synthesis, Micropor. Mesopor. Mater. 79 (2005) 225-233] .
  • zeolite A D. Bretaudeau, F. Delprato, M. Malassis: Preparation of crystalline 4A zeolites, US 5,474,753 (1995); J. Metzger: Process for preparing crystalline sodium silico-aluminate of zeolite A type, GB 2051024A (1980); J. Deabriges: Industrial process for continuous production of zeolite A, US 4,314,979 (1979)].
  • zeolite 4A is of cubic shape particles, usually of median size 4-5 ⁇ m.
  • zeolite P with maximum alumina content [,,zeolite MAP": G. T. Brown, T. J. Osinga, M. J. Parkington, A. T. Steel, EP0384070 A2 (1988) Unilever] .
  • Effective calcium binding capacity of zeolite MAP is at least 145 mg CaO/g, preferably at least 150 mg CaO/g.
  • Zeolite MAP exchanges calcium more rapidly and binds it more firmly than zeolite 4A does, especially at low temperatures. Its magnesium exchange is also more rapid than that of zeolite 4A.
  • zeolite 4A appears in cubic crystals with sharp edges and apexes (see Fig.l). This characteristic is highly unfavorable for use in the detergent formulations because of sharp apexes that cause:
  • zeolite is not only an ion- exchanger, but also a carrier of active washing components, especially non-ionic surfactants.
  • production of this kind of detergent powders demands the builders having not only high ion-exchange capacity and efficacy (for calcium and magnesium cations) , but also a high adsorption capacity for non-ionic surfactants .
  • a shape of zeolite crystals changes from those well known in the art as either cubic (see Fig.l) or eventually cubic with truncated (see Fig.2) or rounded apexes and edges (see Fig.3), into spheroidal one (see Fig.4).
  • Figure 1 SEM photograph of typical cubic crystals of zeolite 4A having sharp edges and apexes (prior art) .
  • Figure 2 SEM photograph of cubic crystals of zeolite 4A with truncated edges and apexes (prior art) .
  • Figure 3 SEM photograph of cubic crystals of zeolite 4A with rounded edges and apexes (prior art) .
  • Figure 4 SEM photograph of zeolite FLA particles magnified for (a) 10.00Ox and (b) for 33.00Ox (invention).
  • Figure 5 Crystal size distributions by number (A) and by volume (B) of zeolite A crystals having the regular cubic shape with sharp edges and apexes (see Fig.l).
  • N 0 and V 0 are the number and volume percentage of the particles (crystals) having the equivalent spherical diameter D.
  • Figure 6 Crystal size distributions by number (A) and by volume (B) of zeolite A crystals having cubic shape with truncated edges and apexes (see Fig.2) .
  • W 0 and V 0 are the number and volume percentage of the particles (crystals) having the equivalent spherical diameter D.
  • Figure 7 Crystal size distributions by number (A) and by volume (B) of zeolite A crystals having cubic shape with rounded edges and apexes (see Fig.3) .
  • N 0 and V 0 are the number and volume percentage of the particles (crystals) having the equivalent spherical diameter D.
  • Figure 8 Crystal size distributions by number (A) and by volume (B) of zeolite FLA particles (see Fig.4) of sample FLA-I.
  • W 0 and V D are the number and volume percentage of the particles (crystals) having the equivalent spherical diameter D.
  • Figure 9 Crystal size distributions by number (A) and by volume (B) of zeolite FLA particles (see Fig.4) of sample FLA-2.
  • N 0 and V 0 are the number and volume percentage of the particles (crystals) having the equivalent spherical diameter D.
  • Figure 10 Crystal size distributions by number (A) and by volume (B) of zeolite FLA particles (see Fig.4) of sample FLA-3.
  • W n and V 0 are the number and volume percentage of the particles (crystals) having the equivalent spherical diameter D.
  • Figure 11 Schematic presentation of RSSA versus GSSA shown on the adsorption of nitrogen of (a) standard cubic zeolite A and b) zeolite FLA.
  • Figure 12 Scheme of a complex of non-ionic surfactant polyoxyethylene (23) laurate after adsorption onto the surface of zeolite FLA particle.
  • Zeolite FLA was synthesized by the following general procedure:
  • aluminosilicate hydrogel (i) Preparation of aluminosilicate hydrogel;
  • the synthesis precursor is prepared by mixing of sodium aluminate solution (having appropriate chemical composition with respect to Na 2 O, Al 2 O 3 and H 2 O) and sodium silicate solution (having appropriate chemical composition with respect to Na 2 O, SiO 2 and H 2 O) at temperatures (Tp) from room temperature (20 0 C) to 90 0 C.
  • Tp room temperature (20 0 C) to 90 0 C.
  • Separated zeolite FLA is subjected to washing with several portions of demineralized water in order to remove all residual reagents (from the mother liquor) adsorbed on the product crystals until pH of filtrate is 9-10.
  • the progress of the reaction was monitored by optical microscope (magnification of 100Ox) , and finally by X-ray diffraction (XRD) of powdered samples.
  • the corresponding average chemical composition of zeolite FLA from the present invention is as follows:
  • Shape of zeolite 4A particles is determined from scanning- electron microscope (SEM) photographs of appropriate samples. Zeolite FLA was compared with all known morphological forms of zeolite 4A:
  • the FLA type of zeolite A from the present invention is characterized by unexpected spheroidal shape of each single particle (not particles aggregates); see Figure 4. More unexpectedly, zeolite FLA is characterized by expressed external surface roughness without distinguishing crystal faces (SEM; magnification 30.00Ox).
  • the high external surface roughness of zeolite FLA is also indicated by unexpectedly high ratio between real specific surface area ratio
  • RSSA Brunauer-Emmett-Teller
  • GSSA geometrical specific surface area
  • the BET method is commonly used for measurement of specific surface areas of solid substances.
  • the BET method is employed for measurement of total SSA meaning a sum of external SSA and SSA of all pores in a given sample. This kind of measurement is carried out at elevated pressures allowing gaseous adsorbate (e.g. nitrogen) to enter into the zeolite pores ⁇ .
  • gaseous adsorbate e.g. nitrogen
  • the BET method offers a possibility of measuring only the external specific surface area (SSA), i.e., sum of external areas of all particles contained in unit mass of sample (without corresponding area of pores inside each particle!), if a working mode is at low pressures. This technique was used for determination of external specific surface area of samples in the present invention.
  • SSA external specific surface area
  • RSSA Real external specific surface area
  • RSSA External real (measured) specific surface area significantly depends on particles size of a given sample. Since it is practically impossible to obtain zeolite FLA and all three known cubic shape- based zeolites 4A of the same particles size distribution, comparable differences can be seen from the ratio of RSSA and geometrical specific surface area (GSSA) . In this manner one can practically exclude the differences in particles size distribution. Practically the ratio of RSSA/GSSA allows us to compare external (without those derived from internal pores) specific surface areas of samples with different particles size distributions. In this context, the ratio RSSA/GSSA represents a measure of the external surface roughness. In this invention high external surface roughness is considered to represent ratio RSSA/GSSA > 2.
  • GSSA geometrical specific surface areas
  • Ni number frequency of the particles (crystals) having the size L 1 ;
  • p 2 g/cm 3 is the density of zeolite A;
  • G 2 surface geometrical shape factor (see Table 2);
  • G 3 volume geometrical shape factor (see Table 2) .
  • Geometrical surface area is the surface area of a geometrically defined body (e.g. cube, cube with truncated edges, cube with truncated edges and apexes, sphere) having the flat level surfaces [A. Peiquey et al., Carbon 39 (2001) 507-514; K. Kaneko, C. Ishii, Colloids and Surfaces 67 (1992) 203-212] . Consequently, geometrical specific surface area is the sum of geometrical surface areas of all bodies (particles) contained in unit mass of solid, as expressed by Eq. (3).
  • the average crystal size (L av ) , specific number of particles N 3 , and geometrical specific surface area (GSSA) are calculated by equations (1-3) , using the values D 1 and N 1 from the corresponding particle size distribution by number shown in:
  • GSSA geometrical specific surface area
  • RSSA real specific surface area
  • RSSA/GSSA of the standard samples do not considerably depend either on the crystal shape (see Table 4) or the corresponding crystal size distributions (see Figs. 8A-10A) .
  • the values of RSSA/GSSA ⁇ 1 indicate that absorption of nitrogen is characterized by formation of mono-layer on the flat surfaces of standard samples, in accordance with BET theory.
  • the ratio RSSA/GSSA of zeolite FLA is 2.22-2.4 times higher than the ratio RSSA/GSSA of zeolite A having cubic crystals with rounded edges and apexes and 2.49-3.1 times higher than the RSSA/GSSA ratios of zeolite A sharp edges and apexes and cubic crystals with truncated edges, respectively.
  • zeolite FLA per unit geometrical surface area (as calculated by Eq. (3)) of zeolite FLA can be adsorbed 2.22-3.1 times more of nitrogen than per the same unit geometrical surface area of standard morphological forms of zeolite A.
  • adsorption ability of zeolite FLA is an average 2.7 times higher than the absorption ability of standard morphological forms of zeolite A having the same geometrical specific surface area and thus, the same particles size distribution as zeolite FLA (see Fig.11)
  • zeolite FLA from the present invention unexpectedly showed improvement of efficacy (rate) of uptake of calcium (Ca 2+ ) and magnesium (Mg 2+ ) cations.
  • the rate of uptake of Ca 2+ (expressed as U Ca o) and Mg 2+ (expressed as U Mg0 ) cations during the exchange process of calcium and magnesium ions from solution with sodium ions from zeolite A is a measure of efficiency regarding the rate of ion-exchange process of zeolites.
  • the ion- exchange process was monitored with known amounts of anhydrous zeolite sample in a solution of calcium (or magnesium) chloride also of known starting concentration, at 20 0 C and 65 0 C. Determination of remained concentrations of Ca 2+ and Mg 2+ cations in supernatant as a function of time were conducted by atomic absorption spectroscopy (AAS) . Then, the uptakes (U Ca o/ U Mg0 ) were calculated from the difference between cation concentrations in the liquid phase before and after exchange for a time t E . Results are shown in Tables 5-8.
  • Table 5 shows that the exchange of calcium ions from solution with sodium ions from (dehydrated) zeolite FLA is very fast and efficient process; 160 mg of CaO is bounded per 1 g of zeolite in less than 3 min, even at room temperature (20 0 C) . Under the same conditions and in the same time (3 min) only about 110-126 mg (21-31% less) of CaO is bonded per 1 g of known morphological forms of zeolite 4A.
  • the present invention relates to the new morphological type of zeolite 4A which is characterized by spheroidal shape ,,face-less" particles (zeolite FLA) .
  • zeolite FLA spheroidal shape ,,face-less particles
  • SSA external specific surface area
  • zeolite FLA serves not only as ion-exchange (thus as water-softening) agent, but also as effective carrier for non-ionic surfactants, presumably due to adsorption onto very large external specific surface area of zeolite FLA (rough) particles. Adsorption process is presumably promoted by formation of complex bonds between the sodium cations (Lewis acids; which are positioned closed to the surface) and oxygen atoms (Lewis bases) from polyethyleneglycol chain of non-ionic surfactants such as ethoxylated fatty alcohols (e.g. polyethyleneglycol (23) laurate; Brij 35).
  • ADM adsorbing molecules
  • carrier of other organic molecules such as various drug molecules like penicillin or acetylsalicylic acid, proteins, nucleic acids, etc., capable of forming coordination bonds (complex) with the surface of the zeolite; and as
  • Infrared transmission spectra of the samples were made by the KBr wafer technique. The spectra were recorded on an FTIR Spectrometer System 2000 FT-IR (Perkin-Elmer) .
  • Particles (crystals) size distribution curves of the crystalline end products (zeolite A) are determined with Mastersizer 2000 (Malvern Instruments) laser light-scattering particle size analyzer.
  • the external specific surface areas (ESSA) of samples were measured by using Gemini 2360 Surface Area Analyzer (Micrometrics) .
  • Example 1 Preparation of standards of cubic shape-based zeolites 4A
  • the aluminosilicate hydrogel precursors having the overall oxide molar batch composition:
  • Crystallizations were carried out by heating of corresponding aluminosilicate gels at elevated temperature, in the range between 80-90 0 C under stirring by propeller in a stainless-steel reaction vessel provided with a thermostated jacket and fitted with a water- cooled reflux condenser and thermometer, until the solid phase of precursor (gel) was completely transformed into crystalline phase (zeolite) .
  • the end-points of crystallizations were determined by monitoring samples of the reaction mixture under optical microscope (at magnification of 100Ox) . Then the products were separated by filtration and washed with several portions of demineralized water until pH of filtrate reached 9-10. Products were dried at 105 0 C for 24 h. After drying, the products (zeolite 4A) appear in the form of white fine microcrystalline powder.
  • Example 2 Preparation of spheroidal shape "face-less" zeolite FLA (sample FLA-I)
  • Crystallization was carried out by heating of aluminosilicate gel at 85-90 0 C under stirring for 135 min, i.e. until the solid phase of the precursor (gel) was completely transformed into crystalline phase (monitoring of samples of reaction mixture by optical microscope at magnification of 100Ox) . Then the product was separated by vacuum filtration and washed with several portions of demineralized water until pH of filtrate reached 9-10. Product was dried at 105 0 C for 24 h. After drying, the product (zeolite FLA-I) appears in the form of white fine microcrystalline powder. Utilization of reactants (because of the "excess" of Al 2 O 3 in the reaction mixture, the utilization is expressed on the basis of spent SiO 2 ) : 95.8% calculated on starting SiO 2 .
  • the dried solid sample of zeolite FLA was kept in a desiccator with saturated NaCl solution for 96 h.
  • Quantitative contents of sodium (Na), aluminum (Al), and silicon (Si) Weighted sample of calcined (waterless) product was dissolved in 1:1 HCl solution. The solution was diluted with distilled water to the concentration ranges available for measuring the concentrations of Na, Al and Si by atomic absorption spectroscopy (AAS) . From the measured concentrations of Na, Al, and Si in the solutions and quantity of the calcinated sample dissolved in known volumes of solution, the average contents of Na, Al, and Si (in oxide forms; Na 2 O, Al 2 O 3 , SiO 2 ) in the sample, the following contents of Na 2 O, Al 2 O 3 , SiO 2 and H 2 O in zeolite FLA were obtained:
  • corresponding average molar oxide composition of the zeolite FLA was: 1.017Na 2 O • Al 2 O 3 • 1.973SiO 2 • 4.725H 2 O.
  • XRD and FTIR analyzes of zeolite FLA had XRD patterns and FTIR spectra are characteristic for fully crystalline zeolite 4A.
  • Particles of zeolite FLA have the sizes in micrometer range (about 0.4-5 ⁇ m by number; see crystal size distribution curve in Fig.8A). 50% of all particles have the size (D 50 ) less than 1.45 ⁇ m and 90% of all particles have the size (D 90 ) less than 2.35 ⁇ m. These data were also used for calculation of geometrical specific surface area (GSSA) of the sample. Results are given in Tables 2 and 3.
  • the external specific surface area (RSSA) of the sample was determined by multiple BET method on Gemini 2360 surface area analyzer by using nitrogen as adsorbate at the temperature of liquid nitrogen (-195.6 0 C). Prior the analysis the samples were dried for one hour at 105 0 C. The external specific surface areas of the analyzed samples are calculated on the basis of BET isotherm. The results are shown in Table 1.
  • the supernatant was carefully removed from solid phase precipitate, and used for measuring the concentration of calcium or magnesium by atomic absorption spectroscopy (AAS) .
  • the exchanged amount of calcium or magnesium ions was calculated from the difference between the initial concentration of calcium or magnesium ions (0.005 mold ⁇ f 3 ) and their concentrations in the liquid phase after the exchange process was interrupted.
  • Results are shown as the amount of CaO (U Ca0 ) and MgO (U Mg0 ) , respectively bounded per gram of dehydrated zeolite versus the exchange time (t E ) at 20 0 C (Tables 5 and 7) and 65°C (Tables 6 and 8) .
  • Reaction yield, Y R defined as the amount of zeolite FLA (in grams) obtained from 100 g of the reaction mixture was determined as follows: Solid phase (zeolite FLA) of the reaction mixture was separated from the liquid phase (supernatant) by vacuum filtration, at the end of crystallization process, i.e. when 95.8% of starting amount of SiO 2 vas spent for the synthesis of zeolite FLA. The solid phase on filter paper (zeolite FLA) was washed with several portions of demineralized water until pH of filtrate reached 9-10. The wet washed zeolite FLA was dried overnight at 105 0 C, and cooled down in desiccators with dry silicagel. From known amount of the reaction mixture and, m z , of crystallized zeolite FLA, the reaction yield, Y R , was calculated as:
  • the reaction yield of zeolite FLA obtained in this example is 9.30 wt. %.
  • Example 3 Preparation of spheroidal shape "face-less” zeolite FLA (sample FLA-2)
  • Crystallization was carried out by heating of aluminosilicate gel at 70-80 0 C under stirring for 60 min, i.e., until the solid phase of the gel was completely transformed into crystalline phase (monitoring of samples of reaction mixture by optical microscope at magnification of 100Ox) . Then the product was separated by vacuum filtration and washed with several portions of demineralized water until pH of filtrate reached 9-10. Product was dried at 105 0 C for 24 h. After drying, the product (zeolite FLA-2) appears in the form of white fine microcrystalline powder. Utilization of reactants: 95.8% calculated on starting SiO 2 .
  • Sample FLA-2 also had XRD patterns and FTIR spectra characteristic for fully crystalline zeolite 4A.
  • sample FLA-2 also showed spheroidal shape of crystals (particles) with no identifiable crystal faces and with high external surface roughness.
  • Particle size (distribution) of zeolite FLA (sample FLA-2) : Particles of zeolite FLA have the sizes in micrometer range (about 0.4-5 ⁇ m by number; see crystal size distribution curve in Fig.9A). 50% of all particles have the size (D 50 ) less than 1.1 ⁇ m and 90% of all particles have the size (D 90 ) less than 1.75 ⁇ m. These data were also used for calculation of geometrical specific surface area (GSSA) of the sample. Results are given in Tables 2 and 3.
  • the reaction yield of zeolite FLA (as described in Example 2) obtained in this example is 14.15 wt . %.
  • Example 4 Preparation of spheroidal shape "face-less” zeolite FIA (sample FLA-3)
  • Crystallization was carried out by heating of aluminosilicate gel at 65-75°C under stirring for 120 min, i.e., until the solid phase of the precursor (gel) was completely transformed into crystalline phase (monitoring of samples of reaction mixture by optical microscope at magnification of 100Ox) . Then the product was separated by vacuum filtration and washed with several portions of demineralized water until pH of filtrate reached 9-10. Product was dried at 110 0 C for 24 h. After drying, the product (zeolite FLA-3) appears in the form of white fine microcrystalline powder. Utilization of reactants : 97.2% calculated on starting SiO 2 .
  • Crystal structure of zeolite FLA (sample FLA-3) : XRD patterns and FTIR spectra characteristic for fully crystalline zeolite 4A.
  • sample FLA-3 also showed spheroidal shape of crystals (particles) with no identifiable crystal faces and with high external surface roughness.
  • Particles of zeolite FIA-3 have the sizes in micrometer range (about 0.4-5 ⁇ m by number; see crystal size distribution curve in Fig.10A) . 50% of all particles have the size (D 50 ) less than 1.3 ⁇ m and 90% of all particles have the size (D 90 ) less than 2.75 ⁇ m. These data were also used for calculation of geometrical specific surface area (GSSA) of the sample. Results are given in Tables 2 and 3.
  • the reaction yield of zeolite FIA-3 (as described in Example 2) obtained in this example is 14.60 wt . %.
  • Example 5 Preparation of spheroidal shape "face-less” zeolite 4A (sample FIA-4)
  • Crystallization was carried out by heating of aluminosilicate gel at 70-75 0 C under stirring for 90 min, i.e., until the solid phase of the precursor (gel) was completely transformed into crystalline phase (monitoring as described in Example 2) . Then the product was separated by vacuum filtration and washed with several portions of demineralized water until pH of filtrate reached 9-10. Product was dried at 105 0 C for 24 h. After drying, the product (zeolite FLA-4) appears in the form of white fine microcrystalline powder. Utilization of reactants: 98 % calculated on starting SiO 2 .
  • Example FLA-4 Chemical composition of zeolite FLA (sample FLA-4) : Corresponds to the sample FLA-I (see Example 2) .
  • sample FLA-4 also showed spheroidal shape of crystals (particles) with no identifiable crystal faces and with high external surface roughness.
  • the reaction yield of zeolite FLA-4 (as described in Example 2) obtained in this example is 17.2 wt. %.
  • Example 6 Preparation of spheroidal shape "face-less” zeolite 4A (sample FLA-5)
  • Crystallization was carried out by heating of aluminosilicate gel at 75-80 0 C under stirring for 60 min, i.e., until the solid phase of the precursor (gel) was completely transformed into crystalline phase (monitoring as described in Example 2) . Then the product was separated by vacuum filtration and washed with several portions of demineralized water until pH of filtrate reached 9-10. Product was dried at HO 0 C for 24 h. After drying, the product (zeolite FLA-5) appears in the form of white fine microcrystalline powder. Utilization of reactants: 98 % calculated on starting SiO 2 . Chemical composition of zeolite FIA (sample FLA-5) : Corresponds to the sample FLA-I (see Example 2) . Crystal structure of zeolite FIA (sample FIA-5) :
  • sample FLA-5 showed spheroidal shape of crystals (particles) with no identifiable crystal faces and with high external surface roughness.
  • the reaction yield of zeolite FIA-5 (as described in Example 2) obtained in this example is 30 wt. %.

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Abstract

L'invention concerne une zéolithe 4A dont la composition molaire d'oxydes est 1,017Na2O • Al2O3 • 1,973SiO2 • 4,725H2O, et qui présente une surface utile spécifique de 2,37-4,43 m2/g selon l'isotherme de Brunauer-Emmett-Teller (BET); et une rugosité de surface externe indiquée par un rapport RSSA/GSSA compris dans la plage de 2,58-2,81. La taille des particules de cette zéolithe 4A est comprise entre 0,4 μm et 5 μm, 50% de toutes les tailles de particules étant inférieures à 1,45 μm, et 90% de toutes les tailles de particules étant inférieures à 2,35 μm. L'invention peut servir d'adjuvant de détergent, d'agent d'échange d'ions, de sorbant et de support de molécules organiques.
EP10725495A 2009-05-06 2010-05-04 Zéolithe 4a présentant de nouvelles propriétés morphologiques, et synthèse et utilisation de celle-ci Withdrawn EP2438010A1 (fr)

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CN103787362B (zh) * 2014-01-20 2016-10-12 石家庄健达高科化工有限公司 一种利用进口三水型铝土矿制备4a分子筛的工艺

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1082131A (en) * 1964-05-20 1967-09-06 Peter Spence & Sons Ltd Manufacture of zeolites
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
FR2398698A1 (fr) 1977-07-29 1979-02-23 Ugine Kuhlmann Procede industriel de fabrication en continu de zeolithe a
GB2040900B (en) 1978-12-20 1983-05-11 Huber Corp J M Zeolites of small particle size
FR2454997A1 (fr) 1979-04-24 1980-11-21 Ugine Kuhlmann Cristallisation de la zeolithe a lors des procedes industriels de fabrication
CA2001927C (fr) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates et detergents
US5474753A (en) 1990-11-09 1995-12-12 Laviosa Rhone-Poulenc Preparation of crystalline 4A zeolites
JP2793376B2 (ja) * 1991-03-19 1998-09-03 株式会社神戸製鋼所 Ａ型ゼオライトの製造方法
RU2248939C1 (ru) 2000-12-19 2005-03-27 Нэшнл Алюминиум Компани Лимитед Способ изготовления цеолита-а, пригодного в качестве детергентной модифицирующей добавки

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010128342A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016135521A1 (fr) 2015-02-23 2016-09-01 Robert Basic Formulation dentaire

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