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
  • C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
• • 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
  • 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
  • C01B39/20—Faujasite type, e.g. type X or Y
• • 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 subject of invention is a method for producing synthetic NaA, NaX; NaY zeolites or their compositions with enlarged grain size.
• the subjects of invention are zeolites, as well as compositions of zeolites produced by the above mentioned method.
• the zeolites with enlarged grain size according to invention have advantages in the usage, like enhanced tenside seizing ability and more homogenous distribution of grain size.
• the homogeneity of the zeolite phase should be assured, however not in any case.
• nuclei were produced by means of aging of gels, according to Breck's original patent dated 1964 (US patent No. 3 130 007) and according to US patents of Registration Nos. 3 518 051 and 3 227 660, as well.
• the US patent of Registration No. 4 264 562 deals with nucleus formation.
• NaX nuclei are used to produce NaA and NaX simultaneously.
• the crystallization of zeolite is promoted by nuclei with significantly larger surface (their size is ⁇ 0.1-0.01 ⁇ m) according to US patent of Registration No. 4 166 099.
• Crystallization nuclei are described in the German documents laid open to public inspection (Auslegeschrift) of Registry No 2 447 206. In the US patents of Registration Nos. 4 178 352 and 4 340 573 a rigid gel suspended in water is used as nuclei and moreover "Al nuclei" are used according to the latter one for crystallization of NaA.
• the "diluted" in water rigid gels have an irreproducible structure and they can lead to difficulties during the large-sized production of zeolites.
• the same relates to the other heterodispersive previously crystallized agents, and it should be added, that the diverse dispersiveness will be transmitted to the inoculated product, too.
• the first requirement is that the production of nuclei should be reproducible both in laboratory and in large-scale environment with a relative divergence of at least ⁇ 20 %. Since the nucleus PC ⁇ 7HU99/00073
• the "solution of nuclei” (this "solution” contains in fact particles of colloidal size, of less than 50 nm) should be mainly considered or preferred.
• nuclei N should be enough to "suppress” "inhibit” the eventual formation of parasitic zeolite nuclei by educing the components formed in the watery (generally in solvent) phase, being necessary to build up crystal grating.
• the fulfillment of this condition is highly dependent on the structure of the zeolite to be crystallized: - the NaA zeolite is "undemanding" in this aspect. A quantity of nuclei of 0.1 *N (g "1 ) is surely enough and 0.01 *N (g "1 ) is even assumably enough to control properly the crystallization of NaA in a sludge composition appropriate to formation of NaA.
• nuclei of NaA, NaX and NaY are the same.
• phase NaA (LTA) always appears depending on the composition of sludge and the conditions of crystallization during crystallization of low modulus zeolite X ("low silica X ", LSX) product, as well.
• the added nuclei must grow to a zeolite product having an optimal for usage grain size ⁇ ( ⁇ m) and homogenous distribution thereof in a charge of sludge of defined quantity.
• the quantity of nuclei N (g "1 ) contained in a mass unit of the nuclei solution can be changed within a certain range at a defined mass of charge so that the condition II) will be fulfilled.
• the grain size of the product can be enlarged slightly reducing the quantity of the nuclei solution added to the charge for the synthesis and the grain size of the product can be reduced slightly increasing the quantity thereof, consequently the conditions II) and III) are simultaneously fulfilled.
• the required grain size ⁇ is smaller than ⁇ m i n , the quantity of the nuclei solution added to the defined charge can be increased.
• the present invention provides a relatively simple procedure to fulfill simultaneously the conditions II) and III) and complying with the requirement to enable the production of a zeolite of any previously defined grain size ⁇ within the range of 1 to 20 ⁇ m preferably in the practically required range of grain size of 3 to 8 ⁇ m.
• our invention relates to the intended, previously defined enlargement of grain size of synthetic zeolites, having the essential point to add a nucleus-free gel to the sludge to be crystallized, expediently at a time t, register ⁇ , and in the quantity required to produce the previously defined grain size ⁇ in such a manner that the highest rate of crystallization being characteristic for the given conditions should remain unchanged during the whole time period of addition.
• This water-glass solution is always doped with aluminum silicate (with content of 1 mole of A1 0 3 rated to 8 to 15 mole of Si0 2 ) and it is highly alkaline with a concentration of free NaOH of 16 to 24 weight %.
• the nuclei formation is quick under these conditions (it takes only a few hours).
• the charging can be performed in any succession. It is more expedient, however, to add water-glass to the ready gel.
• a zeolite product with too small grain size should be received without intervention.
• a quantity of sludge being free of crystallization nuclei is charged into crystallizing apparatus at a defined phase of crystallization according to the rate calculated to zeolite type to be crystallized and to the desired grain size ⁇
• m (g) - is the mass of zeolite (of a grain or a given number of grains);
• f(c) - is a function containing the concentration of aluminum silicate components (c) required to build up the crystal grating
• the charge of nuclei free gel should be begun expediently at the moment t, honor fl and proceed according to the defined program in the time to maintain the optimal crystallization rate.
• the charge rate (g/s) should be adequate that mass ratio of zeolite building components be equal to (dm/dt) i. e. the zeolite building rate. Looking at the equation (2) one can recognize that dm/dt is a square function of time, consequently the charge rate should be evenly accelerating to assure the optimum of crystallization.
• the whole quantity of subsequently charged gel is determined by the desirable grain size ⁇ ( ⁇ m). It can be calculated, but it is preferably defined experimentally for the purposes of a safe production.
• the product obtained by the method according to invention can be significantly more homogeneous, than by any other method, wherein the nucleus building is accomplished with dragging.
• the execution of the procedure according to invention has the feature that a sludge containing components SiO 2 , A1 2 0 3 , Na 2 0 and H 2 0 and nuclei of crystallization is crystallized during the time t, until the conditions of highest crystallization rate are established, then a sludge containing components Si0 2 , A1 2 0 3 , Na 2 0 and H 2 0 and free of crystallization nuclei is charged continuously to the crystallized mixture, until the crystals grow up to the desired average size.
• the procedure according to the present invention is applicable to produce a number of different zeolites.
• ⁇ 3 which can vary between 3 and 10 ⁇ m.
• the required addition of crystallization nuclei is determined by molar ratios of components Si0 2 , Al 2 O 3 and H 2 0 of the sludge used for the first synthesis.
• the procedure consists of the following steps:
• solution 'C made up of the same components as the 'A' one at the adequate moment t ⁇ nfl after the beginning of crystallization of 'A', because this assures to form zeolites NaA and NaX of adequate grain sizes and to avoid the formation of other undesired zeolites: P zeolite, phillipsite, sodalite etc.
• the molar ratios of components of the solution 'A' calculated to 1 mole of A1 0 3 are within the following ranges:
• the molar ratios of the solution 'C have much wider ranges, because the spontaneous nuclei formation makes no disturbance.
• the size of crystals being formed can be controlled very well by choosing the moment of addition of solution 'C.
• solution 'C should be added 1 to 2 hours after the beginning of crystallization of the solution 'A'.
• the subject of invention is a procedure to produce synthetic NaA, NaX, NaY zeolites or their mixtures from solutions of sodium aluminate and water-glass.
• the features of procedure according to invention are as follows:
• a gel is produced, having the composition:
• the gel obtained by this way is crystallized during a slow stirring up to the moment when the highest crystallization rate is achieved (t, n ⁇ ), then a gel of the same molar ratio, free of crystallization nuclei, serving to growing up the crystal size is added in one or several portions to the primary one and the crystallization is continued during slow stirring, the addition of gel for growing up the crystal size and following crystallization can be one or more times repeated if desired, then the obtained crystals are separated, washed and dried by known methods; or
• the subjects of this invention are NaA, NaX and NaY zeolites or their composition produced by the above mentioned method having the feature that the average particle size is at least 1.0 ⁇ m, expediently between 1.0 and 20.0 ⁇ m.
• the zeolites of enlarged grain size according to invention can be applied on wide application field.
• zeolites produced according to invention are as follows: The most adequate product can be used on a specific field of application owing to conscious setting of average grain size.
• the distribution of grain size is more uniform than in case of zeolites produced by a traditional method.
• This homogenous solution can be stored for at least a week in refrigerator.
• composition of this "nuclei” is: (96.6 Si0 2 , 1.0 A1 2 0 3 , 49.8 Na 2 0, 1858.0 H 2 O).
• a quantity of 1 g of said "nuclei” contains 4.3*10" with relative deviation of ⁇ 5 % NaX and NaA nuclei of grain size less than 5 nm (having not particularized structure).
• H 2 0 3670.0 g of H 2 0 is added to 1362 g of aluminate alkali of molar ratio 1.58 Na 0/Al 2 0 3 having concentration of Na of 15.9 weight %.
• the solutions are mixed together under intensive shearing stirring and simultaneous addition of both solutions.
• the gel is stirred thereafter during 15 minutes more.
• This gel is crystallized under a slow stirring without shearing force at temperature of 88 ⁇ 2 C° samples are taken in regular time periods for X-ray diffraction analysis, the results of measurements make up the crystallization diagram shown in the Figure 2.
• the X-ray diffraction is proportional to the mass of crystalline phase being present in the volume of given sample.
• the ordinates of Figure 2 show " eo" the summarized intensity of the net plains having the most intensive reflection of indices [111], [220], [535], [642]/[646], [555], [157]/[751] as function of sampling time.
• Si/Al using atom adsorption system AAS
• Si/Al 1.36
• composition of a primary cell is:
• Na 81 [A10 2 ) 81 (SiO 2 ) ⁇ n ] ⁇ 260 H 2 0 which differs only by 5 to 6 % from that of a NaX cell considered as typical:
• the mass of zeolite containing 1 mole of A1 0 3 shall be:
• the mass of sludge to be crystallized is: 9056.0 g (for the above charge, too).
• gel having the "substantially identical" composition begins at the crystallization time t j i ⁇ 3.2 hours to increase the grain size.
• This gel must not contain crystallization nuclei.
• the gel of following composition is loaded into crystallization vessel in uniform portions during 1.5 hours.
• the two solutions are mixed together at a desirable lower temperature (but at least at room-temperature) with intensive stirring.
• the formed gel is used without aging.
• composition of the gel is as follows:
• composition of basic cells is: Na 83 [Al 2 O 3 ) 83 (SiO 2 ) 109 ] - 260 H 2 O so the difference is only 3.6 % from the NaX composition considered as typical.
• the mass of above described charge is 8584.4 g and at most 1158.0 g zeolite can be produced therefrom.
• This gel is added in a similar manner, beginning from the 7 th hour during 1.5 hours to the sludge being in the crystallization vessel.
• the crystallization is continued under a slow stirring up to the end of 10 th hour.
• the crystals are filtrated, washed and dried as in the previous procedures.
• the devices based on the principle of sedimentation and used for determination of integral "grain size distribution" perform selection, however, not according to edge length but according to sedimentation speed.
• the average grain size ⁇ can be also considered as function of quantity of charges.
• the function (2) describing the change of zeolite mass in the time means at the same time, that the characteristic grain size ⁇ is linear function of time:
• the feeding rate can be easily doubled by using two pumps.
• aluminate alkali having molar ratio of 1.58 Na 2 0/Al 2 O 3 and NaOH concentration of 15.9 weight % is diluted with 647.5 g of water in another vessel.
• the gel is produced by uniting the homogenized solutions at a possible lower temperature (but at least approximately at room temperature) and intensive stirring up. The gel can be stirred hardly in the first minutes, but after 5 to 10 minutes the stirring goes well.
• the gel is poured into a crystallizing vessel and crystallized under an intensive shear stress at 88 ⁇ 2 C°.
• Si/Al 1.05.
• H 2 0 500.0 g of H 2 0 is added to 400 g of water glass solution having concentrations of 8.6 weight % of Na 2 0 and 28.0 weight % of Si0 2 .
• H 2 0 527.9 g of H 2 0 is added to 512.2 g of aluminate alkali having molar ratio of 1.58 Na 2 O/Al 2 O 3 and concentration of 15.9 weight % of NaOH.
• a homogenous gel is produced from the previously homogenized solutions by mixing them together under intensive shear stress.
• the gel is crystallized up to t in ⁇ ⁇ 55 to 60 minutes during the first synthesis, then the whole gel quantity necessary for the growing of crystalline grain size is added along 1.5 hours.
• the product is filtrated, washed up to pH ⁇ 10.5 washed with hot water and dried.
• the first four diffractograms of the product is shown on the Figure 14, which indicates that crystallization degree of the product is excellent.
• the solution 'C is added to the solution 'A' having been crystallizing since 1 hour with an intensive stirring and the temperature is raised to 60 C°.
• the zeolite crystals are filtrated with suction filter and washed with condensation water up to pH ⁇ 10.
• the composition of the obtained product :
• a zeolite skeleton formatting agent well applicable to modern washing powders is obtained.
• aluminate alkali having molar ration of 1.62 Na 2 O/Al 2 O 3 and concentration of NaOH of 15.5 weight % is mixed together with 112 g of solid NaOH dissolved in 1572 g of H 2 0 in another vessel.
• the solution 'C is added to the solution 'A' having been crystallizing since 1 hour with intensive stirring and the temperature is raised to 60 C°.
• the sludge containing zeolite crystals is filtrated with suction filter and washed with condensation water until pH ⁇ 10.
• the composition of the obtained product is:
• aluminate alkali having molar ratio of 1.65 Na 2 0/Al 0 3 and concentration of NaOH of 15.05 weight % is mixed together with 245 g of solid NaOH dissolved in 500 g of H 2 O in another vessel.
• the sludge containing zeolite crystals is filtrated with suction filter and washed with condensation water until pH ⁇ 10.
• the composition of the obtained product is:

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• 1999
  • 1999-10-26 EP EP99952733A patent/EP1140699A1/en not_active Withdrawn
  • 1999-10-26 AU AU64829/99A patent/AU6482999A/en not_active Abandoned
  • 1999-10-26 CZ CZ20011894A patent/CZ20011894A3/cs unknown
  • 1999-10-26 WO PCT/HU1999/000073 patent/WO2001030695A1/en not_active Ceased
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