JPS6229370B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel crystalline borosilicate. Related prior art can be found in US Patent Classifications 423-326, 252-458 and 260-668. Natural and synthetic zeolite-type materials have already been demonstrated in the past to have catalytic ability for many hydrocarbon processes. This zeolite-type material is a regular, porous crystalline aluminosilicate with a certain structure in which large and small cavities are interconnected by channels. The cavities and channels within this crystalline material are generally uniform in size to allow selective separation of hydrocarbons.
For this reason, in many cases these substances belong to molecular sieves and have been used in adsorption selection methods because they have some degree of catalytic activity. The catalytic activity of such materials is also influenced to some extent by the size of the molecules, which can presumably selectively pass through the crystal structure in contact with active catalytic sites within the ordered structure of these materials. receive. Generally, the term "molecular sieve" encompasses a wide variety of cation-containing materials, both natural and synthetic. These are generally characterized as crystalline aluminosilicates, although other crystalline materials are included within the broader definition. This crystalline aluminosilicate has a tetrahedral network structure in which both SiO ₄ and AlO ₄ sites are cross-linked by sharing oxygen atoms between silicon and aluminum atoms. The electron valence of the aluminum atom is balanced by using cations, such as alkali metals or alkaline earth metals. Many synthetic crystalline materials have been produced in the past, and crystalline aluminosilicates are the most common as described in the patent literature. Representative of such materials are Zeolite A (U.S. Pat. No. 2,882,243) and Zeolite X (U.S. Pat. No. 2,882,243).
2882244), Zeolite Y (US Patent No. 3130007)
Zeolite ZSM-5 (US Patent No. 3702886)
Zeolite ZSM-11 (US Patent No. 3709979)
Zeolite ZSM-12 (US Patent No. 3832449)
No.) and others. Related technology is the above-mentioned US Pat. No. 3,702,886, which describes crystalline aluminum silicate zeolite ZSM.
-5 and the method of manufacturing this substance. This patent is limited to zeolites in which oxides of aluminum or potassium are present in the crystal structure together with oxides of silicon or germanium. ZSM in which the zeolite is limited to crystalline alumino- or gallosilicate or germanate and has a specific X-ray diffraction pattern.
A specific ratio of the latter to the former reacts to produce -5. For the production of ZSM materials, sodium aluminate and a silicon-containing material are combined with sodium hydroxide and an organic base (e.g., tetrapropylammonium hydroxide or tetrapropylammonium bromide) under defined reaction conditions. A mixing system is utilized in which the materials are mixed to form the desired crystalline aminosilicate. U.S. Patent No. 3,941,871 has very little aluminum in its crystal structure and ZSM-
The authors claim and teach organosilicates with X-ray diffraction patterns similar to those of the No. 5 compositions. This patent is considered related art. Other related technologies include “zirconosilicate”
and “U.S. Patent No. 3,329,480 for titano-silicates.
No. 3329481 is included. However, the present invention relates to a synthetic, stable, new crystalline material characterized as a borosilicate identified as AMS-1B with a specific X-ray diffraction pattern. AMS claimed -
1B crystalline borosilicate is formed by reacting a boron salt with a silicon-containing material in a basic medium. The present invention has the following oxide composition: 0.9±0.2NiO:B ₂ O ₃ : YSiO ₂ :ZH ₂ O (here, Y is 4 to 500, and Z is 0
160) and the following X-ray diffraction pattern:

[Table] This is a crystalline borosilicate. Many members of the AMS-1B crystalline borosilicate family have a particular distinct crystalline structure. The X-ray diffraction patterns produced by such materials can reportedly be obtained using standard powder diffraction techniques. The X-ray diffractometer is AMR
Focusing monochromator (AMR focusing mono)
chrometer) and theta correction slit (theta)
This is a Philips device that uses C _u K radiation with a compensating slit. Note that the gap between the slits changes with the θ angle. The output from the diffractometer passes through a Canberra hardware/software package and is reported by strip charts and tabular printouts. The compensation slit and the camera wrapper cage are designed for peak/
On the other hand, the peak intensity decreases where the angle of θ is small (where d(Å) is high), and where the angle of θ is large (where d(Å) is low). , the peak intensity increases. All of the X-ray patterns reported here used the analytical method described above. Relative intensity was calculated as (100I/I ₀ ). where I ₀ is the intensity of the strongest recorded peak and I is the actual reading for a particular lattice spacing. To facilitate reporting, relative intensity is arbitrarily divided into the following values: I/I ₀ classification strength 10 or less VW 10-19 W 20-39 M 40-70 MS 70 or more VS 11 or this for AMS-1B crystalline borosilicate after firing at 1000〓 (535℃) A representative X-ray diffraction pattern showing superior lines with higher relative intensity is shown in Table 1.

Table: Strip chart recording of the calcined borosilicate reported in Table 1 above showed that it had the following X-ray diffraction lines:

【table】

[Table] This AMS-1B crystalline borosilicate is useful for catalytic cracking and hydrogen cracking methods. These include the isomerization of normal paraffins and naphthenes, the modification of certain feedstocks, the isomerization of aromatics especially polyalkyl-substituted aromatics (e.g. ortho-xylene), and the isomerization of aromatics such as toluene. It is also relatively effective in other petroleum refining processes such as disproportionation and hydrodealkylation to form mixtures of other valuable products (including benzene, xylenes and other higher methyl-substituted benzenes). It is believed to have catalytic ability. When AMS-1B catalyst borosilicate is used as a catalyst for the isomerization process, the desired isomer can be obtained with high selectivity. If the activity of such substances is stable at elevated temperatures or in the presence of other normal deactivating agents,
Crystalline materials belonging to this class become relatively valuable for high temperature operations involving active catalytic cracking or other cyclic types of processing. The cations found in the AMS-1B crystalline borosilicate can be replaced with a wide variety of other cations according to methods known in the art, as described above. Conventionally known ion exchange methods include U.S. Pat. No. 3,140,249, U.S. Pat.
Disclosed in numerous patents including No. 3140253. ion exchange with another substance to replace the catalytically active substance in or on the borosilicate structure;
Once impregnated or contacted, the material can be washed and then dried at temperatures within the range of about 150° to about 600°C (65° to 316°C). This item was then made for about 500 to about 1500 times at various times.
(260° to 816°C) in air or nitrogen or both.
Can be baked. Ion exchange within the cation positions of crystalline materials is generally relatively unimportant to the overall X-ray diffraction pattern produced by crystalline borosilicate materials. Although small changes occur at various intervals on the X-ray pattern, the overall pattern remains substantially the same. Small changes in the X-ray diffraction pattern can also be caused by processing differences in the production of borosilicate, which can be processed as shown in Table 1 or in the examples below. It falls within the generic genus of AMS-1B crystalline borosilicate defined by these X-ray diffraction patterns. The crystalline borosilicate of the present invention can be incorporated into a catalyst or adsorbent as a pure borosilicate, or it can be mixed with various binders or bases, depending on the intended process application. It's okay. In many cases, the crystalline borosilicate can be pelletized or extruded. The crystalline borosilicate can be used with active or inert materials, synthetic or natural zeolites, as well as inorganic or organic materials that may be useful for binding the borosilicate. Other known substances include:
Mixtures of silica, silica-alumina, alumina sols, clays (eg, bentonite or kaolin) or other binders well known in the art are included. The crystalline borosilicate also contains porous matrix materials such as silica-zirconia, silica-magnesia, silica-alumina, silica-thoria, silica-beryria, silica-titania, and even silica-alumina-thoria. It can also be intimately mixed with many other materials well known in the art, including, but not limited to, ternary compositions. The content of this crystalline borosilicate can vary from a few percent to 100 percent of the total final product. AMS-1B crystalline borosilicate can generally be made by mixing oxides of boron, sodium or any other alkali metal, and silicon with a tetraalkylammonium compound in an aqueous medium. The molar ratios of the various reactants can vary widely to produce the AMS-1B crystalline borosilicate. The reactant molar ratios of various oxides for making borosilicates are shown in Table 2. Table 2 Molar ratio SiO ₂ /B ₂ O ₃ 5-600 (or more) R ₄ N ⁺ /(R ₄ N ⁺ +Na ⁺ ) 0.1-1 OH ^- /SiO ₂ 0.01-10 Here, R is alkyl and preferably propyl. The above amounts can vary in concentration in the aqueous medium. It is generally preferred that the molar ratio of water to hydroxyl ions varies from about 10 to about 500 or more. By simply controlling the amount of boron (as B ₂ O ₃ ) in the reaction mixture, the SiO ₂ /B ₂ O ₃ molar ratio in the final product can be adjusted to approximately 40
It is possible to vary within a range from about 500 to about 500 (or more). In certain conversion methods, the molar ratio of SiO ₂ /Al ₂ O ₃ may be changed to remove alumina from the borosilicate crystal structure due to its negative effects.
It can also be 2000-3000 or more. This ratio is
It is generally only limited by the availability of unreliable raw materials for aluminum. The SiO ₂ /B ₂ O ₃ molar ratio of the final crystalline product can vary from about 4 to about 500 (or more). Those made in the laboratory under the general conditions described herein have a SiO ₂ /B ₂ O ₃ molar ratio of
Starting from 40th place (or lower). Those with low molar ratios can also be produced using manufacturing methods. Based on the known properties of mordenite and ferrierite aluminosilicate, the crystalline borosilicate of the present invention has approximately 4.5 BO ₄ tetrahedra per unit cell at a SiO ₂ /B ₂ O ₃ molar ratio of around 80. will have. In view of this, a single BO ₄
It is thought that the SiO ₂ /B ₂ O ₃ ratio is around 500. If the ratio is larger than this, it is assumed that there are a large number of unit cells, and in this case, it does not contain BO ₄ tetrahedrons, and the resulting crystalline structure is not considered to be a borosilicate. There is no limit to the molar ratio of SiO ₂ /B ₂ O ₃ at which the crystalline material ceases to be a borosilicate. _SiO2 /
At high values of B ₂ O ₃ (above 1000), the influence of the BO ₄ tetrahedra in the crystalline structure will be somewhat reduced and the crystalline material will no longer be called a borosilicate. Based on the above knowledge and under appropriately controlled conditions, the AMS-1B crystalline borosilicate of the present invention will be made. Typical reaction conditions include heating the reactants to a temperature of about 90 to about 250°C for a period of several hours to several weeks. The preferred temperature range is
The temperature is about 150 to about 180°C during the time required to make AMS-1B crystalline borosilicate. Particularly preferred conditions are temperatures of approximately 165°C for a period of about 7 days. The material created in this way can be prepared using known methods.
For example, it is separated and collected by filtration. This material can be gently dried at any temperature for several hours to several days to form a dry cake. This dry cake can then itself be ground into a powder or small particles and then extruded, pelletized or otherwise shaped into a suitable shape depending on the intended use. Typically, after gentle drying, the material contains tetraalkylammonium ions in a solid mass and requires subsequent activation or calcination. Typical high temperature firing conditions are about 800 to about 1600
〓 (426° to about 871°C) (or higher). Extreme calcination temperatures have been found to be detrimental to the crystal structure and may destroy it altogether. To remove the tetraalkylammonium cation from the initial crystalline material,
Generally, temperatures above about 1700㎓ (927℃) are not required. When using AMS-1B crystalline borosilicate as a hydrocracking catalyst, using known molar ratios of hydrocarbon to hydrogen and varying pressures from several to thousands of pounds per square inch (or more), approximately 500 The hydrocracking feedstock can be passed over the catalyst at a temperature of from about 850° C. to about 850° C. (454° C.). Liquid hourly space velocity and other process factors can be varied according to techniques known in the art. When using this borosilicate in the fluid catalytic cracking method, known operating conditions are used, including:
This includes having a reaction zone temperature of about 500 to about 1200° (about 260° to 649°C) and a regeneration zone temperature of about 800 to about 1300° (426 to 704°C). Contact times, feedstocks and other process conditions are known in the art. Certain AMS-1B crystalline borosilicates are also suitable as reforming catalysts and have a
(260 to 566°C) (or higher), pressures from several to 300 to 1000 psig (21 to 70 Kg/cm ² ), and hydraulic space velocities and hydrocarbons to hydrogen well known in the reforming art. well-known reforming conditions including molar ratios of 0 to 1, with appropriate hydrocracking components. The compositions of the invention are also suitable for isomerization and disproportionation of hydrocarbons. This product is particularly useful for isomerizing xylene in the liquid phase or gas phase, particularly for isomerizing mixed xylenes to mainly para-xylene. The conditions for isomerization include about 200 to about
Temperature of 1000〓(93゜~538℃), about 0 to about 20
hydrogen to hydrocarbon molar ratio of , liquid hourly space velocity ranging from about 0.01 to about 90. The catalytically active metal loaded onto the AMS-1B crystalline borosilicate is selected from metals well known in the art. Nickel appears to be particularly suitable for aromatic isomerization. The AMS-1B crystalline borosilicate of the present invention can also be used as an adsorbent for selectively adsorbing specific isomers or hydrocarbons (liquid or gas). The following examples illustrate specific embodiments of the invention and are not intended to limit the scope of the claims. Reference Example 1 AMS-1B crystalline borosilicate was prepared by dissolving 0.25 g of H ₃ BO ₃ and 1.6 g of NaOH in 60 g of distilled water (H ₂ O). Then, 9.4 g of tetra-n-propylammonium bromide (TPA Br) was added and then dissolved. Finally, 12.7 g of Ludox-AS (30% solids) was added with vigorous stirring. This solution was placed in a reaction bomb and sealed. The cylinder was placed in an oven at 165°C and kept there for 7 days. After 7 days, the cylinder was opened and the contents filtered. Wash the recovered crystalline material with plenty of water and place it under forced flow.
Dry in an oven at 165°C. When this dry substance was identified by X-ray diffraction, it was confirmed that it was a crystalline substance having a typical AMS-1B pattern with 100% crystallinity. The yield was approximately 2g.
The explanation of "Ludox-AS" is as follows. Ludox is a colloidal sol of polymeric silicic acid stabilized in the sodium form.
HS” and “Ludox AS” stabilized in the ammonium form. These colloidal sols are available with a solids content of 30% or 40%.
The one used in this example had a solid content of 30% and is sometimes labeled as "Ludox AS-30." EXAMPLE In this example, the AMS-1B crystalline borosilicate of Reference Example 1 was used to prepare a catalyst with isomerization activity. The material of Reference Example 1 was calcined in air at a temperature of 1100°C (535°C) for 4 hours to remove the organic base. This =
Boil 200ml of roasted shives at 190℃ (88℃) for 2 hours.
It was exchanged once with a solution containing 20 g NH ₄ NO ₃ in H ₂ O and then a second time with a solution containing 20 g NH ₄ OAc in 200 ml H ₂ O. After drying the replaced borosilicate, it was calcined in air by heating at 900°C (482°C) for 4 hours;
100ml of calcined material cooled to 100°C (38°C)
The mixture was exchanged with a 5% Ni(NO ₃ ) ₂ ·6H ₂ O solution at 190° C. for 2 hours. The sieve was washed with _H2O to completely rinse off the Ni ⁺⁺ . The sieve was dried and calcined again as described above. Approximately 2g of borosilicate to 16.9g
Dispersed in PHF-Al ₂ O ₃ hydrosol (8.9% solids) and thoroughly mixed. “PHF—Al ₂ O ₃ ” refers to a type of catalytically active alumina that is produced by amalgamating aluminum metal with a small amount of mercury and then adding water with a slightly sour taste. It can be made by converting substances into alumina sol. This is described in detail in US Pat. No. 22,196 (issued October 6, 1942). Once 1 ml of distilled water and 1 ml of concentrated NH ₄ OH were mixed, this mixture was added to the slurry with vigorous stirring. Put the AMS-1B-Al ₂ O ₃ mixture into the drying oven.
It was dried at 165°C for 4 hours. The dried material was calcined again using the method described above. 〓Crush the calcined catalyst into 30-50 meshes and add 5% [Ni (NO ₃ )] ₂ .
Impregnated with 2 ml of 6H ₂ O. Dry this catalyst again and
It was activated by the second firing. The calcined catalyst contains 65 weight percent borosilicate, 35 weight percent amorphous alumina, and approximately 0.5 weight percent nickel based on total solids. 1 g of active catalyst of this size was placed in a microreactor and sulfidized with H ₂ S for 20 minutes at room temperature. The catalyst was then placed under H ₂ pressure and
(316°C). After 1 hour, the raw material was passed through the microreactor under the following conditions. Temperature 800〓 (427℃) Pressure 150psig (10.5Kg/cm ² ) WHSV 6.28hrs ^-1 H/HC molar ratio 7 “WHSV” is an abbreviation for weight per hour space velocity, and the rate per unit weight of catalyst per hour. represents the weight of hydrocarbons. The liquid feedstock and effluents for this run are shown below. Due to equipment limitations of the screening unit, only the analysis of the liquid effluent was performed and reported. Light products through this catalyst were low from gas chromatographic analysis performed on the off-gas stream from the unit. It has been found that the volume of off-gas does not substantially reduce the overall yield of liquid passed through the catalyst.

[Table] Reference Example 2 A borosilicate similar to that prepared in Reference Example 1 was prepared by approx.
It was baked at 1100°C (593°C) and then analyzed to determine its total composition. The results are shown below. Component SiO ₂ % by weight 94.90 B ₂ O ₃ 1.06 Na ₂ O 0.97 Al ₂ O ₃ 0.057 Fe ₂ O ₃ 0.029 Volatile content ^* 2.984 Total 100.00 Molar ratio SiO ₂ /B ₂ O ₃ 104.5 Na ₂ O / B ₂ O ₃ 1.0 SiO ₂ /Al ₂ O ₃ 2824.4 SiO ₂ /Fe ₂ O ₃ 8787.0 SiO ₂ / (Al ₂ O ₃ + Fe ₂ O ₃ ) 2146.2 * Value assuming the total is 100% Same as described in Reference Example 1 In this way, he created another borosilicate. However, the H ₃ BO ₄ content ratio was changed so that the SiO ₃ /B ₂ O ₃ molar ratio before calcination or exchange of the borosilicate was 50 to 160 (or more). SiO ₂ / after exchange with a suitable catalyst material
The molar ratio _{of B2O3} was generally increased to values between 80 and 100. The molar ratio of SiO ₂ /B ₂ O ₃ in the initial borosilicate was approximately 50. Reference Example 3 Three borosilicate materials were prepared in the same manner as described in Reference Example 1. 1000〓(535
After sintering at 10°C, boron and silicon analyzes were performed as shown below.

[Table] After exchange with ammonium acetate, the borosilicate was calcined at 535°C. The results are shown below. Borosilicate SiO ₂ /B ₂ O ₃ molar ratio A 75.1 B 71.2 C 64.2 These were calcined at 1000㎓ (535°C) and powder X-ray diffraction analysis was performed on the above borosilicate sample before ion exchange. Summer. Reported patterns have a relative intensity (I/I ₀ ) of 10 or more. Third
The table shows the lattice spacings shown from strips of two cases of borosilicate before ion exchange and calcined to 1000°C (535°C). Table 3 (Borosilicate A) Lattice spacing d (Å) Relative intensity (I/I ₀ ) 11.34 38 10.13 30 6.01 14 4.35 11 4.26 14 3.84 100 3.72 52 3.65 31 3.44 14 3.33 16 3.04 16 2 .97 22 2.48 11 1.99 20 1.66 12 Table 4 (Borosilicate B) Lattice spacing d (Å) Relative intensity (I/I ₀ ) 11.35 41 10.14 31 6.02 15 4.26 15 3.84 100 3.72 52 3.65 33 3.44 13 3.32 15 3 .04 16 2. 97 22 2.48 11 1.99 20 1.66 12 Table 5 (Borosilicate C) Lattice spacing d (Å) Relative intensity (I/I ₀ ) 11.40 33 10.17 29 6.03 13 5.62 10 4.27 14 3.84 100 3.73 51 3.6 5 30 3.44 13 3.32 16 3.05 16 2.98 21 1.99 19 1.66 12

Claims (1)

[Claims] 1 Composition of the following oxide: 0.9±0.2NiO: B ₂ O ₃ : YSiO ₂ : ZH ₂ O (here, Y is 4 to 500, and Z
is from 0 to 160) and exhibits the following X-ray diffraction pattern: 2. The crystalline borosilicate according to claim 1, wherein Y has a value in the range of 20 to 500. 3. The first claim in which Z is 0 to 40
The crystalline borosilicate described in Section.