JPS6220132B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to zeolites, and more particularly to methods for producing zeolites with large crystal structures. Zeolites, both natural and synthetic, have been known to have catalytic abilities in various hydrocarbon conversion reactions. Some zeolites, which consist of regularly porous crystalline aluminosilicate, have a certain crystalline structure, as determined by X-ray diffraction, with several small pores, and these pores are surrounded by smaller grooves. connected by. These pores and grooves have a certain uniform size depending on the type of zeolite. The size of these pores allows molecules of a certain size to be adsorbed, but molecules larger than that to be excluded.These materials are generally known as "molecular sieves" and have a unique adsorption property. It is used in various ways. Crystalline aluminosilicates are characterized by the presence of aluminum and silicon, the ratio of the total amount of these atoms/oxygen being 1/2. The amount of aluminum present in conventional aluminosilicates appears to be directly related to the acidity properties of the final product. A low aluminum content results in low acidity, low coke formation rate, and low catalyst aging rate. US Patent No. 3941871 has a high SiO ₂ /Al ₂ O ₃ ratio
Discloses the production of ZSM-5 type zeolite. This patent discloses the use of TPA and TMA in combination to produce crystalline metal organosilicate. The method for producing the crystalline zeolite ZSM-5 having a SiO ₂ /Al ₂ O ₃ molar ratio of 25 to 1000 and a crystal size of at least 1 micron according to the present invention is a method for producing crystalline zeolite ZSM-5 having a SiO 2 /Al 2 O 3 molar ratio of 25 to 1000 and a crystal size of at least 1 micron. A combination of other cations having a radius greater than about 1.40 angstroms and large enough to fit into the pores of the zeolite to be produced is present in the reaction mixture. Preferably it is a combination of tetrapropylammonium (TPA) and selected from the group consisting of tetramethylammonium (TMA), tetraethylammonium (TEA), cesium and rubidium cations. The ionic radius of these cations is as follows. TMA ⁺ = 3.2 angstroms (units are the same below), TEA ⁺ = 4.0, Cs ⁺ = 1.7, Rb ⁺ = 1.5. The present invention is utilized for producing ZSM-5 type zeolite. That is, the zeolite of the present invention
Despite the very high SiO ₂ /Al ₂ O ₃ ratio, the product still has zeolite properties and has a specific zeolite crystal structure. They are active despite having a low alumina content, ie a very high silica/alumina ratio, and are very active even when the silica/alumina ratio exceeds 25. Considering that the catalytic activity generally depends on the aluminum atoms in the framework,
This high level of activity is a surprising fact. These catalysts can be combined with other zeolites, such as X
It retains its crystallinity for long periods of time even in the presence of water vapor at such high temperatures that it irreversibly disintegrates the framework, such as type or type A. Furthermore, even if carbonaceous precipitates form, they can be removed and activity restored by combustion at higher than normal temperatures. In many cases, zeolites of this type have very low coke formation and can be operated for very long periods, with long intervals between regeneration treatments. An important feature of the crystal structure of ZSM-5 zeolite is that the pore size is greater than about 5 angstroms, with the pore windows being sized so that they are defined by a 10-membered ring of oxygen atoms. The goal is to control the entry and exit of molecules into the free space within the crystal. It should be understood, of course, that these rings are formed by the regular arrangement of tetrahedra that form the anionic framework of the crystalline zeolite. Briefly, the preferred types of catalysts useful in the present invention have a silica/alumina ratio of at least about 25 and have a structure that controls the entry and exit of molecules into and out of intracrystalline free space. The silica/alumina ratio referred to herein can be measured by conventional methods. This ratio is meant to be as close as possible to the ratio in the hard anionic framework of the zeolite crystal, excluding aluminum in the binder, cations in the grooves, etc. Zeolites of the type useful in this invention freely adsorb n-hexane and have pore sizes greater than about 5 angstroms. Furthermore, the structure must control the approach of molecules larger than a certain standard. Whether or not a material has such control characteristics can be determined by knowing its crystal structure. For example, if the pore windows of the crystal are constituted by eight-membered rings of oxygen atoms, access of molecules with a cross section larger than n-hexane is excluded, and this zeolite is not of the desired type. Generally, those having a window the size of a 10-membered ring are preferred. However, if the hole becomes excessively blocked for some reason, it will no longer be effective. Although those with a 12-membered ring size generally do not have sufficient control properties to produce the desired conversion reactions, TMA
Some materials with a moderately constricted structure, such as offretite, are effective. In addition, there are cases where the hole is appropriately closed for some reason and becomes effective. Rather than determining from the crystal structure whether a catalyst has the required control properties, the following procedure is used to deposit n on small catalyst samples of about 1 g or less at atmospheric pressure.
The "control index" can be easily determined by continuously passing a mixture of equal weights of -hexane and 3-methylpentane. Catalyst samples in the form of pellets or extrudates were ground to coarse sand particle size and packed into glass tubes. Before testing, the catalyst is treated with a stream of air at 537.8°C (1000°) for at least 15 minutes. The catalyst was then flushed with helium to a temperature of 287.8~
Adjust the temperature to 510.0℃ (550-950〓) to make the overall conversion rate 10-60%. A mixture of hydrocarbons diluted with helium to a helium/total hydrocarbon molar ratio of 4/1 is passed over this catalyst at a liquid hourly space velocity of 1 (liquid hydrocarbon volume/catalyst volume/time=1).
After running for 20 minutes, a sample of the effluent is taken and analyzed (most conveniently by gas chromatography) to determine the fraction remaining unchanged for each of the two hydrocarbons. The "control index" is calculated as follows. Control index = log ₁₀ (remaining n-hexane fraction)/log _1
0 (remaining 3-methylpentane fraction) The control index approximates the ratio of the cracking rate constants of the two hydrocarbons. Catalysts suitable for the present invention have control index values of about 1 to 12. Control index values for some representative catalysts are shown below. Catalyst control index ZSM-5 8.3 ZSM-11 8.7 ZSM12 2 ZSM-35 4.5 Beta 0.6 ZSM-4 0.5 H-zeolon 0.5 REY 0.4 Amorphous silica-alumina 0.6 Erionite 38 The value of the control index mentioned above depends on the specific zeolite. Although characterized, its value is the cumulative result of several variables used in its measurement and calculation. Therefore, when considering any zeolite, the control index changes within the range of 1 to 12 depending on the temperature within the range of 287.8 to 510.0℃ (550 to 950〓) and the conversion rate is within the range of 10 to 60%. . Similarly, factors such as the crystal size of the zeolite, the presence of occluded contaminants and the presence of binders tightly bound to the zeolite influence the value of the control index. Therefore, although the control index values listed here are a very useful means of characterizing important zeolites, they are only rough approximations and may vary depending on the combination of measurement methods and extreme values of variables. It is necessary to take this into account. However, in any case, 287.8
At temperatures in the range of ~510.0°C (550-950〓), the important control index values of zeolites exhibit values of about 1-12. Details of ZSM-5 are described in US Pat. No. 3,702,886. When zeolites are produced in the presence of organic cations, they become catalytically inactive because the intracrystalline free space is occupied by the organic cations in the production solution. However, they are activated by firing at 400-600°C for 15 minutes to 24 hours in air or an inert atmosphere. The calcined product is then ion-exchanged with NH ₄ salts or acids and then calcined to further activate the catalyst. Zeolites may be used in any form: ammonium form, hydrogen form or other monovalent or polyvalent cationic forms. Preferably either of the latter two forms is used. These may be intimately combined with hydrogenating components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metals such as platinum or palladium that have a hydrogenating function.
These components may be ion exchanged, impregnated or physically intimately mixed. These components, for example in the case of platinum, are impregnated into or deposited onto the catalyst by treating the zeolite with platinum metal-containing ions. Examples of suitable platinum compounds include dichloroplatinic acid, platinum chloride, and various compounds containing platinum amine complexes. Useful compounds of platinum or other metals are divided into those in which the metal is present as a cation and those in which the metal is present as an anion. Both types containing the metal in ionic form can be used.
Platinum metal is in the form of a cation or a cationic complex,
For example, solutions in the form of pt(NH ₃ ) ₆ Cl ₄ are particularly useful. For some hydrocarbon conversion processes, catalysts in the form of this noble metal are required. If a zeolite is used as either an absorbent or a catalyst in one of the above processes, the zeolite must be at least partially dehydrated. In this dehydration treatment, the zeolite can be heated in an atmosphere of air, nitrogen, etc. at a temperature in the range of 200 to 600° C. at atmospheric pressure or at a pressure below atmospheric pressure for 1 to 48 hours. Dehydration can also be carried out at lower temperatures by simply placing the catalyst under vacuum, but this requires longer times to achieve sufficient dehydration. The zeolite of the present invention is produced from a reaction mixture having the following composition expressed in molar ratios of oxides.

[Table] Typical reaction conditions are to heat the above mixture at approximately 80-200°C.
It consists of heating at a temperature of about 4 hours to about 30 days. As in the case of the synthesis of ZSM-5 aluminosilicate, digestion of the gel particles is carried out until complete formation of crystalline zeolite. The product crystals are then cooled, separated by filtration, washed with water,
Dry at approximately 80-150℃. Zeolites of this type may also have other cations bound to them. Various cations can be attached by methods known in the art. Examples of representative cations include hydrogen, ammonium and metal cations and mixtures thereof. Particularly preferred among the metal cations are the rare earth metals, manganese and calcium, as well as metals from groups of the periodic table (eg zinc) and metals from groups of the periodic table (eg nickel). Typical methods include impregnating zeolite with a desired cation salt or ion-exchanging it. Although a variety of salts can be used, particularly preferred are chlorides, nitrates and sulfates. For typical ion exchange technology, see US Patent No.
There are No. 3140249, No. 3140251 and No. 3140253. After ion exchange with a solution of the salt of the desired cation, the zeolite is preferably washed with water and 65.6~
Dry at a temperature of 315.6°C (150-600°) and then calcined in air or other inert gas for 1-48 hours or more at a temperature of about 260.0-815.6°C (500-1500°). The impregnation procedure is carried out in a conventional manner. That is, the zeolite is contacted with a solution of salt, then dried and calcined in the usual manner. Despite the presence of cations bound in the synthetic form of the catalyst by replacing sodium or other alkali metals, as seen from the X-ray powder diffraction pattern of ion-exchanged zeolites, the present invention The spatial arrangement of aluminum, silicon and oxygen atoms forming the basic crystal lattice of zeolites remains essentially unchanged. For example, the X-ray diffraction pattern of some ion-exchanged ZSM-5 zeolites is substantially the same as that shown in US Pat. No. 3,702,886. As is the case with many catalysts, the catalyst of the present invention is mixed with materials that are resistant to the temperatures and other conditions used in the organic conversion process. Examples of such durable materials are synthetic or natural zeolites as well as inorganic materials such as clays, silicas and/or metal oxides. The latter can be either a gel or gelatinous precipitate containing a mixture of silica and metal oxides or a natural one. The use of the catalyst of the present invention in combination with certain materials improves conversion and/or selectivity in certain organic conversion processes. Inert substances suitably act as diluents and control the amount of conversion in a given step, so that the product can be obtained economically and in an orderly manner without using other means to control the reaction rate. A product is obtained. Zeolitic materials are usually mixed with natural clays such as bentonite and kaolin to improve the crush strength of the catalyst under commercial operating conditions. These materials, clays, oxides, etc., act as binders for the catalyst. In petroleum refineries, catalysts are handled roughly and may be broken into powder, which may interfere with the process, so it is desirable to provide catalysts with good crushing strength.
Clay binders have been used for the purpose of improving the crush strength of catalysts. Examples of natural clays that are composited with catalysts include montmorillonite and kaolins, which include subbentonite and kaolin, which are commonly known as Dixie, McNamee-Georgia, and Florida clays, and whose main minerals are Ingredients include halloysite, kaolinite, dateskite, nacrite, or anorkisite. These clays may be used in their raw state as mined, but they may also be used after being calcined, treated with acid, or chemically modified. In addition to the above-mentioned materials, the catalysts may be silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryria and silica-titania, as well as ternary systems such as silica-alumina-thoria,
It may also be composited with porous matrix materials such as silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.
This matrix may be in the form of a co-gel. The relative proportions of finely ground crystalline aluminosilicate and inorganic oxide gel matrix can vary within a wide range, with the content of crystalline aluminosilicate accounting for about 1-90% by weight of the composite, especially for composites. When the body is manufactured in the form of beads, it accounts for about 2 to 80% by weight. A typical reaction step contemplated for silica is the disproportionation of toluene to benzene and xylene, where the amount of p-xylene obtained is much higher than the normal equilibrium concentration. This reaction is about 400
It is effectively carried out at temperatures of ~700°C, pressures of about 1 to 100 atmospheres, and weight hourly space velocities of about 1 to 50. The raw material suitable for use in the silica method is _C2
The stream is rich in ~ _C15 olefin content. That is, ethylene, propylene, butene, pentene, hexene, dienes (e.g. butadiene, pentadiene), cycloolefins (e.g. cyclopentene and cyclohexene), alkyl-substituted cycloolefins (e.g. ethylcyclopentene), cyclopentadiene and cyclohexadiene, etc. It is effectively converted to obtain para-dialkyl-substituted benzene in high yield. The conversion reaction using such an olefin feedstock is carried out at a temperature of about 300 to 700°C, a pressure of about 1 to 100 atmospheres, and a weight hourly space velocity of about 1.
~1000 and done. As a feedstock for the olefin reactant, a substantially pure stream of _C2 - _C15 olefins may be used, or a refined petroleum product rich in such reactants, i.e., generally containing a proportion higher than 25% by volume. A factory or chemical plant flow may be used. Other raw materials that can be effectively used in the present invention to selectively produce paradialkyl-substituted benzenes having alkyl groups having 1 to 4 carbon atoms include paraffinic hydrocarbons having 3 to 44 carbon atoms; There is. Representative raw materials for these paraffins include butane, pentane, hexane, heptane, octane, dodecane, eicosane, dotriacontane, tetracontane, and alkyl-substituted derivatives of these paraffins. When these paraffinic raw materials are used, the reaction conditions are such that the raw materials are contacted with a large crystalline aluminosilicate zeolite catalyst at a temperature of approximately 400 to 700°C, a pressure of approximately 1 to 100 atm, and a weight hourly space velocity of approximately 0.1 to 100. consists of causing. Mixed aromatics can also be used as raw materials. For example, a mixture of ethylbenzene and toluene is selectively converted to a mixture rich in p-diethylbenzene and p-ethyltoluene, with the latter predominating when the toluene/ethylbenzene ratio in the feed is high. p-Dialkylbenzenes are produced by reacting benzene, toluene, ethylbenzene, propylbenzene or butylbenzene with _C2 - _C20 olefins or _C5 - _C25 paraffins at 250-500<0>C. This reaction is preferably carried out under pressure greater ^than 200 psig. For example, benzene/ethylene is 1/2 to 10/1
When reacting at a molar ratio of , p-diethylbenzene is produced in addition to ethylbenzene (pressure = 28.1
Kg/cm ² gauge pressure (400psig); Temperature = 426.6℃
(800〓). When toluene and 1-octene are reacted, p-ethyltoluene and a mixture of n-propyltoluene and isopropyltoluene enriched in the para isomer are produced. Without the addition of aromatics, the _C2 - _C15 olefins and _C3 - _C44 paraffins each produce a mixture of aromatics rich in p-dialkylbenzene.
Olefins and higher paraffins are more reactive and require less severe handling, for example reaction temperatures of 250-600°C, preferably 300-550°C. Lower paraffins, such as C ₃ to C ₅ paraffins, do not produce aromatics at a practical rate unless the temperature is higher than 400°C. Aromatization can be carried out under atmospheric pressure or elevated pressure, and low partial pressures of hydrogen may be used to retard the rate of catalyst aging, but only if the hydrogen partial pressure is 14.1 Kg/cm ² gauge pressure. (200 psig), aromatic production decreases. The preparation of p-dialkylated benzenes with alkyl groups larger than C ₁ is advantageous at higher pressures and lower temperatures. For example, p-ethyltoluene is produced from either dodecane or 1-butene at 400°C, whereas p-xylene is produced at higher temperatures. The invention will be explained in more detail by the following examples. Example 1 Q brand sodium silicate (28.5%
SiO ₂ , 8.9% Na ₂ O) 6872 g, H ₂ O 3976 g and
A silicate solution was prepared by mixing 20 g of Daxad27 surfactant. The specific gravity of this solution is 15.6℃ (60〓)
It was 1.297. 238g Al ₂ (SO ₄ ) ₃ ×H ₂ O
(17.2% Al ₂ O ₃ ), 574 g H ₂ SO ₄ (100%), 1200 g
of TMACl (50% by weight), 1200 g H ₂ O and 3200 g
of TPABr solution (obtained by pre-reacting a mixture of equal equivalents of tri-n-propylamine and n-propyl bromide, the nitrogen content of the pre-reacted organic mixture was 1.43% by weight). An acidic alum solution was prepared by mixing the following: The above-mentioned "pre-reacted organic mixture" will be referred to as "pre-reacted organic substance" in the following examples.
Its specific gravity was 1.102 at 15.6℃ (60〓). Add the silicate solution and acidic alum solution to 18.9
(5 gallon) autoclave to form a gel. The gel was stirred at room temperature for 30 minutes to obtain a homogeneous mixture. Crystallization was carried out at 160.0°C (320°C) with stirring at 90 rpm. The time required for complete crystallization was approximately 23 hours.
The obtained solid product was filtered, washed with water, dried and subjected to X-ray analysis, and it was found to be 115% ZSM-5.
The SiO ₂ /Al ₂ O ₃ ratio was 77.5. When the crystal size was measured with a scanning electron microscope, it was 12 x 7 x 5 μ ~
It was within the range of 2×2×1μ. Example 2 A silicate solution was prepared by mixing Q brand sodium silicate, Daxad 27 and H ₂ O as shown in Example 1. 238g Al ₂ (SO ₄ ) ₃ ×H ₂ O
(17.2% Al ₂ O ₃ ), 570 g H ₂ SO ₄ (100%), 1345 g
An acidic alum solution was prepared by mixing 1,175 g of TEABr, 1175 g of H ₂ O, and 3680 g of "pre-reacted organics" (1.22 wt% N). These solutions were mixed and the gel was stirred and heated to 160.0°C (320°C) with stirring at 90 rpm. It took 12 hours for crystallization to complete. X-ray analysis of the washed and dried product showed that it was 110% ZSM-5 and the SiO ₂ /Al ₂ O ₃ ratio was 71.1. According to scanning electron microscopy, the crystal size is 8×5×4μ~1.5×
It was 1×1μ. Example 3 1374g Q brand sodium silicate,
A silicate solution was prepared by mixing 800 g H ₂ O and 4 g Daxad27. 47.6g Al ₂ (SO ₄ ) ₃ ×
_H2O (11.2% _Al2O3 ) _{, 114g H2SO4} (100%),
An acidic alum solution was prepared by mixing 200 g CsCl, 800 g H ₂ O and 640 g TPA solution (see Example 1). The two solutions were mixed into a gel and an additional 100 g of CsCl was added to the gel.
Crystallization was completed within 14 hours at 160.0°C (320°C) with constant stirring. This product is 95%
The silica/alumina ratio of ZSM-5 was 62.3.
When measured with a scanning electron microscope, the crystal size was 7x6x3μ to 2x2x1μ. Example 4 (Comparative Example) A silicate solution was prepared according to Example 2. 238
g of Al ₂ (SO ₄ ) ₃ × H ₂ O (17.2% Al ₂ O ₃ ), 574 g
_{H2SO4 ,} 239g KCl, 1400g _H2O and 3756g
An acidic alum solution was prepared by mixing the "pre-reacted organics" (1.45% by weight of N).
These solutions were placed simultaneously in a 5 gallon autoclave to form a gel. The gel was stirred at 250 rpm for 30 minutes. Crystallization is
Completed within 20 hours at 160.0°C (320〓) with stirring at 90 rpm. The product was washed, dried and analyzed and found to be 115% ZSM-5 and SiO ₂ /
The Al ₂ O ₃ ratio was 73.8. When examined with a scanning electron microscope, the crystal size was 0.7×0.7×0.1μ to 0.4×
It was 0.3×0.1μ. Example 5 (Comparative Example) A silicate solution was prepared according to Example 1 by mixing Q brand sodium silicate, _H2O and Daxad27. 238g Al ₂ (SO ₄ ) ₃ ×
_H2O (17.2% _Al2O3 ) _{, 574g H2SO4} (100%),
Acidic alum solutions were prepared by mixing 136 g of LiCl, 535 g of H ₂ O, and 4618 g of pre-reacted organics (1.22 wt% N). These solutions were placed in a 18.9 (5 gallon) autoclave. The gel was stirred at 250 rpm for 30 minutes. Crystallization was completed within 19 hours. The product was washed, dried and analyzed and found to be 115% ZSM-5. and the silica/alumina ratio was 68.6. When examined with a scanning electron microscope, the crystal size was 0.5 × 0.3 × 1μ ~ 0.3 × 0.2 × 0.1
It was μ. Examples 4 and 5 show that when a cation with an ionic radius smaller than 1.4 is added, the crystal size is 1.
This shows that ZSM-5 smaller than μ can be obtained. Example 6 A silicate solution was prepared according to Example 1. 238
g of Al ₂ (SO ₄ ) ₃ × H ₂ O (17.2% Al ₂ O ₃ ), 574 g
_{H2SO4 ,} 3000g _H2O , 700g TMACl (50%)
An acidic alum solution was prepared by mixing and 1524 g of pre-reacted organic matter (1.22 wt% N). The TPA/TMA molar ratio in the solution was 0.41. These solutions were placed in a 5 gallon autoclave. Crystallization was carried out at 160.0°C (320°C) with stirring at 90 rpm. Crystallization was completed within 20 hours and the final product was found to contain 85% ZSM-5. According to a scanning electron microscope, the crystal size is 4 x 3
×2 μ to 2×1×1 μ. Example 7 A silicate solution was prepared according to Example 1. 238
g of Al ₂ (SO ₄ ) ₃ × H ₂ O (17.2% Al ₂ O ₃ ), 574 g
_{H2SO4 ,} 185g _H2O , 700g TMACl (50%)
An acidic alum solution was prepared by mixing 4618 g of "pre-reacted organic matter" (1.22 wt% N). The TPA/TMA molar ratio in the solution was 1.25. These solutions were placed in a 5 gallon autoclave. Crystallization was carried out at 160.0°C (320°C) with stirring at 90 rpm. Crystallization is 12
Completed within hours. The product was washed, dried and analyzed to be 115% ZSM-5. The crystal size was 13 x 10 when examined using a scanning electron microscope.
It was ×6μ to 2×2×1μ. Example 8 A silicate solution was prepared by mixing 41.3 Kg (90.9 lbs) Q brand sodium silicate, 120 g Daxad 27 and 20.2 Kg (44.6 lbs) _H2O . 1428g _Al2 ( _SO4 ) ₃ × _H2O
(17.2% Al ₂ O ₃ ), 3444 g H ₂ SO ₄ , 4200 g
An acidic alum solution was prepared by mixing TMACl (50%) and 35.9 Kg (79.0 lbs) of "pre-reacted organics" (1.58 wt% N).
The TPA/TMA molar ratio was 2.1. The solution,
It was placed in a 114 (30 gallon) autoclave containing 1180 g of _H2O . These solutions were introduced simultaneously through a mixing nozzle. The resulting gel was stirred at 90 rpm for 1 hour at room temperature. Crystallization was carried out at 160.0°C (320°C) with stirring at 90 rpm. Crystallization was completed within 21 hours. When this product was washed, dried and analyzed, it was found to be 90% ZSM-5 and the SiO ₂ /Al ₂ O ₃ ratio was 74.1. When examined with a scanning electron microscope, the crystal size was 20 x 12 x 5.
μ~4×3×2μ. As can be seen from Examples 6 to 8, when the TPA/TMA molar ratio was increased from 0.41 to 2.1, the maximum crystal size of the obtained crystals increased from 4 × 3 × 2 μ to 20 × 12 × 5 μ. Ta. Example 9 A silicate solution was prepared by mixing 90.9 pounds of Q brand sodium silicate, 118 grams of Daxad 27, and 52.6 pounds of _H2O . 238g _Al2 ( _SO4 ) ₃ × _H2O ( _17.2 % _Al2O3 ),
3444 g H ₂ SO ₄ , 7.2 Kg (15.9 lb) H ₂ O,
7200 g TMACl (50%) and 19.2 Kg (42.3 lbs) "pre-reacted organics" (N1.47 wt%)
An acidic alum solution was prepared from. Add the solution to 1180
The mixture was placed in a 30 gallon autoclave containing 114 g of H ₂ O. These solutions were simultaneously introduced into the autoclave through a mixing nozzle. The resulting gel was then stirred at 90 rpm for 1 hour at room temperature. Crystallization at 160.0℃ with stirring at 90rpm
I went with (320〓). Crystallization was completed within 17 hours. This product was washed, dried and examined.
It was 130% ZSM-5, and the SiO ₂ /Al ₂ O ₃ ratio was 270. Crystal size is 7 x 5 x 3μ ~ 2 x 1.5 x 1
It was μ. Example 10 A silicate solution was prepared according to Example 9. 2856
g of Al ₂ (SO ₄ ) ₃ × H ₂ O (17.2% Al ₂ O ₃ ), 2837 g
H ₂ SO ₄ , 7.4 Kg (16.4 lb) H ₂ O, 842 g
TMACl (50%) solution and 18.0Kg (39.6lb)
An acidic alum solution was prepared by mixing the "pre-reacted organics" (1.51% by weight of N).
The gel formation, mixing and crystallization steps were carried out exactly as in Example 9. Crystallization took 30 hours to complete. When the obtained product was washed, dried and analyzed, ZSM-5 with a SiO ₂ /Al ₂ O ₃ ratio of 37.3 was found.
It was 125%. Crystal size is 11×8×4μ~0.5
It was ×0.5×0.3μ. Example 11 A silicate solution was prepared by mixing 20.7 Kg (45.5 lbs) Q brand sodium silicate, 60 g Daxad 27 and 23.9 Kg (52.6 lbs) _H2O . 714g _Al2 ( _SO4 ) ₃ × _H2O
(17.2% Al ₂ O ₃ ), 1785 g H ₂ SO ₄ , 20.2 Kg (44.4 lb) H ₂ O, 8424 g TMACl (50%) solution and 17.9 Kg (39.5 lb) “pre-reacted organics” ( An acidic alum solution was prepared by mixing N (1.51% by weight). The gel formation, mixing and crystallization steps were all the same as in Example 9. To complete crystallization
It took 43 hours. The product was washed, dried and analyzed to be 85% ZSM-5, SiO ₂ /
The Al ₂ O ₃ ratio was 71.3. Crystal size is 20×8×
It was 4 μ to 0.7×0.5×0.2 μ. Example 12 A silicate solution was prepared according to Example 11. 357
g of Al ₂ (SO ₄ ) ₃ × H ₂ O (17.2% Al ₂ O ₃ ), 1962 g
H ₂ SO ₄ , 20.2 Kg (44.4 lb) H ₂ O, 8424 g
TMACl (50%) solution and 17.9Kg (39.5 lbs)
An acidic alum solution was prepared by mixing the "pre-reacted organics" (1.45% by weight of N).
The gel formation, mixing and crystallization steps were exactly the same as in Example 9. Crystallization was completed within 50 hours. The product was washed, dried and analyzed.
It was 110% ZSM-5, and the SiO ₂ /Al ₂ O ₃ ratio was 139.9. Crystal size is 25×8×4μ ~ 6×3×1
It was μ. Example 13 238g Al ₂ (SO ₄ ) ₃ ×H ₂ O (17.2% Al ₂ O ₃ ), 202
g H ₂ SO ₄ , 400 g NaOH, 1200 g TMACl
(50%) solution and 3682 g of "pre-reacted organic matter" (1.22 wt% N) to prepare an alum solution. The solution was placed in a 5 gallon autoclave and 2132 g of Hi-Sil (in the form of precipitated SiO ₂ ) was added to the solution. This mixture was crystallized at 160.0° C. (320°) at 90 rpm. Crystallization was completed within 114 hours. This product was washed, dried and analyzed and found to be 100% ZSM-5.
The SiO ₂ /Al ₂ O ₃ molar ratio was 65.2. The crystal size was 20×10×5μ to 8×6×4μ. Example 14 A silicate solution was prepared according to Example 1. 238
g of Al ₂ (SO ₄ ) ₃ × H ₂ O (17.2% Al ₂ O ₃ ), 574 g
H ₂ SO ₄ , 1200 g TMACl (50%) solution and 3480
An acidic alum solution was prepared by mixing g of _H2O . The two solutions were placed simultaneously in a 5 gallon autoclave to form a gel. After stirring the gel at room temperature for 30 minutes at 250 rpm, 1148 g of n-propylamine was added. The autoclave was closed again. Crystallization took 31 hours to complete at 160.0°C (320°C) with stirring at 90 rpm. The product was washed, dried and analyzed and found to be SiO ₂ /Al ₂ O ₃
ZSM-5 with a ratio of 62.8 was 80%. The sodium content of this product was 0.4, which was lower than that of the regular ZSM-5 product. The crystal size was 10×4×4 μ to 2×1×1 μ. Example 15 A silicate solution was prepared according to Example 9. 1428
g of Al ₂ (SO ₄ ) ₃ × H ₂ O (17.2% Al ₂ O ₃ ), 3444 g
H ₂ SO ₄ , 7200 g TMACl (50%) solution and 20.9
An acidic alum solution was prepared by mixing 46.1 pounds of _H2O . Add the solution to 114
(30 gallons) in an autoclave, Example 9
A homogeneous gel mixture was obtained by mixing in the same manner as above. After that, 3005 g of tri-n-propylamine and
2584 g of n-propyl bromide was added to the top of the gel. This mixture was crystallized at 160.0°C (320°C) with stirring at 90 rpm. Crystallization took 18.3 hours. The product was washed, dried and analyzed and found to be 105% ZSM-5 with a SiO ₂ /Al ₂ O ₃ molar ratio of 73.9. Crystal size is 15×12×6μ~1
It was ×0.7×0.5μ. Example 16 (Comparative Example) A silicate solution was prepared by mixing 41.3 Kg (90.9 lbs) of Q brand sodium silicate, 118 g of Daxad 27, and 23.9 Kg (52.6 lbs) of _H2O . 1430g Al ₂ (SO ₄ ) ₃ ×H ₂ O
(17.2% Al ₂ O ₃ ), 3440 g H ₂ SO ₄ , 1840 g
NaCl, 9.4Kg (20.8 lbs) 'pre-reacted
An acidic alum solution was prepared by mixing "TPABr solution" (1.43 wt% N) and 17.7 Kg (38.9 lbs) of _H2O . 1180g of the above two solutions
It was placed through a mixing nozzle into a 30 gallon autoclave containing _H2O . After the gel formed, 5840 g of NaCl was added to the gel. Close the autoclave and heat to 160.0℃ as soon as possible
(320〓). The stirring speed was 90 rpm. It took approximately 10 hours for crystallization to complete.
This product was washed, dried and analyzed.
It is 100% ZSM-5, and the silica/alumina ratio is
It was 66.2. Crystal size is small, 0.3×0.2μ
It was ~0.1~0.05μ. This example shows a typical manufacturing example of ZSM-5 and serves as the basis. Due to this
It can be seen that the addition of cations such as TMA, TEA, cesium and rubidium affects the crystal size.

Claims (1)

[Claims] 1. A crystalline aluminosilicate zeolite with a SiO ₂ /Al ₂ O ₃ molar ratio of 25 to 1000, a control index of 1 to 12, and a crystal size of at least 1 micron.
In the method for producing ZSM-5, the reaction mixture for producing the zeolite contains an alkyl ammonium cation, an alkali metal or alkaline earth metal cation source, and an ionic radius of 1.40 angstroms or more, together with an alumina source and a silica source. The method for producing crystalline aluminosilicate zeolite as described above, characterized in that another cation having a size that can enter the pores of the zeolite to be produced is present. 2. The production method according to claim 1, wherein the alkylammonium cation is tetrapropylammonium. 3 Cations with an ionic radius larger than 1.40 angstroms are tetramethylammonium,
The method according to claim 1, wherein the metal is selected from the group consisting of tetraethylammonium and cesium. 4 A cation with an ionic radius larger than 1.40 angstroms is tetramethylammonium,
3. The method of claim 2, wherein the metal is selected from the group consisting of tetraethylammonium and cesium. 5. The production method according to claim 1, wherein the alkali metal or alkaline earth metal cation is sodium. 6. The production method according to claim 2, wherein the alkali metal or alkaline earth metal cation is sodium. 7. The production method according to claim 3, wherein the alkali metal or alkaline earth metal cation is sodium. 8. The production method according to claim 4, wherein the alkali metal or alkaline earth metal cation is sodium.