PROCESS FOR PREPARATION OF HIGH-SILICA FAUJASITE TYPE ZEOLITE

Abstract: A faujasite type zeolite having a high SiO₂/Al₂O₃ ratio is prepared by simultaneously and continuously supplying an aqueous solution of an alkali metal silicate and an aqueous so­ lution of an aluminium-containing compound whereby the al­ kali metal silicate is continuously reacted with the aluminium-­ containing compound to prepare a homogeneous phase com­ pound of a granular amorphous aluminosilicate containing alu­ minium in an amount of 10 to 16% by weight, as Al₂O₃ and based on the anhydride; and then, crystallizing the granular homogeneous phase amorphous aluminosilicate in an aqueous alkali metal hydroxide solution having a concentration of 4 to 10% by weight.

Description: The present invention relates to a process for the preparation of a faujasite type zeolite, especially a faujasite type zeolite having a high silica content. A faujasite type zeolite ordinarily has an oxide molar composition represented by the following formula: 0.9±0.2M₂O·Al₂O₃·xSiO₂·wH₂O wherein M stands for an alkali metal cation, x is a number of from 2.5 to 6, and w is a number of from 6 to 9. Faujasite type zeolites are used as a cracking catalyst for petroleum, and an adsorptive separating agent for use in separation of paraxylene or the like. Ordinarily, these catalysts or adsorptive separating agents are required to have good heat resistance and acid resistance. In case of a faujasite type zeolite, the SiO₂/Al₂O₃ molar ratio has close relations to these properties, and a faujasite type zeolite having a higher SiO₂/Al₂O₃ molar ratio is excellent in these properties. A faujasite type zeolite having a relatively low silica ratio, that is, an SiO₂/Al₂O₃ molar ratio of 2.5 to 4, is poor in the heat resistance and the acid resistance because of this low silica molar ratio, and therefore, faujasite type zeolites having an SiO₂/Al₂O₃ molar ratio of at least 4 are widely used industrially and high-silica faujasite type zeolites having an SiO₂/Al₂O₃ molar ratio of at least 4.5 are especially desired. However, it has been considered difficult to synthesize faujasite type zeolites having an SiO₂/Al₂O₃ molar ratio of at least 4.5, especially at least 5, on an industrial scale with a good reproducibility. In the synthesis of faujasite type zeolites, the intended zeolites are produced only under very restricted conditions. Accordingly, the kinds and quantitative ratios of starting materials should be strictly and carefully selected and the reaction should be carefully carried out while strictly controlling such conditions as the mixing state, the degree of aging, the reaction temperature and the reaction time. These difficulties are increased when it is intended to prepare a faujasite zeolite having such a high SiO₂/Al₂O₃ molar ratio as described above and having a high purity. Various processes have heretofore been proposed for preparing high-silica faujasite type zeolites. According to a typical process disclosed in Japanese Examined Patent publication No. 36-1639 or No. 42-16941, a silica source such as silica sol, silica gel or finely divided solid silicic acid, sodium aluminate and sodium hydroxide are used as the starting materials and these starting materials are reacted under strictly controlled conditions to form a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of at least 4. In this process, however, it is indispensable that expensive amorphous solid silica should be used as the silica source and therefore, a faujasite type zeolite cannot be produced at a low cost. Furthermore, a fatal defect is encountered when it is intended to synthesize a faujasite type zeolite in an industrial scale with a good reproducibility. Namely, it is impossible to carry out the reaction while stirring and mixing the reaction system. Especially when stirring is effected at the step of converting an amorphous reaction product of an aqueous gel, formed through long-time aging after mixing of the starting materials, (this product is considered to be a precursor before crystallization) to a faujasite type zeolite, crystallization to the intended faujasite type zeolite is inhibited and the majority of the product is converted to an aluminosilicate mineral of no practical utility such as a naturally occurring phillipsite mineral analogues (hereinafter referred to as "phillipsite") and gmelinite. Accordingly, in order to synthesize a high-silica faujasite type zeolite having a high purity, it is indispensable that the synthesis should be carried out while the reaction mixture in the form of an aqueous gel is allowed to stand still and mixing under stirring should be avoided. However, if this synthesis process under the stationary condition is carried out on an industrial scale, it is required to effect the heat transfer for maintaining the reaction temperature, stirring is not conducted and, thus, the heat transfer in the reaction system becomes difficult and the temperature becomes uneven, resulting in such a disadvantage as simultaneous formation of phillipsite and gmelinite. Various attempts have been made to avoid simultaneous formation of phillipsite and gmelinite in the above-mentioned stationary synthesis process, but the problem of simultaneous formation of phillipsite and gmelinite could not be completely solved. Moreover, as means for reducing the manufacturing cost of a high-silica faujasite type zeolite, there have been proposed various improved processes. For example, Japanese Examined Patent Publication No. 49-13720 discloses a process for preparing a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of at least 4 by using as the silica source cheap sodium silicate which has been considered to be unable to give a high-silica faujasite type zeolite, wherein an aqueous mixture comprising hydrous solid silica, sodium aluminate and sodium hydroxide is aged to form an intermediate product and a small amount of this intermediate product is added as a crystal nucleus to a gel formed from a second aqueous mixture comprising sodium silicate and sodium aluminate. Furthermore, Japanese Unexamined Patent Publication No. 47-4866 discloses a process for preparing a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of at least 4 by using cheap sodium silicate, wherein an amorphous nucleus-forming core substance (seed) which has been prepared in advance and has an average particle size of 0.01 to 0.1 µm is added to a reaction mixture comprising sodium silicate, sodium aluminate and aluminum sulfate. Moreover, Japanese Examined Patent Publication No. 53-33556 discloses a process for preparing a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 4.5, wherein a mixture of sodium silicate and kaolin is used as the silica and alumina source and a zeolite seed prepared in advance from an aqueous mixture of sodium silicate and sodium aluminate is added to the above mixture. In each of these processes, a specific combination of the starting materials is used and specific means such as addition of a seed is adopted. In these processes, the manufacturing cost can be reduced by using cheap sodium silicate as the silica source, but the process steps become complicated as compared with the steps adopted in the conventional processes and hence, these processes are not especially preferred from the industrial viewpoint. Moreover, the problem how to effect the synthesis under stirring of the reaction mixture for a large-scale production has not been solved in these processes. French Patent No. 1 477 542 describes the preparation of synthetic faujasite in which an intermediate amorphous aluminosilicate is first obtained and is thereafter crystallized in an alkaline solution to form faujasite. The alumina content of the intermediate amorphous aluminosilicate is relatively high. It is a primary object of the present invention to provide a process for the preparation of a faujasite type zeolite, which is quite different from the conventional processes, wherein an aqueous solution of an alkali metal silicate is used as the silica source, and a faujasite type zeolite having a silica/alumina molar ratio of at least 4.5 and a high purity can be obtained with a good reproducibility and in a large production scale. In this process, an aqueous solution of a cheap alkali metal silicate can be used as all of the silica source and the reaction can be carried out under stirring. According to the present invention there is provided a process for the preparation of a high-silica faujasite type zeolite having a silica/alumina molar ratio of at least 4.5, comprising: (a) simultaneously and continuously supplying an aqueous solution of an alkali metal silicate and an aqueous solution of an aluminum-containing compound into a reaction zone whereby the alkali metal silicate is continuously reacted with the aluminum-containing compound to prepare a homogeneous phase compound of a granular amorphous aluminosilicate containing 10 to 16% by weight of aluminum, as Al₂O₃ and based on the weight of the dry homogeneous phase compound, the alumino-silicate being in the form of an aqueous slurry being a pH value of 5 to 9, and having a substantially spherical shape and a particle size of from 1 to 500µm,; (b) subjecting the aqueous slurry of the alminosilicate to solid-liquid separation; (c) aging a part of the aluminosilicate in an aqueous alkali metal hydroxide solution at a temperature of 10 to 95°C for 0.5 to 12 hours; and (d) crystallizing a mixture of the aged aluminosilicate and the non-aged aluminosilicate in an aqueous alkali metal hydroxide solution having a concentration of 4 to 10% by weight and being maintained at a temperature of from 75°C to 130°C.. The invention will be further described, by way of example, with reference to the drawings, in which: Fig. 1 is an electron microscope photograph of the homogeneous phase compound of the granular amorphous aluminosilicate obtained in Example 1; and Fig. 2 is a powder X-ray diffraction pattern of the dry product obtained in Example 1, as determined by using a Kα doublet of copper. The homogeneous compound is obtained by simultaneously and continuously supplying into a reaction zone an aqueous alkali metal silicate solution and an aluminum-containing aqueous solution whereby these reactants are continuously reacted with each other. It is preferable that these reactants are supplied into the reaction zone at a substantially constant molar ratio. As the aqueous alkali metal silicate solution, there are preferably used aqueous solutions of sodium silicate, potassium, silicate and lithium silicate, and as the aluminum-containing aqueous solution, there are preferably used aqueous solutions of aluminum sulfate, aluminum nitrate, aluminum chloride, sodium aluminate and potassium aluminate. If necessary, a caustic alkali may be added to the former solution or a mineral acid may by added to the latter solution, so that the amount of the acid or alkali is adjusted. A commercially available aqueous solution of an alkali metal silicate and a commercially available aqueous solution of an aluminum salt of a mineral acid or an alkali metal aluminate may be used as the above-mentioned aqueous solutions. Moreover, an aqueous solution formed by dissolving a silica source such as siliceous sand or hydrous solid silicic acid with a caustic alkali, or an aqueous solution formed by dissolving an aluminum source such as aluminum hydroxide or active alumina with a caustic alkali or mineral acid may be used. The concentrations of both the aqueous solutions are not particularly critical, but aqueous solutions having an optional concentration may be used. According to a most preferred embodiment for the production of the homogeneous compound, both the aqueous solutions are simultaneously and continuously supplied into an overflow-type reaction tank provided with a stirrer where the reaction is carried out. The granular homogeneous compound obtained according to this preferred embodiment has a substantially spherical shape, and most of particles have a particle size distributed in the range of from 1 to 500 µm and the number of fine particles having a size smaller than 1 µm is very small. In carrying out the present invention, it is preferred that a homogeneous compound having a particle size of 10 to 100 µm be used. The supply ratio of both the aqueous solutions may optionally be determined according to the intended composition of the homogeneous compound. The liquid reaction mixture is a slurry in which the formed spherical homogeneous compound is suspended. The pH value of the slurry is adjusted by the amount of the alkali or acid to be added to the starting aqueous solutions. The pH value of the slurry is adjusted to 5 to 9 preferably 6 to 8. The time for the residence of the slurry in the reaction tank is preferably at least 3 minutes. By the term "residence time" is meant a time from the point of simultaneous and continuous supply of both the aqueous solutions to the reactor to the point of flowing out of the reaction slurry from the reactor. When the residence time is shorter than 3 minutes, the proportion of formation of fine particles having a size smaller than 1 µm is undesirable increased, and, in the course of formation of high- silica faujasite type zeolite having a high purity by carrying out the reaction while stirring the reaction mixture, an undesirable phenomenon such as simultaneous formation of impurities is caused to occur. On the other hand, if the residence time is at least 3 minutes, the product is composed substantially of spherical particles and formation of fine particles is remarkably reduced. As the residence time is prolonged, the particle size is increased and simultaneously, the hardness of the spherical particles is increased. Therefore, the size and hardness of the formed spherical particles can be varied by controlling the residence time, and hence, the reactivity of the homogeneous compound can be adjusted according to the object. As another embodiment for the production of the homogeneous compound, there may be adopted a so-called semi-continuous process in which both the aqueous solutions are simultaneously and continuously supplied at constant rates into a reactor under stirring conditions. In this case, it is preferred that both the aqueous solutions be not promptly added but necessary amounts of the aqueous solutions be added over a period of at least 10 minutes, especially at least 30 minutes. The reaction temperature for formation of the homogeneous compound is not particularly critical, and spherical particles can be obtained at either a low temperature or a high temperature and the formed particles can be used in the present invention. One of the characteristic feature of the present invention is that since both the aqueous solutions having a concentration adjusted are simultaneously and continuously supplied, preferably at a constant ratio, into a reactor where the reactants are continuously reacted with each other, the formed spherical homogeneous compound always has a constant composition and the product has no heterogeneous portion and hence, co-presence of impurities due to the heterogeneous composition can be completely avoided at the crystallizing step. For example, if one aqueous solution is added to the other aqueous solution according to the conventional batchwise method, a pasty product having a high viscosity is formed and homogenization of the product cannot be attained however violently the stirring may be carried out. Even if homogenization is seemingly attained by sufficient mixing, microscopic heterogeneity of the composition cannot be avoided. Another characteristic feature of the present invention is that by using the homogeneous compound, it is made possible to perform stirring of the reaction mixture at the crystallizing step. Since the homogeneous compound has a uniform composition with no heterogeneity and is in the form of spherical particles having a certain size, formation of a faujasite type zeolite is advanced uniformly in the individual particles at the crystallizing step. Because of this peculiar reaction mode, crystallization is advanced in the interiors of the respective particles in the stationary state. Accordingly, synthesis under stirring, which has been impossible according to the conventional methods and improvements thereof, can be carried out conveniently, and it is rendered possible to prepare a high-purity faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of at least 4.5, especially at least 5, on an industrial scale with a goods reproducibility. According to the conventional batchwise method, the above-mentioned pasty reaction product has a very high viscosity, and therefore, the concentration of the effective component is considerably limited. In contrast, in the present invention, since the homogeneous compound is in the form of spherical particles having a particle size of 1 to 500 µm, the viscosity of the reaction slurry is low and such a strong stirring as required in the above-mentioned batchwise method is not necessary and the concentration of the reaction slurry can be considerably increased. The homogeneous compound used in the present invention is obtained in the form of spherical particles having an appropraite size, and therefore, solid-liquid separation and washing can be performed very easily. Since the homogeneous compound is in the form of spherical particles having a particle size of 1 to 500µm, the homogeneous compound is easy to dehydrate. Thus, even if the homogeneous compound is in the wet state, it can be obtained in the form of a gel containing an extremely reduced amount of water. Accordingly, the concentration of the reactants in the slurry for the preparation of the homogeneous compound can be varied in a broad range. This is still another characteristic feature of the present invention. It is preferred that the washed homogeneous compound be used in the wet state, but of course, it may be used after drying. Various homogeneous compounds differing in the composition can be obtained according to the above-mentioned method. In carrying out the present invention, it is indispensable that the homogeneous compound should contain aluminium in an amount of 10 to 16% by weight as Al₂O₃ (based on the anhydride). If the Al₂O₃ content of the homogeneous compound is outside the above-mentioned range, impurities such as phillipsite and gmelinite are simultaneously formed and contained in the product. The homogeneous compound having an Al₂O₃ content of 10 to 16% by weight can be obtained by adjusting the flow rate ratio of both the aqueous solutions while taking the concentrations of SiO₂ and Al₂O₃ in both the aqueous solutions into consideration. For example, a homogeneous compound having a higher Al₂O₃ can be obtained by increasing the Al₂O₃ concentration or flow rate of the aluminum-containing solution. Then, crystallization is accomplished by heating the homogeneous compound in an aqueous solution of an alkali metal hydroxide. In the present invention, crystallization can be carried out under stirring, but crystallization may be performed in the stationary state as in the conventional method. As the aqueous solution of the alkali metal hydroxide, there may be used aqueous solutions of sodium hydroxide, potassium hydroxide and lithium hydroxide and mixtures thereof. Among them, an aqueous solution of sodium hydroxide is most preferred. The concentration of the aqueous alkali metal hydroxide solution used for crystallization is 4 to 10% by weight. If the concentration of the alkali metal hydroxide is too high and exceeds the above-mentioned range, the SiO₂/Al₂O₃ molar ratio in the formed faujasite type zeolite is reduced, and the intended high-silica faujasite type zeolite cannot be obtained. If the above molar ratio is too low and below the above-mentioned range, crystallization becomes difficult. The amount of the aqueous solution of the alkali metal hydroxide is set so that the content of the homogeneous compound in the starting slurry to be used for crystallization is 15 to 35% by weight based on the total amount of the starting slurry (based on the dry weight.) At the step of crystallization the homogeneous compound in the aqueous alkali metal hydroxide solution, a part of the homogeneous compound to be used is aged in the aqueous alkali metal hydroxide solution in advance and a mixture of the aged homogeneous compound and the non-aged homogeneous compound is crystallized. It is preferred that the amount of the homogeneous compound to be aged in advance be 10 to 30% by weight based on the total amount of the homogeneous compound to be used, and good results are obtained when the concentration of the aqueous solution of the alkali metal hydroxide be at least 25% by weight in case of an aqueous sodium hydroxide solution. Aging is carried out under stirring at a temperature of 10 to 95°C, preferably 20 to 70°C, for 0.5 to 12 hours, preferably 1 to 4 hours. If this aging step is adopted, the time required for crystallization can be remarkably shortened. For example, in the conventional method, a crystallization time to 72 to 96 hours is necessary for synthesizing a high-purity faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5 to 5.5, but in the present invention, crystallization is completed within such a short time as 10 to 24 hours. Moreover, in the conventional method, since an extremely long time is necessary for obtaining a high-purity faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of at least 5.5, production of this faujasite type zeolite on an industrial scale is very difficult though possible on a bench scale. In the present invention, by using the homogeneous compound as the intermediate product and adopting the aging step, a high-purity faujasite type zeolite having an SiO₂/Al₂O₃ ratio of 5.5 to 6.5 can easily be obtained on an industrial scale for a very short crystallization time, for example, 20 to 40 hours. In the present invention, the particle size of the formed faujasite type zeolite can be controlled by appropriately setting the aging conditions. For example, if aging is carried out at a high temperature for a short time, the particle size is increased, and if aging is carried out at a low temperature for a long time, a faujasite type zeolite having a small particle size is obtained. If the step of adding a seed crystal, as adopted in the improved technique of the conventional method, is adopted instead of the above-mentioned aging step, the crystallization step can be effectively shortened, but in this case, a part of the added crystal is likely to be converted to impurities such as phillipsite or gmelinite, and hence, addition of the seed crystal is not preferred for attaining the object of obtaining a high-purity faujasite type zeolite. After completion of the aging operation, the remainder of the homogeneous compound and water or a dilute aqueous solution of an alkali metal hydroxide are added, and the concentration and amount of the alkali metal hydroxide are adjusted and the crystallization step is started. The crystallization temperature is 75 to 130°C. If the crystallization temperature is lower than 75°C, the crystallization time becomes too long, and if the crystallization temperature is higher than 130°C, impurities such as phillipsite and gmelinite are simultaneously formed. The time required for crystallization depends on the temperature but the crystallization time is ordinarily 10 to 40 hours. In the present invention, in order to obtain a high-purity high-silica faujasite type zeolite, in the case where the content of the alumina component Al₂O₃ in the homogeneous compound is low, it is preferred that the alkali metal hydroxide concentration in the starting slurry relative to Al₂O₃ be maintained at a high level within the range of the crystallizing composition, and in the case where the Al₂O₃ content is high, it is preferred that the alkali metal hydroxide concentration relative to Al₂O₃ be maintained at a low level. After completion of crystallization, the formed crystals are subjected to solid-liquid separation and washing to remove the excess alkali component adhering to the surface, and are then dried to obtain a high-purity faujasite type zeolite having a high SiO₂/Al₂O₃ molar ratio. The mother liquor left after separation of the crystal still contains excess silica component and alkali component. In the present invention, all of the mother liquor left after separation of the crystal can be recycled as the aqueous solution of the alkali metal silicate to the step of preparing the homogeneous compound. Since reaction in the presence of excess silica and alkali components is indispensable for formation of a faujasite type zeolite, it has been a serious problem how to effectively utilize and treat the mother liquor left after separation of the crystal, that is, a dilute aqueous solution of the alkali metal silicate. In the present invention, since an aqueous alkali metal silicate solution is used as all of the silica source and a homogeneous compound having a certain composition is obtained from this silicate solution and an aluminum-containing aqueous solution irrespectively of the concentrations of both the aqueous solutions, effective utilization of the mother liquor left after separation of the crystal becomes possible, and a high-silica faujasite type zeolite can be prepared at a more reduced cost. This is another characteristic feature of the present invention. The faujasite type zeolite obtained according to the present invention has a high purity and a high SiO₂/Al₂O₃ molar ratio of 4.5 to 6.3, and the powdery zeolite is used widely as an adsorptive separating agent, a catalyst or the like in the powdery form or after it is calcined, molded and ion-exchanged with an appropriate cation according to need. The present invention will now be described in detail with reference to the following examples. Example 1 An aqueous solution of the aluminum sulfate (Al₂O₃ = 9.89 w/v%, H₂SO₄ = 28.52 w/v%) and an aqueous solution of sodium silicate (SiO₂ = 15.00 w/v%, Na₂O = 6.06 w/v%, Al₂O₃ = 0.077 w/v%) were simultaneously and continuously supplied at constant rates of 1 ℓ/hr and 4 ℓ/hr, respectively, to an overflow type reactor provided with an ordinary paddle agitator, where reaction was carried out with stirring. An overflowing opening was arranged so that 1 ℓ of the reaction liquid (slurry) was always kept in the reactor and the excessive reaction liquid overflew the tank, and the residence time was 12 minutes. The pH value of the slurry was 6.7 and the reaction temperature was 32°C. The overflowing slurry product from the reaction tank was subjected to solid-liquid separation using a centrifugal separator and washed with water until no SO - / 4² ion was detected in the washing liquid, whereby a homogeneous compound having a composition shown in Table 1 was obtained. An electron microscope photograph of this homogeneous compound is shown in Fig. 1. Then, a reactor of the external heating type provided with an ordinary paddle agitator and a reflux condenser at the top thereof was charged with 1926.8 g of an aqueous sodium hydroxide solution having a concentration of 33.2% by weight, and 899 g of the homogeneous compound, corresponding to 14% by weight of the total amount of the homogeneous compound to be used, was added and the mixture was stirred. Aging was conducted at a temperature of 30°C for 3 hours. After completion of aging, the added homogeneous compound was completely dissolved and a transparent aqueous solution was formed. Subsequently, 2766 g of deionized water and 5521.2 g of the homogeneous compound, corresponding to 86% by weight of the total amount of the homogeneous compound, were added to the transparent aqueous solution formed by aging, and the mixture was stirred and maintained at a temperature of 30°C for 1 hour. The added homogeneous compound was hardly dissolved, and the mixture became a low viscosity slurry in which the concentration of sodium hydroxide was 5.76% by weight. Then, the temperature of the slurry was elevated and the mixture was maintained at an ambient temperature of 95°C for 20 hours with stirring to effect crystallization. After completion of crystallization, the product was separated from the mother liquor by filtration, washed with water and then dried at 110°C. The composition of the separated mother liquor is shown in Table 2. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.6 and a crystallinity of 105%. Incidentally, the SiO₂/Al₂O₃ molar ratio was determined by the measurement of the lattice constant by X-ray diffractometry. The crystallinity was determined by measuring the sum I₁ of the intensities of the following planes from the x-ray diffraction pattern: and calculating the relative value based on the sum I₂ of the intensities of a zeolite of the type Y supplied by Union Carbide Corporation (SK-40) as the crystallinity of 100 according to the following formula: Crystallinity (%) = (I₁/I₂) x 100 The X-ray powder diffraction pattern is shown in Fig. 2. From the results of electron microscope observation it was found that the average particle size of the obtained faujasite type zeolite was 0.5 µm. Example 2 The procedures of Example 1 were repeated in the same manner except that crystallization was carried out in the stationary state to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that the SiO₂/Al₂O₃ molar ratio of the product was 5.6 and the product was a faujasite type zeolite having a crystallinity of 106%. The mean particle size of the product was 0.5 µm as in case of the product obtained in Example 1. Example 3 The procedures of Example 1 were repeated in the same manner except that the compositions of the aqueous solutions of aluminum sulfate and sodim silicate were changed to (Al₂O₃ = 9.77 w/v%, H₂SO₄ = 32.94 w/v%) and (SiO₂ = 21.00 w/v%, Na₂O = 6.76 w/v%, Al₂O₃ = 0.107 w/v%), respectively, to obtain a homogeneous compound having a composition shown in Table 1. The reactor of the external heating type used in Example 1 was charged with 2474 g of an aqueous sodium hydroxide solution having a concentration of 32.4% by weight, and 832.9 g of the homogeneous compound, which corresponded to 14% by weight of the total amount of the homogeneous compound to be used for the reaction, was added and the mixture was stirred. Aging was conducted at a temperature of 30°C for 3 hours. The homogeneous compound added was completely dissolved and a transparent solution was formed. Subsequently, 2872.8 g of deionised water and 5116.5 g of the homogeneous compound, which correspond to 86% by weight of the total amount of the homogeneous compound, were added and the mixture was maintained at a temperature of 30°C for 1 hour. The mixture became a low viscosity slurry in which the concentration of sodium hydroxide was 7.1% by weight. Then, the crystallization and post treatment were carried out in the same manner as described in Example 1 to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.5 and a crystallinity of 102%. The mean particle size was 0.5 µm as in case of the product of Example 1. Example 4 The procedures of Example 1 were repeated in the same manner except that the compositions of the aqueous aluminum sulfate solution and the aqueous sodium silicate solution were change to (Al₂O₃ = 9.95 w/v%, H₂SO₄ = 28.69 w/v%) and (SiO₂ = 12.00 w/v%, Na₂O = 6.09 w/v%, Al₂O₃ = 0.061 w/v%), respectively, to obtain a homogeneous compound having a composition shown in Table 1. The reactor of the external heating type used in Example 1 was charged with 1126.8 g of an aqueous sodium hydroxide solution, and 767.2 g of the homogeneous compound, which corresponded to 14% by weight of the total amount of the homogeneous compound to be used, was added and the mixture was stirred and aged at a temperature of 30°C for 3 hours. The added homogeneous compound was completely dissolved to form a transparent solution. Subsequently, 1920.2 g of a deionized water and 4713.8 g of the homogeneous compound, which corresponded to 86% by weight of the total amount of the homogeneous compound to be used, were added and the mixture was stirred and maintained at a temperature of 30°C for 1 hour. The mixture became a low viscosity slurry in which the concentration of sodium hydroxide was 4.65% by weight. The crytallization and post treatment were carried out in the same manner as described in Example 1 to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.7 and a crystallinity of 105%. The mean particle size was 0.5 µm as in case of the product of Example 1. Example 5 899 g of the homogeneous compound obtained in Example 1 was added to 1471.9 g of an aqueous sodium hydroxide solution having a concentration of 34.79% by weight, and the mixture was stirred and aged at a temperature of 30°C for 3 hours. The added homogeneous compound was completely dissolved and a transparent solution is formed. Subsequently, 2113.2 g of deionized water and 5521.2 g of the homogeneous compound were added to the solution and the mixture was stirred and maintained at a temperature of 30°C for 1 hour. The mixture became a low viscosity slurry in which the concentration of sodium hydroxide was 5.13% by weight. The crystallization and post treatment were carried out in the same manner as in Example 1 except that the crystallization time was changed to 40 hours, whereby a dry product was obtained. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 6.3 and a crystallinity of 107%. The mean particle size was 0.5 µm as in case of the product of Example 1. Example 6 899 g of the homogeneous compound obtained in Example 1 was added to 2949.3 g of an aqueous sodium hydroxide solution having a concentration of 31.46% by weight, and the mixture was aged at a temperature of 30°C for 3 hours. The added homogeneous compound was completely dissolved to form a transparent solution. Subsequently, 4234.3 g of deionized water and 5521.2 g of the homogeneous compound were added to the solution, and the mixture was stirred and maintained at a temperature of 30°C for 1 hour. The mixture became a low viscosity slurry in which the concentration of sodium hydroxide was 6.82% by weight. The crystallization and post treatment were carried out in the same manner as described in Example 1 except that the crystallization time was changed to 16 hours, whereby a dry product was obtained. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.0 and a crystallinity of 106%. The mean particle size was 0.5 µm as in case of the product of Example 1. Example 7 599.3 g of the homogeneous compound obtained in Example 1 was added to 2420.9 g of an aqueous sodium hydroxide solution having a concentration of 30.84% by weight. The mixture was stirred and aged at a temperature of 30°C for 3 hours. The added homogeneous compound was completely dissolved to form a transparent solution. Subsequently, 3475.2 g of deionized water and 3680.8 g of the homogeneous compound were added to the solution, and the mixture was maintained at a temperature of 30°C for 1 hour. The mixture became a low viscosity slurry in which the concentration of sodium hydroxide was 7.35% by weight. The crystallization and post treatment were carried out in the same manner as described in Example 1 except that the crystallization time was changed to 12 hours, whereby a dry product was obtained. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 4.5 and a crystallinity of 104%. The mean particle size was 0.5 µm as in case of the product of Example 1. Example 8 The procedures of Example 1 were repeated in the same manner except that aging was carried out at an ambient temperature of 60°C for 0.5 hour and the crystallization time was changed to 40 hours, to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.6 and a crystallinity of 103%. From the results of electron micrscope observation, it was found that the mean average particle size was 2 µm. Example 9 The procedures of Example 1 were repeated in the same manner except that aging was carried out at an ambient temperature of 20°C for 8 hours and crystallization was carried out at a temperature of 95°C for 16 hours, to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.6 and a crystallinity of 106%. From the results of electron microscope observation, it was found that the mean particle size was 0.2 µm. Example 10 The procedures of Example 1 were repeated in the same manner except that crystallization was carried out in an autoclave at a temperature of 120°C for 10 hours, to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar raio of 5.5 and a crystallinity of 100%. From the results of electron microscope observation, it was found that the mean particle size was 1 µm. Example 11 The procedures of Example 1 were repeated in the same manner except that aging was carried out at an ambient temperature of 30°C for 5 hours and crystallization was carried out at a temperature of 80°C for 72 hours, to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.7 and a crystallinity of 105%. The mean particle size was 0.5 µm as in case of the product of Example 1. Example 12 A commercially available aqueous solution of sodium silicate and aqueous solution of sodium hydroxide were added to the mother liquor left after separation of the crystal in Example 1 to form an aqueous Solution of sodium silicate having the same composition as the composition described in Example 1. The procedures of Example 1 were repeated in the same manner except that a homogeneous compound was prepared by using this aqueous solution of sodium silicate as the silica source, to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.6 and a crystallinity of 104%. Comparative Example 1 A kneader type kneading machine (Model FM-NW-40 supplied by Fuji Sangyo K.K.) was charged with 2721.1 g of commercially available white carbon, that is, finely divided amorphous silica (SiO₂ = 88.2% by weight), as the silica source, 1990.2 g a commercially available aqueous solution of sodium aluminate (Al₂O₃ = 20.5% by weight, Na₂O = 19.0% by weight), 481.6 g of sodium hydroxide (NaOH = 98% by weight) and 5919.1 g of deionized water in succession, and aging was carried out at a temperature of 30°C and a rotational speed of 30 rpm for 24 hours. The slurry mixture became a viscous aqueous gel having the same composition as that of the slurry mixture subjected to crystallization in Example 1. Then, a part of the aqueous gel was charged in a sealed vessel, and crystallization was carried out in the stationary state at a temperature of 95°C for 72 hours. The remainder of the aqueous gel was charged in the same reactor as used in Example 1 and crystallization was carried out under stirring at a temperature of 95°C for 72 hours. After completion of crystallization, the post treatment was carried out in the same manner as described in Example 1 to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that the product obtained by carrying out crystallization in the stationary state was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.0, a crystallinity of 98% and a mean particle size of 0.5 µm, and that the product obtained by carrying out crystallization under stirring was composed mainly of phillipsite and gmelinite and a faujasite type zeolite was formed only to a slight extent. Comparative Example 2 The same starting materials as used in Example 1 were used, and 4 ℓ of the aqueous sodium silicate solution was added to 1 ℓ of the aqueous aluminum sulfate solution with stirring over a period of 10 minutes to effect reaction. After completion of addition, stirring was continued for 1 hour to obtain a viscous pasty slurry product having a pH value of 6.7. The reaction temperature was 35°C. The product was subjected to solid-liquid separation using a centrifugal separation and the solid was washed with water until no SO₄ = ion was detected in the washing liquid. The product was amorphous sodium aluminosilicate having a composition shown in Table 1. Then, the reaction vessel of the external heating type used in Example 1 was charged with 1603.2 g of an aqueous sodium hydroxide solution having a concentration of 39.9% by weight, and 1222.4 g of the amorphous sodium aluminosilicate, which corresponded to 14% by weight of the total amount of the amorphous sodium aluminosilicate to be used for the reaction, was added to the aqueous sodium hydroxide solution. The mixture was stirred and aged at a temperature of 30°C for 3 hours. After completion of aging, the added amorphous sodium aluminosilicate was completely dissolved to form a transparent solution. Subsequently, 777.6 g of deionized water and 7509 g of the amorphous sodium aluminosilicate, which corresponded to 86% by weight of the total amount of the amorphous sodium aluminosilicate to be used for the reaction, were added to the solution, and the mixture was maintained at an ambient temperature of 30°C for 1 hour. The slurry mixture became a viscous aqueous gel having the same composition as that of the slurry mixture subjected to crystallization in Example 1. A part of the aqueous gel was charged in a sealed vessel and crystallization was carried out in the stationary state at a temperature of 95°C for 48 hours. The remainder of the aqueous gel was crystallized at a temperature of 95°C for 48 hours under stirring in the same manner as described in Example 1. After completion of crystallization, the post treatment was carried out in the same manner as described in Example 1 to obtain a dry product. From the results of X-ray diffractometry, it was confirmed that each of the product obtained by carrying out crystallization in the stationary state and the product obtained by carrying out crystallization under stirring was composed mainly of phillipsite and gmelinite and a faujasite type zeolite was not formed at all. Comparative Example 3 The procedures of Example 1 were repeated in the same manner except that the compositions of the aqueous solutions of aluminum sulfate and sodium silicate were changed to (Al₂O₃ = 9.65 w/v%, H₂SO₄ = 45.52 w/v%) and (SiO₂ = 27.00 w/v%, Na₂O = 8.69 w/v%, Al₂O₃ = 0.138 w/v%), respectively, to obtain homogeneous compound having a composition shown in Table 1. Then, the same reactor of the external heating type as used in Example 1 was charged with 2955.2 g of an aqueous sodium hydroxide solution having a concentration of 31.62% by weight, and 774.1 g of the homogeneous compound, which corresponded to 14% by weight of the total amount of the homogeneous compound to be used for the reaction, was added to the aqueous sodium hydroxide solution and the mixture was stirred and aged at a temperature of 30°C for 3 hours. The added homogeneous compound was completely dissolved to form a transparent solution was formed. Subsequently, 3332.5 g of deionized water and 4754.7 g of the homogeneous compound, which corresponded to 86% by weight of the total amount of the homogeneous compound, were added to the solution, and the mixture was stirred and maintained at a temperature of 30°C for 1 hour to obtain a low viscosity slurry in which the concentration of sodium hydroxide was 7.91% by weight. The crystallization and post treatment were carried out in the same manner as described in Example 1 to obtain a dry product. From the results of X-ray diffractometry of the product, it was confirmed that phillipsite and gmelinite were simultaneously formed and the crystallinity was 85%. Comparative Example 4 The procedures of Example 1 were repeated in the same manner except that the compositions of the aqueous solutions of aluminum sulfate and sodium silicate were changed to (Al₂O₃ = 8.06 w/v%, H₂SO₄ = 28.78 w/v%) and (SiO₂ = 10.50 w/v%, Na₂O = 6.96 w/v%, Al₂O₃ = 0.054 w/v%), respectively, to obtain a homogeneous compound having a composition shown in Table 1. Then, the same reactor of the external heating type as used in Example 1 was charged with 1006 g of an aqueous sodium hydroxide solution having a concentration of 34.99% by weight and 695.9 g of the homogeneous compound, which corresponded to 14% by weight of the total amount of the homogeneous compound to be used for the reaction, was added to the aqueous sodium hydroxide solution. the mixture was stirred and aged at a temperature of 30°C for 3 hours. The added homogeneous compound was completely dissolved to form a transparent solution. Subsequently, 1924.6 g of deionized water and 4274.5 g of the homogeneous compound, which corresponded to 86% by weight of the total amount of the homogeneous compound, were added to the solution, and the mixture was stirred and maintained at a temperature of 30°C for 1 hour. The mixture became a low viscosity slurry in which the concentration of sodium hydroxide was 4.46% by weight. The crystallization and post treatment were carried out in the same manner as described in Example 1 to obtain a dry product. From the results of X-ray diffractometry of the product, it was confirmed that phillipsite and gmelinite were simultaneously formed and the crystallinity was 54%. Comparative Example 5 899 g of the homogeneous compound obtained in Example 1 was added to to 1017.3 g of an aqueous sodium hydroxide solution having a concentration of 37.74% by weight, and the mixture was stirred and aged at a temperature of 30°C for 3 hours. The added homogeneous compound was completely dissolved to form a transparent solution. Subsequently, 3836.9 g of deionized water and 5521 g of the homogeneous compound were added to the solution, and the mixture was stirred and maintained at a temperature of 30°C for 1 hour. The mixture became a low viscosity slurry in which the concentration of sodium hydroxide was 3.40% by weight. The crystallization and post treatment were carried out in the same manner as described in Example 1 except that the crystallization time was changed to 96 hours, whereby a dry product was obtained. From the results of X-ray diffractometry of the product, it was confirmed that the product was amorphous and a faujasite type zeolite was not formed at all. Comparative Example 6 899 g of the homogeneous compound obtained in Example 1 was added to 4200 g of an aqueous sodium hydroxide solution having a concentration of 30.5% by weight, and the mixture was stirred and aged at a temperature of 30°C for 3 hours. The added homogeneous compound as completely dissolved to form a transparent solution. Subsequently, 629 g of deionized water and 5521 g of the homogeneous compound were added to the solution, and the mixture was stirred and aged at a temperature of 30°C for 3 hours. The mixture became a low viscosity slurry in which the concentration of sodium hydroxide was 11.4% by weight. The crystallization and post treatment were carried out in the same manner as described in Example 1 except that the crystallization temperature was changed to 20 hours, whereby a dry product was obtained. From the results of X-ray diffractometry, it was confirmed that the product was a faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 4.0 and a crystallinity of 90%, which contained a minute amount of phillipsite. Comparative Example 7 The procedures of Example 1 were repeated in the same manner except that aging was carried out at a temperature of 30°C for 0.25 hour. The crystallinity of the faujasite type zeolite obtained by carrying out crystallization for 72 hours was 42%. Comparative Example 8 The procedures of Example 1 were repeated in the same manner except that aging was carried out at a temperature of 30°C for 20 hours. When crystallization was carried out for 20 hours, phillipsite was simultaneously formed and the crystallinity of the faujasite type zeolite was 80%. Comparative Example 9 The procedures of Example 1 were repeated in the same manner except that the crystallization temperature was changed to 65°C. The crystallinity of the faujasite type zeolite obtained by carrying out crystallization for 72 hours was 12%. Comparative Example 10 The procedures of Example 1 were repeated in the same manner except that the crystallization temperature was changed to 140°C. When crystallization was conducted for 20 hours, phillipsite was simultaneously formed and the crystallinity of the faujasite type zeolite was 72%. Comparative Example 11 The same reactor of the external heating type as used in Example 1 was charged with 4836.3 g of an aqueous sodium hydroxide solution having a concentration of 13.46% by weight, and 6420 g of the homogeneous compound was added to the aqueous solution to form a starting slurry, in which the concentration of sodium hydroxide was 5.76% by weight as in Example 1. Then, 100 g, as calculated as the anhydride, of the faujasite type zeolite having an SiO₂/Al₂O₃ molar ratio of 5.6, which was obtained in Example 1, was added as the seed crystal to the slurry, and the slurry was maintained at a temperature of 30°C for 1 hour. The crystallization and post treatment were carried out in the same manner as described in Example 1, whereby a dry product was obtained. From the results of X-ray diffractometry, it was confirmed that phillipsite and gmelinite were simultaneously formed and the crystallinity was 92%.

Claims: A process for the preparation of a high-silica faujasite type zeolite having a silica/alumina molar ratio of at least 4.5, comprising: (a) simultaneously and continuously supplying an aqueous solution of an alkali metal silicate and an aqueous solution of an aluminum-containing compound into a reaction zone whereby the alkali metal silicate is continuously reacted with the aluminum-containing compound to prepare a homogeneous phase compound of a granular amorphous aluminosilicate containing 10 to 16% by weight of aluminum, as Al₂O₃ and based on the weight of the dry homogeneous phase compound, the alumino-silicate being in the form of an aqueous slurry being a pH value of 5 to 9, and having a substantially spherical shape and a particle size of from 1 to 500µm,; (b) subjecting the aqueous slurry of the aluminosilicate to solid-liquid separation; (c) aging a part of the aluminosilicate in an aqueous alkali metal hydroxide solution at a temperature of 10 to 95°C for 0.5 to 12 hours; and (d) crystallizing a mixture of the aged aluminosilicate and the non-aged aluminosilicate in an aqueous alkali metal hydroxide solution having a concentration of 4 to 10% by weight and being maintained at a temperature of from 75°C to 130°C. A process according to claim 1, in which the aqueous alkali metal silicate solution and the aqueous aluminum-containing compound solution are supplied at a substantially constant molar ratio. A process according to claim 1 or 2, in which the aqueous alkali metal silicate solution is an aqueous solution of at least one of sodium silicate, potassium silicate and lithium silicate. A process according to any preceding claim in which the aluminum-containing aqueous solution is an aqueous solution of at least one of aluminum sulfate, aluminum nitrate, aluminum chloride, sodium aluminate and potassium aluminate. A process according to any preceding claim in which the residence time of the aqueous slurry in the reaction zone is at least 3 minutes. A process according to any preceding claim in which the alkali metal hydroxide used in step (d) is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide. A process according to any preceding claim in which the amount of aqueous alkali metal hydroxide solution used in step (d) is such that the content of the granular homogeneous phase amorphous aluminosilicate as dry granular homogeneous phase amorphous aluminosilicate in the starting slurry to be used for crystallization is in the range of from 15 to 35% by weight based on the total amount of the starting slurry. A process according to any preceding claim in which the granular homogeneous phase amorphous aluminosilicate is aged in step (c) at a temperature of 20 to 70°C for 1 to 4 hours. A process according to any preceding claim in which the amount of granular homogeneous phase amorphous aluminosilicate to be aged is in the range of from 10 to 30% by weight based on the total weight of aluminosilicate to be crystallized. A process according to any preceding claim in which the aqueous alkali metal hydroxide solution in step (c) is an aqueous sodium hydroxide solution having a concentration of at least 25% by weight. A process according to any preceding claim in which the crystallization is carried out over 10 to 40 hours. A process according to any preceding claim in which the reaction mother liquor left after crystallization is separated and is used as an alkali metal silicate source for the preparation of the granular homogeneous phase amorphous aluminosilicate.

Inventors: AIMOTO, MICHIYUKI, ARIKA, JUNJI, MIYAZAKI, HIROSHI
Applicants: TOSOH CORPORATION
Application year: 1984
Main classification: C01B33
IPC codes: C07C1, C10G11, C07C67, C07C4, C07C7, B01J29, C10G25, C01B39