Molecular sieve boron ITQ-21 and synthesis and application thereof

Abstract

The invention provides a novel synthetic crystal molecular sieve material which is named as boron ITQ-21. The boron ITQ-21 may be synthesized using a N, N-diethyl-5, 8-dimethyl-2-azoniumbicyclo [3.2. 2] nonane cation as a structure directing agent, and a method for synthesizing the boron ITQ-21 using the N, N-diethyl-5, 8-dimethyl-2-azoniumbicyclo [3.2. 2] nonane cation. The boron ITQ-21 may be used in organic compound conversion reactions and / or adsorption processes.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 578,493, filed August 24, 2023, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] This disclosure relates to a novel synthetic crystalline germanium silicate molecular sieve (named Boron ITQ-21) and its synthesis. Background Technology

[0004] Molecular sieves are a class of commercially important materials that exhibit unique X-ray diffraction (XRD) properties. picture The case demonstrates a unique crystal structure with a defined pore structure. Molecular sieves also possess specific chemical compositions. The crystal structure defines cavities and pores, which are characteristics of a particular type of molecular sieve. Providing new molecular sieves that offer differences in both crystal structure and composition can lead to unique catalysts or adsorption / separation materials. Modifying the crystal structure is always challenging, but success can be rewarded with new catalysts for organic compound conversion reactions. US Patent No. 6,849,248 discloses the preparation of ITQ-21. However, it does not disclose boron ITQ-21. Summary of the Invention

[0005] According to this disclosure, a novel crystalline germanium silicate molecular sieve, named boron ITQ-21, was synthesized using N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclo[3.2.2]nonane cation as a structure-directing agent (SDA). This synthesis has been found to successfully provide a boron-containing molecular sieve with the ITQ-21 crystal structure.

[0006] On the other hand, a method for synthesizing the molecular sieve described herein is provided, the method comprising (1) preparing a reaction mixture comprising: (a) a silicon source; (b) a germanium source; (c) a boron source; (d) a structure directing agent comprising an N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclic [3.2.2]nonane cation (Q); (e) a fluoride ion source; and (f) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of a boron molecular sieve. The boron-containing ITQ-21 molecular sieve is then treated to remove SDA, which can be achieved by calcination or by ozone treatment.

[0007] In another aspect, a method is provided for converting a feedstock containing an organic compound into a conversion product, the method comprising contacting the feedstock with a catalyst containing the boron ITQ-21 molecular sieve described herein under organic compound conversion conditions.

[0008] Among other factors, the method of this invention allows for the preparation of boron ITQ-21 molecular sieves. This novel molecular sieve, prepared by the method of this invention, can provide unique properties as a catalyst in organic compound conversion reactions. This molecular sieve also has significant value as an adsorption / separation material. Appendix picture illustrate

[0009] picture X-ray diffraction of the calcined form of the boron-germanium silicate ITQ-21 molecular sieve of the present invention. picture case. Detailed Implementation

[0010] definition

[0011] The term "skeleton type" is found in Ch. Baerlocher, LB McCusker, and D. Holson's "Zeolite Skeleton Types". picture The meaning described in the Elsevier Collection (Sixth Revised Edition, 2007).

[0012] The term "as-synthesized" is used here to refer to the molecular sieve in its crystallized form, but before the removal of the structure-directing agent.

[0013] The term "anhydrous" is used here to refer to molecular sieves that are essentially free of both physically and chemically adsorbed water.

[0014] As used herein, the numbering scheme for the periodic table families is disclosed in Chem. Eng. News 1985, 63(5), 26-27.

[0015] Synthesis of boron molecular sieves

[0016] The boron ITQ-21 molecular sieve of the present invention can be synthesized by: (1) preparing a reaction mixture comprising: (a) a silicon source; (b) a germanium source; (c) a boron source; (d) a structure directing agent comprising an N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclic [3.2.2]nonane cation (Q); (e) a fluoride ion source; and (f) water; and then (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the boron ITQ-21 molecular sieve. If aluminum is present, it is present only in small amounts. Therefore, the framework contains a large amount of boron.

[0017] In one embodiment, the silicon source may comprise an FAU framework-type zeolite. In another embodiment, the silicon source is aluminum-free.

[0018] The reaction mixture may have a composition (in molar ratio) within the range listed in Table 1:

[0019] Table 1

[0020]

[0021] Wherein Q contains the N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclic [3.2.2]nonane cation. In one embodiment, the molar ratio of (SiO2+GeO2) / B2O3 is in the range of 15 to 20.

[0022] The silicon source may comprise FAU framework-type zeolites. FAU framework-type zeolites can be ammonium-type or hydrogen-type zeolites and are the silica source used for the reaction. FAU zeolites will typically have a SiO2 / Al2O3 molar ratio of at least 300 or greater. Examples of FAU framework-type zeolites include zeolite Y (e.g., CBV720, CBV760, CBV780, HSZ-HUA385, and HSZ-HUA390). Zeolite Y may have a SiO2 / Al2O3 molar ratio of 300 to 500. FAU framework-type zeolites may comprise two or more zeolites. The two or more zeolites may be Y zeolites with different silica to alumina molar ratios. FAU framework-type zeolites may be the sole or primary source of silicon. In some respects, a separate silicon source may be added. Separate silicon sources include colloidal silica, fumed silica, precipitated silica, alkali metal silicates, and tetraalkyl orthosilicates. Aluminum-free silicon sources may be very useful. In one implementation, the silicon source does not contain Al.

[0023] Suitable sources of germanium include germanium oxide and germanium alkoxides (e.g., ethoxy germanium, isopropoxy germanium).

[0024] Silicon and germanium can be present in the reaction mixture at a SiO2 / GeO2 molar ratio of 4 to 12 (e.g., 6 to 10).

[0025] Suitable sources of boron may include boric acid (which is preferred).

[0026] Suitable sources of fluoride ions include hydrogen fluoride, ammonium fluoride, and ammonium hydrogen fluoride.

[0027] The structure-directing agent is an N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclic [3.2.2]nonane cation with the following structure:

[0028]

[0029] X is an anion that does not impair the formation of boron ITQ-21. Representative anions include halogens, such as fluorides, chlorides, bromides, and iodides, hydroxyl, acetate, sulfate, tetrafluoroborate, carboxylates, etc. Hydroxide is the most preferred anion.

[0030] Suitable sources of Q are hydroxides, chlorides, bromides, and / or other salts of the compound.

[0031] The reaction mixture may have a Q / F molar ratio in the range of 0.80 to 1.20 (e.g., 0.85 to 1.15, 0.90 to 1.10, 0.95 to 1.05, or 1 to 1).

[0032] The reaction mixture may contain seed crystals of a molecular sieve material, such as previously synthesized boron ITQ-21, in an amount of 0.01 to 10,000 ppm by weight of the reaction mixture (e.g., 100 to 5,000 ppm by weight). Adding seed crystals is advantageous in reducing the time required for complete crystallization. Furthermore, adding seed crystals can increase the purity of the obtained product by promoting the nucleation of boron ITQ-21 and / or forming more than any undesirable phase. While boron ITQ-21 seed crystals are preferred, in one embodiment, seed crystals of a previously synthesized ITQ-21 zeolite without boron may be used.

[0033] It should be noted that the components of the reaction mixture may be supplied from more than one source. Alternatively, two or more reaction components may be supplied from a single source. The reaction mixture may be prepared in a batch or continuous manner.

[0034] Crystallization and post-synthesis treatment

[0035] The crystallization of boron ITQ-21 molecular sieves from the above reaction mixture can be carried out in a suitable reactor vessel (e.g., a polypropylene tank or a Teflon-lined or stainless steel pressure vessel) at a temperature of 100°C to 200°C (e.g., 150°C to 175°C) under static, tumbling, or stirring conditions for a time sufficient for crystallization to occur at the temperature used (e.g., 1 to 14 days, or 2 to 10 days). Hydrothermal crystallization is typically carried out under pressure, such as in a pressure vessel, and preferably under autogenous pressure.

[0036] Once the molecular sieve crystals are formed, the solid product can be recovered from the reaction mixture using standard mechanical separation techniques such as centrifugation or filtration. The recovered crystals are washed with water and then dried to obtain the synthesized molecular sieve crystals as is. The drying step can be carried out at elevated temperatures (e.g., 75°C to 150°C) for several hours (e.g., about 4 to 24 hours). The drying step can be carried out under vacuum or atmospheric pressure.

[0037] As a result of the crystallization process, the recovered crystalline molecular sieve product contains at least a portion of the structure-directing agent used in the synthesis within its pore structure.

[0038] The synthesized molecular sieve can also be treated to remove some or all of the structure-directing agent used in its synthesis. This can be conveniently achieved by heat treatment (i.e., calcination), wherein the synthesized material is heated at a temperature of at least about 370°C for at least 1 minute and typically not more than 20 hours. Although heat treatment can be performed at pressures below atmospheric pressure, atmospheric pressure is preferred for convenience. Heat treatment can be performed at a temperature of up to about 925°C. Heat treatment can be performed in an atmosphere selected from air, nitrogen, or mixtures thereof. For example, heat treatment can be performed in air at a temperature of 400°C to 600°C for a period of 3 to 8 hours. Alternatively, the structure-directing agent Q can be removed by ozone treatment. Ozone treatment may include heating the synthesized molecular sieve in the presence of ozone, which can be performed at a temperature of 50°C to 350°C (e.g., 100°C to 300°C, or 125°C to 250°C).

[0039] Characterization of molecular sieves

[0040] In its synthesized, original and anhydrous forms, the boron-containing molecular sieve ITQ-21 can have a chemical composition including the following molar relationships described in Table 2:

[0041] Table 2

[0042]

[0043] Q contains the N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclic [3.2.2]nonane cation.

[0044] Therefore, the composition can be considered to contain the molar relationship of B2O3∶(n)(SiO2), wherein in one embodiment n≥10, in another embodiment n≥15, and in one embodiment n ranges from about 15 to 20.

[0045] Boron molecular sieve ITQ-21 exhibits powder X-ray diffraction (XRD) properties. picture The case, picture The molecular sieve, in its original form after synthesis, must include at least the peaks listed in Table 3 below. In the calcined form of the molecular sieve, XRD... picture Case (such as) picture (As shown) It should include at least the peaks listed in Table 4 below.

[0046] Table 3

[0047] Characteristic XRD peaks of the original boron ITQ-21 after synthesis

[0048]

[0049] Table 4

[0050] Characteristic XRD peaks of calcined boron ITQ-21

[0051]

[0052] These diffractions were obtained using a Philips X-Pert diffractometer equipped with a graphite monochromator and an autodivergent slit, and using Kα radiation from copper. picture Diffraction data were recorded using 2θ-step scans of 0.01° (where θ is the Bragg angle), with a counting time of 10 seconds per step. The interplanar spacing d was calculated in Å, and the relative intensity of the lines was calculated as a percentage relative to the most intense peak, and was designated as very strong (vs) = 80–100, strong (s) = 60–80, moderate (m) = 40–60, weak (w) = 20–40, or very weak (vw) = 0–20.

[0053] diffraction picture The minute variations in the sample may originate from changes in the molar ratio of the framework material due to variations in the lattice constant. Furthermore, disordered materials and / or sufficiently small crystals will affect the shape and intensity of the peaks, resulting in significant peak broadening. Diffraction picture The minute changes in the case could also be caused by variations in the organic compounds used in the preparation. Calcination can also lead to changes in XRD. picture The case exhibits minute shifts. Despite these minute perturbations, the fundamental crystal lattice structure remains unchanged.

[0054] Industrial applicability

[0055] Boron-based molecular sieve ITQ-21 (in which some or all of the structure-directing agents are removed) can be used as an adsorbent or as a catalyst to catalyze various organic compound conversion processes. It is particularly suitable for use in reforming processes.

[0056] Catalytic reforming is one of the fundamental petroleum refining processes used to upgrade light hydrocarbon feedstocks (commonly known as naphtha feedstocks). Products of catalytic reforming can include high-octane gasoline suitable for use as automotive fuel, aromatic compounds (such as benzene, toluene, xylene, and ethylbenzene), and / or hydrogen. Reactions typically involved in catalytic reforming include the dehydrogenation, cyclization, isomerization, and dehydrogenation of hydrocarbons in the naphtha range, where the dehydrogenation, cyclization, and dehydrogenation of linear and slightly branched alkanes, as well as the dehydrogenation of cycloalkanes, results in the formation of aromatic compounds. Due to the low value of the resulting light hydrocarbon products, dealkylation and hydrocracking are generally undesirable.

[0057] Boron ITQ-21 catalysts used in reforming reactions typically include a Group VIII metal, such as platinum or palladium, or a Group VIII metal plus a second catalytic metal that acts as a promoter. Examples of useful promoter metals include rhenium, tin, tungsten, germanium, cobalt, nickel, rhodium, ruthenium, iridium, or combinations thereof. One or more catalytic metals may be dispersed on a support such as alumina, silica, or silica-alumina.

[0058] The boron ITQ-21 reforming catalyst can be used in a fixed bed within the reaction zone in the form of pellets, granules, pellets, fragments, or various special shapes, and the feed can be in liquid, vapor, or mixed phase and flow upward, downward, or radially. Alternatively, the reforming catalyst can be used in a moving bed or fluidized solids process, where the feed is passed upward through a turbulent bed of finely granulated catalyst. However, a fixed bed system or a dense-phase moving bed system is preferred due to less catalyst attrition and other operational advantages. In a fixed bed system, the feed is preheated (by any suitable heating method) to the desired reaction temperature and then introduced into the reaction zone containing the catalyst in the fixed bed. This reaction zone can be one or more separate reactors with suitable means of maintaining the desired temperature at the reactor inlet. Temperature must be maintained because reforming reactions are typically endothermic.

[0059] Actual reforming conditions typically depend at least in part on the feed used, whether it is highly aromatic, paraffinic, or cycloalkyl, and on the desired octane number and desired hydrogen yield of the product.

[0060] Example

[0061] The following illustrative examples are intended to be non-limiting.

[0062] Example 1

[0063] Synthesis of N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclic [3.2.2]nonane cation

[0064] A three-necked, 5-liter flask with a feeding funnel equipped with a balance arm was set up. A diaphragm was placed over the funnel. Nitrogen gas was passed through the system. An in-situ reagent was first developed by placing 104.55 g of diisopropylamine in 1859 mL of tetrahydrofuran (THF), followed by the slow addition of 401.7 mL of n-butyllithium (2.5 M in hexane) while maintaining the temperature close to -70 °C. The n-butyllithium was loaded into the feeding funnel using a sheath. The addition to THF took approximately 1.25 hours, after which the resulting mixture was stirred for another hour. 104.53 g of 3-methyl-2-cyclohexen-1-one was added dropwise in 1117 mL of THF over a period of 0.75 hours. Finally, 161.73 g of methacrylate was added over a period of 0.25 hours. The reaction was gradually heated to room temperature and its progress was monitored by TLC. The reaction appeared to continue overnight.

[0065] Product recovery begins by adding 1N HCl until the solution becomes acidic. The reaction product is transferred to a separatory funnel, and the aqueous phase is recovered for subsequent treatment with dichloromethane (2 × 250 ml). The combined organic phases are dried over sodium sulfate, and the solvent is removed. The residue is dissolved in ether to remove any small amount of viscous material. The ether is removed, and the resulting oil is distilled; a Vigreaux column (30 cm) is set and run at 2–4 mmHg. Most of the product elutes between 123–137 °C.

[0066] The product was reduced using lithium aluminum hydride. Reduction yielded a diol, 1-methyl-2-methanol-7-hydroxybicyclo[2.2.2]octane. The side methanol group was tosylated by reacting p-toluenesulfonyl chloride (96.92 g) with the diol (85.68 g) in anhydrous pyridine (500 ml). The p-toluenesulfonyl chloride was added to the other two components under nitrogen using a powder feeding funnel while the reaction was cooled to -5 °C. The addition was carried out over 0.75 hours, and the reaction mixture was heated to room temperature and allowed to react overnight. 500 ml of dichloromethane was added, and the resulting mixture was transferred to a separatory funnel and washed with water (2 × 250 ml). The product was dried over sodium sulfate, filtered, and removed to give 150 g of oil.

[0067] The product was purified by column chromatography. 1 kg of silica gel (230-400 mesh) was suspended in hexane, and the oil was loaded onto the top of 50 mL of dichloromethane. Elution was performed using 25 / 75 ethyl acetate (ETOAC); hexane, and the fractions were monitored by TLC. 83 g of product was collected. Toluenesulfonate was then reduced using LAH (as described above) to give 1,2-dimethyl-7-hydroxybicyclo[2.2.2]octane. Next, the alcohol was reoxidized to a ketone. 37.84 g of alcohol was reacted in a three-necked, 2 L flask as follows: 34.60 g of oxaloyl chloride and 604 mL of dichloromethane were loaded and covered under nitrogen. Using a feeding funnel with a side arm, 46 g of anhydrous dimethyl sulfoxide (DMSO) was added to 122.7 mL of dichloromethane. The bath was cooled to -60 °C using a dry ice / acetone bath, and the addition took 0.5 hours. The alcohol was added to 53.4 ml of dichloromethane at this temperature, and then stirred for another 0.5 hours. Then 126.65 g of triethylamine was placed in a dropping funnel and added over 0.25 hours. All additions produced an exothermic response, so cooling continued. The reaction mixture was slowly heated to room temperature and allowed to proceed overnight.

[0068] The post-treatment of the reaction product began with the addition of 500 ml of water. The separated aqueous phase was then extracted with dichloromethane (2 × 250 ml). The combined organic phases were then dried over magnesium sulfate and removed. The resulting oil was ground with ether to separate a small amount of insoluble material. The ether was removed to give 37 g of product.

[0069] Place 37 g of the ketone and 240 ml of 96% formic acid into a 1 L round-bottom flask connected to a feeding funnel. Stir the components using a magnetic stir bar. Add 125 ml of formic acid along with 43 g of hydroxylamine-O-sulfonic acid dissolved and suspended therein to the funnel. The addition is carried out over 20 minutes with stirring. The solution darkens. Replace the feeding funnel with a reflux condenser and reflux the reaction mixture for 15–20 hours under TLC sampling observation.

[0070] Carefully pour the mixture into 2 kg of ice. After cooling in the ice, slowly adjust the pH of the mixture to 12 by adding 50% NaOH. Perform three extractions using 500 cc of dichloromethane. Dry the extracts on sodium sulfate. After drying, remove the solvent, leaving approximately 45 grams of black oil.

[0071] The oil was dissolved in a minimal amount of chloroform and packed into a column (750 g of 230-400 mesh silica gel, already slurried in chloroform). The process was eluted using chloroform containing 2% by volume methanol. The eluted fractions were tracked by TLC (fraction 7-21 gives the same product). Similar fractions were combined and the eluting solvent was removed to give approximately 30 g of lactam.

[0072] 25 g of the lactam was used in the reduction step. A 2 L three-necked round-bottom flask was used, with nitrogen introduced into the system and evacuated through a reflux condenser and into a bubbler. The system had a feeding funnel. 460 mL of anhydrous ether was added to the flask. 18 g of lithium aluminum hydride was also carefully introduced into the flask. Some gas was produced. The lactam was dissolved in 230 mL of anhydrous dichloromethane. After cooling the flask in an acetone / dry ice bath, the lactam was added dropwise. The reaction is exothermic, so more ice needs to be added periodically as the temperature rises. The reduction could be tracked by changes in TLC data (monitored by iodine and eluted on silica gel with 98 / 2 chloroform / methanol). The reaction was allowed to proceed overnight to room temperature.

[0073] Slowly add 18 g of water, resulting in the expected exothermic gas production. Remove the ether and replace its volume with dichloromethane. Add 18 g of 15% NaOH solution, followed by 55 g of water. Filter off the formed solid, wash with additional dichloromethane, and combine with the organic distillate and dry on sodium sulfate (Note: Do not allow the NaOH solution to contact with dichloromethane overnight). Remove the solvent to recover approximately 15 g of the oil / solid mixture. This is crude amine.

[0074] The quaternization of 10 g of the amine was carried out as follows: The amine, 10 g of KHCO3, 65 ml of methanol, and finally 30 g of iodoethane were added to a 250 ml flask equipped with a stir bar and a reflux condenser. The mixture was refluxed and maintained in this state for 48 hours. After cooling, the solvent was removed. The solid was treated with chloroform. The chloroform-soluble fraction was then removed to obtain another solid, which was recrystallized from minimal amounts of hot acetone and methanol. Recrystallization at cold yielded three separate batches of product, totaling 11 g of salt. The melting points of these batches were all in the range of 252–256 °C.

[0075] The salt was converted to its hydroxide form by ion exchange on BioRad AG1-X8 resin.

[0076] Example 2

[0077] Synthesis of ITQ-21 Boron

[0078] 0.32 g of GeO2 and 0.085 g of boric acid were dissolved in 11.25 g of N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclo[3.2.2]nonane hydroxide solution, the concentration of which was 1.48 mol / kg. In the resulting solution, 6.30 g of tetraethyl orthosilicate was hydrolyzed with stirring until all the ethanol formed during hydrolysis evaporated. Then, 0.69 g of hydrofluoric acid solution (48.1% HF by weight) was added and evaporation continued.

[0079] The gel was heated at 160°C for 5 days with stirring in a steel pressure vessel with an internal Teflon lining. The solid obtained after filtration, washing with distilled water, and drying at 100°C was Boron ITQ-21. It is shown in the diffraction peak list in Table 3.

[0080] Example 3

[0081] Although boron ITQ-21 can be calcined, it is preferable to first treat the zeolite with ozone at 150°C to remove SDA guest molecules. Additionally, it has been found that most SDA can be removed first by treatment with dimethylformamide at 150°C in a closed reactor; 1 gram of the prepared zeolite and 7 ml of dimethylformamide were statically heated for 3-5 days.

[0082] The prepared boron ITQ-21 sample was placed in a tank, and ozone was passed through it while the temperature was raised to 150°C. This treatment lasted for 16-20 hours. The mass loss (if not treated with dimethylformamide) was approximately 40%.

[0083] XRD picture The case is essentially the same as the previously described calcined XRD. picture The case is the same.

[0084] Example 4

[0085] Platinum Additives

[0086] After initial treatment with dimethylformamide and ozone to remove organic matter, the boron-germanium ITQ-21 zeolite was neutralized with cesium hydroxide (50%) (0.11 g in 10 ml water). The solution was stirred at room temperature for 24 hours. The zeolite was then filtered, dried, and calcined to 300°C. 0.68 g of the exchanged zeolite was then treated with 0.013 g of platinum from platinum tetraamine chloride hydrate in 16 g of water. The solution was stirred at room temperature for 24 hours, filtered, dried, and calcined to 300°C (3 hours at maximum temperature). The solid was then crushed, sieved (24 / 40 flakes), and loaded into a reactor for testing.

[0087] Example 5

[0088] Pretreatment of catalytic naphtha reforming catalyst

[0089] The catalytic naphtha reforming catalyst prepared in Example 4 was sulfided. The sulfidation reaction was carried out in a downflow fixed-bed reactor system. The process is described below:

[0090] The catalyst was sieved into 24-40 pieces and then loaded into the center of a stainless steel tubular reactor. First, the catalyst (0.53 g dry weight, determined by TGA (thermogravimetric analysis) at 1112℉) was dried from room temperature to 400℉ in a stream of N2 (300 ml / min) at a heating rate of 10℉ / min and held at 400℉ for 30 minutes. To reduce the platinum in the catalyst, it was then heated from 400℉ to 900℉ in a stream of H2 (300 ml / min) at a heating rate of 5℉ / min and held at 900℉ for 30 minutes. Finally, the catalyst was cooled to 800℉ to initiate the sulfidation reaction.

[0091] The feedstock for the sulfidation reaction was anhydrous n-octane containing 200 ppm sulfur (as dimethyl disulfide). Sulfidation was carried out for 60 minutes at 800℉ and atmospheric pressure. The H2 and liquid feed flow rates were 30 ml / min and 0.43 ml / min, respectively. After sulfidation, the catalyst was heated from 800℉ to 900℉ in an H2 stream (300 ml / min) over several minutes, and then held at 900℉ for another 30 minutes to remove excess sulfur adsorbed in the pores and / or on the surface of the catalyst. Finally, the catalyst was heated or cooled to a predetermined reaction temperature (e.g., 850℉ or 950℉) over 2 hours in the same H2 stream (300 ml / min) to prepare for the catalytic naphtha reforming test in Example 6.

[0092] Example 6

[0093] Procedure for catalytic naphtha reforming testing

[0094] Following the sulfidation process described in Example 5, a catalytic naphtha reforming reaction is carried out as described below.

[0095] The catalyst was heated or cooled to a predetermined reaction temperature (950°F for Example 8) over 2 hours in the same H2 flow (300 ml / min) to prepare for the catalytic naphtha reforming test in this example, as described in Example 5. Simultaneously, the reactor system was pressurized to a predetermined pressure (150 psig for Example 8). The H2 flow was adjusted to a predetermined rate (14 ml / min for Example 8). The feed rate was 1.55 ml / hour (for Example 8).

[0096] In the following examples, catalytic naphtha reforming experiments were conducted using the naphtha feed described in Example 7, with a hydrocarbon WHSV of 2.2 and a hydrogen to hydrocarbon molar ratio of 3.0.

[0097] Example 7

[0098] Feed for catalytic naphtha reforming tests

[0099] GC analysis data from the feedstock used in the catalytic naphtha reforming test of this invention are shown in Table 5 below, along with GC results for the catalytic naphtha reforming test product of Example 8 on the catalyst described in Example 5. GC data were obtained through online analysis.

[0100] Example 8

[0101] Products from catalytic naphtha reforming tests

[0102] GC analysis data from the feed from Example 7 are shown in Table 5 below, along with the results of catalytic naphtha reforming tests conducted on the catalyst described in Example 5. Catalytic naphtha reforming experiments were performed at 950°F, 150 psig, a hydrocarbon WHSV of 2.2, and a hydrogen-to-hydrocarbon molar ratio of 3.0.

[0103] Table 5

[0104]

[0105] The products in Table 5 show an increase in aromatic compounds and octane number in gasoline. Boron ITQ-21 successfully reformed the feedstock of Example 7.

[0106] As used herein, the terms “comprises” or “comprising” are open-ended transitional terms meaning that the stated elements are included, but other unstated elements are not excluded. The phrases “consists essentially of” or “consisting essentially of” mean that other elements of any importance to the composition are excluded. The phrases “consisting of” or “consists of” are transitional terms meaning that all elements other than those stated are excluded, with the exception of only minor trace impurities.

[0107] All patents and publications cited herein are incorporated by reference to the extent that they are not inconsistent with them. It should be understood that some of the structures, functions, and operations described above are not essential to practicing the invention and are included in the description merely as a plurality of exemplary embodiments for the sake of completeness. Furthermore, it should be understood that the specific structures, functions, and operations described in the cited patents and publications may be implemented in conjunction with the invention, but they are not essential to its implementation. Therefore, it should be understood that the invention may be practiced in ways different from the specific description without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. A molecular sieve having a powder X-ray diffraction pattern in its original form after synthesis, said powder X-ray diffraction pattern having at least the following diffraction lines: Furthermore, the molecular sieve contains boron in its framework.

2. The molecular sieve according to claim 1, having a composition comprising the following molar relationships: B2O3:( n (SiO2 + GeO2) in n It is ≥10.

3. The molecular sieve according to claim 1, having a composition comprising the following molar relationships: B2O3:( n (SiO2 + GeO2) in n It is ≥15.

4. The molecular sieve according to claim 2, wherein n ranges from about 15 to 20.

5. The molecular sieve according to claim 1, wherein the SiO2 / GeO2 molar ratio is in the range of 4 to 12.

6. The molecular sieve according to claim 1, wherein the SiO2 / GeO2 molar ratio is in the range of 6 to 10.

7. The molecular sieve according to claim 1, wherein the SiO2 / Al2O3 molar ratio is ≥300.

8. The molecular sieve according to claim 1, wherein the SiO2 / Al2O3 molar ratio is ∞ (without Al).

9. A molecular sieve, in its calcined form, having at least the following diffraction lines: Furthermore, the molecular sieve contains boron in its framework.

10. The molecular sieve according to claim 9, having a chemical composition comprising the following molar relationships: Q includes N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclic [3.2.2]nonane cation.

11. The molecular sieve according to claim 10, wherein the molar ratio of (SiO2 / GeO2) / B2O3 ranges from about 15 to 20.

12. A method for synthesizing the molecular sieve according to claim 4, the method comprising: (1) Preparing a reaction mixture, the reaction mixture comprising: (a) Silicon source; (b) Germanium source; (c) Boron source; (d) A structure-directing agent comprising an N,N-diethyl-5,8-dimethyl-2-aza-onium bicyclic [3.2.2]nonane cation; (e) Fluoride ion source; and (f) Water; and (2) subject the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.

13. The method of claim 12, wherein the silicon source comprises a FAU framework zeolite having a SiO2 / Al2O3 molar ratio of 300 or greater.

14. The method of claim 12, wherein the silicon source does not contain Al.

15. The method of claim 12, wherein the reaction mixture has the following composition in molar ratio: 。 16. The method of claim 12, wherein the reaction mixture has the following composition in molar ratio: 。 17. The method of claim 15, wherein the molar ratio of (SiO2+GeO2) / B2O3 is in the range of about 15 to 20.

18. The method of claim 12, wherein the crystallization conditions include a temperature from 100°C to 200°C.

19. The method of claim 12, wherein the reaction mixture has a Q / F molar ratio in the range of 0.8 to 1.

2.

20. A method for converting a feedstock containing an organic compound into a conversion product, the method comprising contacting the feedstock with a catalyst containing a molecular sieve according to claim 8 under organic compound conversion conditions.

21. The method of claim 20, wherein the reaction is a reforming reaction and the catalyst comprises platinum.

22. A molecular sieve prepared by the method according to claim 12.

23. A molecular sieve prepared by the method according to claim 14.

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