JPS6126493B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a method for synthesizing crystalline aluminosilicate zeolites. A large number of synthetic crystalline zeolites have been produced in the past. They are distinguishable from each other from other synthetic crystalline zeolites and from naturally occurring zeolites on the basis of their composition, crystal structure and sorption properties. The existence of a large number of zeolites with similar, but distinguishable properties from one another is advantageous as it allows selection of a particular zeolite with the best properties for a particular application. Such synthetic crystalline aluminosilicates are usually initially prepared in the crystalline form of the alkali metal. Their preparation consists of preparing a mixture of predetermined oxides or substances whose chemical composition can be completely expressed as a mixture of oxides in an aqueous liquid, namely alkali metal oxides, silica, alumina and water at about 100°C for 15 minutes. consisting of heating for 90 hours or more. The product which crystallizes in this hot mixture is separated and washed with water. The resulting aluminosilicate is then activated by heating until dehydration is achieved. It was previously known to synthesize zeolites from systems containing quaternary ammonium ions, in particular tetramethylammonium (TMA) cations. Tetraethylammonium (TEA)
and 1,4-diazabicyclo-[2,2,2]
Other types of organic bases have also been used, including large cations derived from octane. The latter is a U.S. patent regarding the synthesis of zeolite Zk-20.
It is described in detail in the specification of No. 3459646. A representative example of a zeolite crystallized from a reaction mixture containing tetramethylammonium cations is described in U.S. Pat.
This is Zk-4 described in the specification of No. 3314752. Needless to say, crystalline aluminosilicate zeolite consists of a three-dimensional lattice made up of AO ₄ tetrahedra and SiO ₄ tetrahedrons that are intersected and crystallized by sharing _oxygen atoms. The negative charge is balanced by the inclusion in the lattice of a cationic charge equal to the negative charge on the aluminum lattice. According to the invention, at least a portion of the cationic charge is provided by positively charged nitrogen atoms forming part of the ionene or ionomer present in the reaction mixture from which the zeolite is crystallized. For purposes of this invention, ionene is defined as a polymer whose main chain contains periodically positively charged nitrogen atoms. Ionomers, on the other hand, are defined as polymers in which the main chain has side chains containing positively charged nitrogen atoms. Polymers useful in this invention include those that acquire a positive charge (which is neutral in a different environment (eg, as part of an amino group)) as a result of the presence of nitrogen in the reaction mixture. Conventionally, in the synthesis of zeolites, the AO ₄ of the crystal lattice of the final crystal is modified by including monatomic or monovalent cations in the reaction mixture.
It was standard operation to satisfy the negative charge on the tetrahedron. In addition to balancing the negative charge, such cations also act as local building blocks that direct crystallization into aluminosilicates with different structures. According to the invention, the advantages of using cations in which such cations are immobilized in a polymeric arrangement are manifold. First, the fact that these charges are bonded to nitrogen atoms (which, in the case of Aineon, occur periodically on groups pendant to the polymer backbone) is due to the fact that the zeolite's crystal lattice is It is determined that crystallization of the zeolite proceeds to accommodate the chains. The spatial extent (in radial direction) of the main chain of the polymer in question is such that the synthesis method according to the invention yields a zeolite with slotted holes defined by at least eight tetrahedral rings. It is a wide spread. Crystallization is therefore not directed toward compact structures, but favorably toward more open structures, which are known to be useful as adsorbents or catalysts by allowing relatively large adsorbed molecules to enter inside the crystal structure. Another significance of the fact that ionene and ionomers have a considerable spatial extent is that in some crystal systems the presence of said polymers in nucleating the crystal lattice reduces the amount of sodium present in the reaction mixture. is to exclude other cations such as As a result, the zeolite becomes more siliceous, and the lack of cations is expressed in a corresponding lack of aluminum. In many uses of zeolites as catalysts, the more silicic the zeolite is, the more preferable it is. Conversely, in the absence of a polymer, a siliceous zeolite is obtained from the reaction mixture in its typical form (with respect to the silica/alumina ratio). As a result of the openness or porosity of the crystal structure described above, the operation according to the invention can in some cases provide existing zeolites with crystal structures that were not obtainable by conventional synthesis. be. For example, gmelinite has a crystal lattice structure that has been known for many years and has a diameter of about 7
It has a crystal lattice structure that produces grooves of Å. Although this diameter is larger than the diameter sufficient to accommodate a large amount of cyclohexane, synthetic gmelinite always grows with interlaced chaavatite throughout, and this chaavatite acts as an obstacle that prevents cyclohexane molecules from passing through. Since the material is introduced into the 7 Å groove, the cyclohexane sorption capacity of the synthetic gmelinite is small. The use of polymeric cations as described herein makes it possible to crystallize only gnellinite from the chabatite togumelinite system as described above. This is because the small pores of chabatite are clearly too small to form the pores themselves around the polymer backbone. In this way, synthetic gmelinite is produced that exhibits theoretical cyclohexane sorption ability, unlike gmelinite that has been previously reported. The polymers used in the synthetic methods of this invention have molecular weights of at least about 300, and up to about 100,000, generally
It is characterized by having a molecular weight in the approximate range of 500 to 5000. _{The preferred} ionene used _{has the} general _{formula :} ，
C ₁₂ H ₆ or (CH ₂ ) _p (p is a number from 1 to 18)]
Dihalide 1 represented by and the general formula (a), 1,4-diazabicyclo[2, 2,2]octane (b), ditertiary amines (c) bridged by aromatics such as N,N,N',N'-tetramethylbenzidine, and 1,2-bis(4- (pyridyl) ethylene or a ditertiary amine 2 selected from the group consisting of heterocyclic diamines such as 4,4'-bipyridyl.
In the case of ditertiary amines of group (a), the resulting ionenes have the following general formula: (wherein R, R′, R″ and R are alkyl groups of 1 to 6 carbon atoms, derived from diamines, m is 2 to 20, preferably 4 to 6, derived from dihalides) n is 3 to 20, preferably 4 to 6, m
and n is greater than 5, but not greater than 40, and x is a number from 2 to 1000). The groups (CH ₂ ) _n and (CH ₂ ) _o mean that the nitrogen atoms of the ditertiary amine are separated by at least two carbon atoms and the halogen atoms in the dihalide are separated by at least three carbon atoms. They may be straight or branched, with the restriction that they must be separated by carbon atoms. R, R′,
R'' and R may be the same or different alkyl groups. The blocking or terminal group of the polymers described above is usually a halide or its hydrolysis product group, such as a hydroxy group, or an unreacted ditertiary amine. Of the dihalides used, dibromide is particularly preferred due to its ease of reaction with ditertiary amine reactants.Diiodide and dichloride are slightly less preferred than dibromide; It has poor reactivity and requires the use of higher polymerization temperatures than either of the above two. Typical examples of ionene used are as follows. and Other algae useful in the method of this invention are (In the formula, y is a number from 3 to 10, preferably 4 to 6, and z
is a number from 2 to 1000). Other suitable ionenes include (where t is a number from 2 to 1000) and (in the formula, s is a number from 2 to 1000) and (In the formula, f is a number from 2 to 20, preferably from 4 to 6, and r
is a number from 2 to 1000). Iomers useful in the practice of this invention carry the requisite positively charged nitrogen atom (or its precursor) in a variety of different side groups (dangling groups).
Contains in. When nitrogen forms part of the pyridinium group, we use poly(2 - and 4-vinylpyridinium) salts. The repeating unit of the resulting ionomer (poly 4
- In the case of vinylpyridinium salt) is the general formula (wherein R is hydrogen or an alkyl group of 1 to 6 carbon atoms). The repeating unit structure for poly(2-vinylpyridinium) salts is also similar. In this particular case, the polymerization results in a polymer that is both an ionene and an ionomer in which pyridinium groups occur in both the main chain and side chain groups. Suitable ionomers in which positively charged nitrogen atoms form part of the common quaternary groups of the side chains are obtained by quaternizing poly(epichlorohydrin) with trialkylamines such as trimethylamine. . Repeating unit of structure below (wherein and m are 0-10 and 1, respectively). Accordingly, the present invention provides a method for synthesizing crystalline aluminosilicate zeolites from an aqueous reaction mixture containing a silicate, an aluminate, and a source of cations in an amount at least equivalent to the alumina in the reaction mixture, the method comprising: 1~100%
characterized in that the cation source material contains a polymer selected from ionene and ionomers in an equivalent and amount such that the negative charge on the aluminum-containing tetrahedron of There is a way to do it. In most cases, the charge on the aluminum-containing tetrahedra will be balanced by 10-90%, preferably 40-70%, with the charge on the polymeric nitrogen atoms. In one embodiment of the invention, the zeolite is a mixture of oxides of substances whose chemical composition in aqueous solution can be expressed entirely as a mixture of oxides, namely Na ₂ O, SiO ₂ , A ₂ O ₃ , H ₂ O and M ₂ O (where M is the sum of Na ₂ O and the quaternary ammonium polymer expressed as the oxide). Made from a mixture. Generally, colloidal silica sols or alkali metal silicates are used as the source material for silica, and alkali metal aluminates are used as the source material for alumina. Alkali metal hydroxides are suitable for use as sources of alkali metal ions. Heating is preferably carried out at a temperature of from about 80°C to about 200°C until the desired crystalline zeolite is obtained, generally from about 10 hours to 75 days, preferably from about 2 days to about 15 days. . The composition of the reaction mixture, expressed in molar ratios of oxides, is within the following ranges:

The product crystallized from the hot reaction mixture is preferably separated by centrifugation or filtration and washed with water until the pH of the effluent wash water in equilibrium with the zeolite is from about 8 to about 13. The material thus obtained is then activated by heating in an inert atmosphere, for example nitrogen, helium, argon or a mixture of these gases with an oxygen content of less than 5% by volume. Heating is carried out at a temperature of about 200°C to 600°C. During the latter stages of this heat treatment, the atmospheric oxygen concentration may be increased to 20% by volume (air) if care is taken to prevent an uncontrollable violent exothermic oxidation reaction of the polymer residue. This heat treatment serves to decompose and remove the polymer intact from the zeolite, producing hydrogen cations in its place. The resulting hydrogen-alkali metal crystalline aluminosilicate zeolite contains ammonium ions or metal cations such as calcium, magnesium, manganese, vanadium, chromium, potassium, aluminum, lanthanum, praseodymium, neodymium, samarium, and other rare earth metals. ions and solutions containing mixtures of these ions with other ions such as ammonium. As previously mentioned, zeolites made using the method of this invention are useful as adsorbents. The adsorbent can be made into any suitable shape. For example, columns of powdered zeolite give excellent results similar to those in pellet form made by pressing a mixture of zeolite and a suitable binder such as clay into pellets. Although we have stated that the use of polymers according to the present invention directs the reaction mixture toward producing relatively large-pore zeolites, this phenomenon is similar to that in the absence of the polymer when the reaction mixture produces small-pore zeolites. often observed. Thus, by simply incorporating into the analcyte-producing reaction mixture an amount of ionene that provides approximately 30% of the total cation requirement of the reaction mixture in the form of positively charged nitrogen atoms. Mordenite is obtained from. Furthermore, in a similar synthesis, ZEM-12 with relatively large pores is obtained instead of ZSM-5 by incorporating polymeric nitrogen that provides about 20-50% of the total reaction mixture cation requirement; With a % of relevance of about 10-20%, zeolite Y is obtained instead of zeolite P, and with a % of relevance of about 20%, gmelinite is obtained instead of chabatite. The amount of polymer required to be present in the reaction mixture to affect crystallization and bring about the advantageous results of this invention can vary over a wide range. Without wishing to limit the invention to our theory, it is believed that the polymer acts as a support member for the zeolite nucleation and determines at least the pore size of the crystal lattice that is initially assembled in the reaction mixture. It is thought that then. In some systems, only this initially formed lattice subsequently grows, so that a relatively small amount of polymer dominates the total crystallization. On the other hand, in other cases, it is necessary for the polymer to be continuously incorporated into the lattice in order for crystallization to proceed, and therefore a relatively large amount of polymer is required. However, in all systems, crystallization is suppressed by the presence of very high concentrations of polymer, for example in some cases equal to the residual cations of the reaction mixture. Depending on the particular polymer and temperature used, the optimum crystallization control effect for the polymer is determined when the polymer/total cation equivalent ratio in the reaction mixture is approximately
0.07 to about 0.45. We have stated that this invention enables the synthesis of gmelinite that does not contain chabatite. Both of these well-known zeolites are formed from the same building block, the so-called "gmelinite framework", but
However, the way these frameworks are assembled differs depending on each crystal lattice. That is, in the chabatite crystal lattice they are assembled to produce slots that are only about 4 Å in diameter, whereas in gmelinite the largest slots are about 7 Å in diameter. The idealized unit crystal lattice composition for chabatite is Ca ₂ [(AO ₂ ) ₄
(SiO ₂ ) ₈ ]・13H ₂ O, for gmelinite
It is Na ₈ [AO ₂ ) ₈ (SiO ₂ ) ₁₆ ]・24H ₃ O. It is clear that these cations can be exchanged and the Si/A ratio can also be varied, for example from about 1.5 to 4 for each zeolite. The main crystal lattice spacings (dÅ) in the X-ray powder diffractograms of chabatite and gmelinite are calculated from known structural data and are shown in Table A below. In table A I/I ₀
is the ratio of peak height to highest peak height.

[Table] In reality, gmelinite does not contain chabatite, but it is extremely rare, if at all, to be produced. As a result, the adsorption properties of gmelinite virtually become that of chabatite (due to the blockage of gmelinite slots of 7 Å diameter by the interruption of the slot sections of chabatite, whose slot diameter is only 4 Å), and The actual reported line powder diffractogram will be different from the value obtained from the true diffractogram calculated from the ideal structure (and described above) as described above. Therefore, gmelinite is reported to be unable to adsorb molecules larger than propane. The structural features of chabatite that give rise to this occlusion are evidenced by strong X-ray powder diffraction reflections at lattice spacings of 9.39 Å, 5.58 Å and 4.35 Å (corresponding to 101, 201 and 220 crystal planes). (On the other hand, the corresponding aspect of gmelinite is
(reflections occur at lattice spacings of 7.69 Å, 5.067 Å, and 3.44 Å). The presence of one or more of these strong chabatite reflections in the X-ray powder diffraction pattern of the "gmelinite" sample proves that gmelinite crystals are growing within the crystals of the gmelinite sample, and is inevitable. This means that the gmelinite sample is unable to adsorb molecules larger than propane in significant amounts. According to the method of this invention, gmelinite is synthesized to be free or substantially free of chabatite. There is no record that such a synthesis has ever been successfully carried out. The criteria for judging that we have succeeded in such a synthesis is that the gmelinite we synthesize usually does not have any of the three lattice spacings attributed to chabatite identified above, or has an I of less than 2 in the lattice spacing. /I ₀ ratio, and the gmelinite absorbs cyclohexane by 3
% by weight, usually more than 5% by weight, and in many cases up to 8% by weight. Less than 1% of cyclohexane molecules were adsorbed on conventional synthetic gmelinite. In addition to thus providing zeolites that could not be synthesized heretofore, the process of the present invention also allows known zeolites, such as mordenite and zeolite Y, to be synthesized in higher yields than was possible using conventional synthetic methods. This makes it possible to manufacture. According to the invention, mortenite is obtained in a higher siliceous morphology than that reported for conventionally produced large-channel mortenites. That is, it is possible to obtain mordenite having a silica/alumina ratio of about 18 instead of the usual silica/alumina ratio of 10 to 12. Using the polymers specified in Examples 1 to 7 of this specification, the following structures are obtained: SiO ₂ /A ₂ O ₃ = 15-40 H ₂ O/OH = 10-50 OH/SiO ₂ = 0.5-1.5 M It can be obtained from a reaction mixture with ₂ O/SiO ₂ =0.4-1.0 R ₂ O/M ₂ O = 0.1-0.5, where R is defined as one equivalent of polymer cation. According to this invention, the zeolite ZSM-12 can be obtained from a reaction mixture containing less silicon (and in less silicon form than before) (this zeolite and its preparation are described in US Pat. No. 3,832,449). (described in the book). Using the polymers specified in Examples 43-51 of _this specification, the following composition: _SiO2 / _A2O3 = 20-40 _H2O /OH = 50-150 OH/ _SiO2 = 0.2-0.8 M ₂ O/SiO ₂ =0.2-0.7 R ₂ O/M ₂ O = 0.2-0.5, where M is a cation other than R ⁺ , such as an alkali metal. If non-polymeric organic cations of similar structure are used, many such reaction mixtures are ZSM
- produces 5. Gmelinite that does not contain chabatite is Example 1~
The following composition was used: SiO ₂ /A ₂ O ₃ = 10 to 75 H ₂ O/OH ^- = 10 to 50 OH/SiO ₂ = 0.7 to 1.5 M ₂ O/SiO ₂ = 0.3-0.9 _R2O / _M2O =0.01-0.3 (wherein R and M have the same meanings as stated above). Next, the method of this invention will be explained using an example.
This invention is not limited to these. Examples 1 to 7 The polymers used in these examples were made from 1,4-diazabicyclo[2,2,2]octane (Dabco) and 1,4-dibromobutane and had the following structures: be. More specifically, 208 g (1.85 moles) of 1,4-diazabicyclo[2,2,2,]octane were dissolved in 400 g (1.85 moles) of dibromobutane, each in one portion of a 4:1 volume ratio mixture of dimethylformamide:methanol. The resulting mixture is stirred and cooled to maintain a temperature below 35°C. 1
After a week, a white product was formed which was identified as the above polymer with an average molecular weight in the approximate range of about 1000-10000. The product was filtered, pre-purified with ether and air dried. A reaction mixture was prepared by mixing a 30% by weight colloidal silica sol with an aqueous solution of the above polymer, sodium hydroxide, and aqueous sodium aluminate. The composition of the reaction mixture is expressed in molar ratios as follows: SiO ₂ /A ₂ O ₃ = 30 OH ^- /SiO ₂ = 1.1 H ₂ O/OH ^- = 17. _M2O / _SiO2 ratio and R ⁺ /Na ⁺ R ⁺
The ratios were varied as shown in Table 1 below. The latter ratio is the mole fraction of ammonium cation (R ⁺ ) added as bromide, and M ₂ O is the sum of Na ₂ O and quaternary ammonium polymer expressed as oxide. The crystallization operation, carried out in a Teflon vessel without agitation, was essentially complete after 7 days at 170°C to 190°C. Helium was added to maintain the pressure at 70 Kg/cm ² gauge (1000 psig). The type of zeolite product was determined by X-ray diffraction analysis.

[Table] The above results, particularly those of Examples 1 to 4, indicate that as the amount of polymer added to the reaction mixture increases, the product shifts from a dense structure, that is, analsite, to large-pore zeolite, that is, mortenite. shows. If an equivalent amount of sodium bromide is added (instead of polymer), the product will always be asarcite and the effect described above will not occur. Chemical analysis of the mordenite product established the following composition: 0.40N ₂ O・0.79Na ₂ O・A ₂ O ₃・19.7SiO ₂ The carbon/nitrogen molar ratio is 6.8, and compared to the carbon/nitrogen molar ratio of the polymer of 5, the polymer It showed some decomposition. The product, mortenite, is stable to calcination at 550°C for 16 hours and easily adsorbs cyclohexane (at 25°C,
6.3% at 60 mm Hg). Examples 8 to 24 Reaction mixtures were prepared by mixing 30% by weight colloidal silica sol with the aqueous polymer solutions described above, sodium hydroxide, and aqueous sodium aluminate solutions. The reaction mixture has the following composition expressed in molar ratios. OH ^- /SiO ₂ = 1.2 H ₂ O / OH ^- = 17 SiO ₂ /A ₂ O ₃ , M ₂ O / SiO ₂ and R ⁺ /Na ⁺ +
The molar ratio of R ⁺ was varied as shown in Table 2 below. Each ratio of actors has the same significance as mentioned above.
Crystallization was achieved after the number of days listed in Table 2 at 90° C. with occasional mixing in a polypropylene container. The results are listed in Table 2.

【table】

[Table] From the results presented above, it can be seen that in the reaction mixtures that normally produce zeolites Y and P, even small amounts of polymer direct crystallization to gmelin-type zeolites. Importantly, increasing the amount of polymer results in a zeolite product that exhibits the expected X-ray diffraction pattern for gmelinite without chabatite.
The gmelinite obtained here exhibits adsorption properties that are substantially different from the available naturally occurring and synthetic gmelinites. These latter zeolites, in their hydrocarbon adsorption, do not exhibit the behavior dynamics of large pores with a pore size of about 7 angstroms, as expected from the structural data, but rather with the characteristic behavior of small pores with a pore size of about 4 angstroms. indicate a property. This adsorption behavior is attributed to stacking faults in chabatite that block or restrict large gmelinite slots. The present method for gmelinite synthesis eliminates such defect surfaces. The analysis of the product of Example 14 is as follows: 0.43N ₂ O.0.67Nba ₂ O.A ₂ O _{3.7.05SiO 2} 73% adsorption of cyclohexane (at 25° C. and 60 mm Hg). That is, 3.7% is adsorbed rapidly at first, and reaches the limit capacity of 7.3% in about 1 hour. For comparison, sodium chabatite and naturally occurring gmelinite (Na, Ca types) adsorb 0.8% and 1.0% of total cyclohexane, respectively. The ability of the gmelinite zeolite produced by the method of the present invention to adsorb a relatively large amount of cyclohexane is attributable to the absence of stacking faults of chabatite within the gmelinite. Examples 25 to 28 The following structure: SiO ₂ /A ₂ O ₃ = 50, OH ^- /H ₂ O
= 1.2, H ₂ O/OH ^- = 17, M ₂ O/SiO ₂ = 0.6 and
A reaction mixture was prepared with R ⁺ /Na ⁺ +R ⁵ =a1.
The reaction mixture was prepared by mixing a 30% colloidal silica sol with a polymer water bath solution and an aqueous NaOH/NaAO ₂ solution. The resulting mixture is heated to 80~
Crystallization was carried out by placing in an oven at 90°C and taking samples from time to time. At crystallization periods of 3, 7 and 13 days, the solid product contained the following contents of crystalline zeolite Y:

[Table] ｜
_CH3
Polymer was added as bromide. The remainder of the solid product was essentially zeolite P. The highest production of zeolite Y at all triplicate sampling times was obtained with the polymer used in Example 27. Examples 29-38 The following polymers were used in these examples. Polymer was added as bromide. A reaction mixture using the above polymer was made by mixing a 30% colloidal silica sol with an aqueous solution of the above polymer and an aqueous NaOH/NaAO ₂ solution. The composition of the reaction mixture is SiO ₂ /A ₂ O ₃ = 31,
OH ^- /SiO ₂ =1.1 and H ₂ O/OH ^- =20. Crystallization occurs at 180℃ and 90℃ as shown in Table 3.
Achieved at °C.

Table: The unknowns in some of the zeolite products mentioned above are only present in small amounts. Example 39 One property that distinguishes polymers from monomers is that the viscosity of an aqueous solution of the former increases with increasing concentration. Correspondingly, highly purified polymers were prepared for viscosity measurements. More specifically, 1,4-dibromobutane
177.6 g (0.82 mol) of dimethyl sulfoxide 800
ml of 1,4-diazabicyclo[2,2,2,]octane (92.2 g (0.82 mol)) was added dropwise at 45°C with stirring. When these reactants were mixed, the temperature rose to about 80°C. The temperature is approximately 110℃ when mixing is complete.
and kept at this temperature for 4 hours. The mixture was then cooled and the precipitated polymer was filtered and extracted repeatedly with ether until the odor of dimethyl sulfoxide was no longer perceptible, forming a slurry. The polymer was a free-flowing, water-soluble, pale yellow powder.
According to elemental analysis, sulfur was 0.51%. The analytical values after correction for residual dimethyl sulfoxide were as follows. Calculated value Actual value Carbon 36.59 3380 Hydrogen 6.10 710 Nitrogen 8.53 818 Bromine 48.78 5092 The kinematic viscosity at 37.8℃ (100〓) of the above polymer aqueous solution and 1,4-dimethyldiazabicyclo[2,2,2,]octane was obtained for the corresponding solution of the niodide monomer. The data for viscosity in centistokes and concentration in grams per 100 cc of 0.4M KBr solution are as follows:

Table: A kinematic viscosity of 0.68 centistokes was measured in the absence of organic compounds. Example 40 The polymers used in this experiment are N, N, N',
It was made from N'-tetramethylbenzidine and α,α',-dibromo-p-xylene. More specifically, dimethylformamide 1,5
100 g (0.38 mol) of the above dibromide in the same solvent 3 and 93 g (0.38 mol) tetramethylbenzidine
was added to the solution. The temperature was kept below 50℃ and stirred for one week. The precipitate formed was filtered, washed with ether, and air dried. Structure below: SiO ₂ /A ₂ O ₃ = 62, OH ^- /SiO ₂
= 0.84, H ₂ O/OH ^- = 19 and Na ₂ O/SiO ₂ = 0.4
A reaction mixture was prepared with The polymers were added such that the R ⁺ /R ⁺ +Na ⁺ molar ratio varied within the range of 0.01 to 0.10. 30% colloidal silica sol
Zeolites were prepared by mixing with a slurry of the above polymer in an aqueous solution of NaOH/NaAO ₂ . Crystallization is carried out at 80℃ with periodic sample collection.
This was achieved after being placed in an oven at ~90°C. After 14-23 days the product was filtered and analyzed by X-ray diffraction. Zeolite beta was identified in the product mixture. Examples 14 to 42 These examples illustrate what happens when zeolites made by the process of this invention are contacted with a mixture of paraffin and aromatics. For these examples, the products of Examples 4 and 14 were converted to the ammonium form by conventional methods known in the art. The zeolite catalyst obtained after calcination at 500° C. for 2 hours was charged into a reactor and tested as follows. Reaction conditions were 427℃ (800〓), WHSV2-3,
H ₂ :CH=3.7, 14Kg/cm ² gauge pressure (200peig). The feedstock was an equal weight mixture of n-hexane, 3-methylpentane, 2,3-dimethylbutane, benzene and toluene. After 5 hours of contact reaction, the product was sampled and analyzed, and the following results were obtained.

[Table] Of the decomposed hexane, 8% and 1% were observed as aromatic alkyl side chains for mordenite and gmelinite, respectively. Preferential conversion of Norman paraffin is desirable for post-modification applications. This is because these linear isomers are the low octane component of typical modifications. However, this type of conversion does not normally occur in mordenite. Conventional mordenite synthesized in the absence of organic quaternary ammonium cations shows preferential conversion of the branched chain isomer, 2,3-
17 each for DMB, 3-MP and N-C6
%, 6% and 7%. Such preferential conversion of branched isomers observed for gmelinite samples indicates that large pore zeolites are generally more suitable for cracking, isomerization and hydrocracking applications. The gmelinite used in this example exhibits X-ray diffractogram values showing the following significant lines:

[Table] This diffraction diagram does not contain any traces of peaks at crystal lattice spacings of 9.39 Å, 5.58 Å, and 4.35 Å, indicating that gmelin does not contain chaavatite completely. Example 43-Example 52 The effect of various polymers in synthesizing zeolite ZSM-12 was studied. Silica sol is used as the source material of silicate, and the silica/alumina ratio is
Various experiments were carried out using 28-30 reaction mixtures under static autoclave conditions at 180°C. Five different polymers were used. In Table 4 listing the experimental results, the symbols in the polymer column refer to the following substances. "4-PX": α,α'-dibromo-p-xylene and N,N,N',N'-tetramethyl-
Polymer obtained from 1,4-butanediamine, molecular weight approximately 5500, "6-PX": α,α'-dibromo-p-xylene and N,N,N',N'-tetramethyl-
Polymer obtained from 1,6-hexanediamine, molecular weight approximately 9500, "Dab-4": polymer of Examples 1 to 7 "Dab-10": similar to Dab4, but dibromobutane monomer is replaced with dibromodecane molecular weight approximately 5500, "6-4": N, N, N', N'-tetramethyl-
Polymer obtained from 1,6-hexanediamine and 1,4-dibromobutane, molecular weight approximately 6000.

Attempts to crystallize ZSM-12 from similar reaction mixtures using monomeric cations structurally related to the above polymer components were unsuccessful. This is because these reaction mixtures are undoubtedly not highly inducing for the formation of this particular zeolite. It is also noteworthy that the ZSM-12 product obtained is at the lower end of the range of silica/alumina ratios for ZSM-12. Thus, the polymer is ZSM-12 with a silica/alumina ratio of 20 to 30.
This provides a reliable route to crystallization. EXAMPLE 53 - EXAMPLE 62 The effect of various polymers was investigated in the synthesis of zeolite Y. Various experiments were carried out under static autoclave conditions at 85° C. using silica sol as the source material for silicate. Reaction mixture silica/
The alumina ratio is 28. The polymer names in Table 5 have the following meanings. "6-4": Same as in Examples 43-52 "6-2" and "6-6": Same as "6-4", but with symmetric dibromoethane and 16-dibrom as the second monomers, respectively. using hexane

【table】

Table: From Examples 53, 56 and 59 without polymer (sodium being the only cation present), the use of polymer increased the silica/alumina ratio of the product in each case. I understand.

Claims (1)

Claims: 1. A method of synthesizing a crystalline aluminosilicate zeolite from an aqueous reaction mixture containing a silicate source material, an aluminate source material, and a cation source material in an amount at least equivalent to the aluminum in the reaction mixture, comprising: 1~ of generated zeolite
Ionene is a polymer whose main chain periodically contains positively charged nitrogen atoms in an equivalent and amount such that the negative charge on the 100% aluminum-containing tetrahedrons balances the positively charged polymeric nitrogen atoms. and ionomers, which are polymers whose main chains have side chains containing positively charged nitrogen atoms, wherein the cation source substance contains a polymer selected from ionomers. 2. The method of claim 1, wherein the nitrogen atoms of the polymer balance the negative charge of 10 to 90% of the aluminum-containing tetrahedra of the zeolite produced. 3. The method of claim 1, wherein the nitrogen atoms of the polymer balance the 40-70% negative charge of the aluminum-containing tetrahedra of the zeolite produced. 4 Ionene is an α,ω dihalide of 3 to 20 carbon atoms, a dihalide with 2 to 20 carbon atoms separating the nitrogen atoms, and 1 to 6 carbon atoms in each alkyl substituent. The method according to claim 1, which is a reaction product with a tertiary amine and has a degree of polymerization of 2 to 1000. 5. The method of claim 4, wherein the ditertiary amine is 1,4-diazabicyclo[2,2,2]octane. 6. The method of claim 4, wherein the ditertiary amine is N,N,N',N'-tetramethylbenzidine. 7. The method of claim 4, wherein the ditertiary amine is 1,2-bis(4-pyridyl)ethylene or 4,4-bipyridyl. 8. The method according to claim 4, wherein the dihalide is Benzilik. 9. The method according to claim 4, wherein the dihalide is dibromide. 10. The method of claim 1, wherein the polymer is an ionomer, the positively charged nitrogen atoms forming part of the pyridinium groups. 11. The method according to claim 10, wherein the ionomer is a poly(2-alkynylpyridinium) salt or a poly(4-alkenylpyridinium) salt. 12. The salt is a poly(2-vinylpyridinium) salt or a poly(4-vinylpyridinium) salt. pyridinium) salt,
A method according to claim 11. 13. The method of claim 1, wherein the polymer is an ionomer and the positively charged nitrogen atom is a quaternary atom. 14. The method of claim 13, wherein the ionomer is poly(epichlorohydrin) quaternized with trimethylamine. 15. The method according to claim 1, wherein the nitrogen atoms of the polymer have acquired a charge as a result of the presence of the polymer in the reaction mixture. 16. The method of claim 1, wherein the polymer has a molecular weight of at least 300. 17. The method of claim 16, wherein the polymer has a molecular weight in the range of 3,000 to 18,000. 18 The reaction mixture has the following composition: _SiO2 / _A2O3 = _{20-40 H2O} /OH=50-150 OH/ _SiO2 =0.2-0.8 _M2O / _SiO2 =0.2-0.7 _R2O / 9. The method of claim 8, wherein _M2O =0.2-0.5 and the zeolite is ZSM-12. 19 The reaction mixture has the following composition: _SiO2 / _A2O3 = _{15-40 H2O} /OH = 10-50 OH/ _SiO2 = 0.5-1.2 _M2O / _SiO2 = 0.4-1.0 _R2O / 5. The method of claim 4, wherein _M2O =0.1 to 0.5 and the zeolite is mordenite. 20. The method according to claim 5, wherein the zeolite is gmelinite. 21 Gmelinite is 5~5 at 25℃ and 60mmHg
21. The method of claim 20, wherein 8% by weight of cyclohexane is adsorbed. 22 Gmelinite has an X-ray diffraction diagram value with the lattice spacing shown below.
21. The method of claim 20, wherein the lattice spacing of has a relative intensity of less than 2. 23 The reaction mixture has the following composition: SiO ₂ /A ₂ O ₃ = 10-75 H ₂ O/OH = 10-50 OH/SiO ₂ = 0.7-1.5 M ₂ O/SiO ₂ = 0.3-0.9 R ₂ O/ 21. The method according to claim 20, wherein _M2O =0.01 to 0.3.