Zeolites with improved hydroisomerization reactivity

Abstract

According to one aspect of the invention, a zeolite catalyst having an MRE structure for a hydroisomerization reaction is provided. The zeolite catalyst uses dimethylpyridine and trimethylpyridine as adsorbents, and the adsorption ratio of dimethylpyridine to trimethylpyridine, measured by FTIR, is greater than 3 and less than 10. According to another aspect of the invention, a hydroisomerization method for supplying feedstock is provided, comprising, in the presence of the zeolite catalyst, subjecting the feedstock to a temperature of 200 to 500°C, a hydrogen pressure of 1 to 200 atmospheres, and a flow rate of 1.0 to 10.0 hr. ‑1 Liquid space velocity (LHSV) and 45 to 1780 Nm 3 / m 3 The hydroisomerization reaction is carried out under conditions of a hydrogen / feed ratio. The zeolite catalyst according to the invention can maximize the prevention of cracking of the hydrocarbon feedstock used in the manufacture of lubricating base oils while simultaneously increasing the yield of hydroisomerization.

Description

[0001] This application is a divisional application of Chinese patent application No. 202310892962.1, filed on July 20, 2023, entitled "Zeolite with Improved Hydroisomerization Reaction Activity". Technical Field

[0002] This invention relates to a zeolite with improved hydroisomerization activity and a hydroisomerization process using the same as a feedstock. More specifically, this invention relates to a zeolite catalyst with an MRE structure having acidic sites located near the pore mouth and a hydroisomerization process using the same for C22+ hydrocarbons. Background Technology

[0003] In oil refining processes such as lubricant manufacturing, the hydroisomerization reaction of converting orthoparaffin to isoparaffin is becoming increasingly important. This is because long-chain orthoparaffin has poor low-temperature fluidity, thus failing to meet the specifications required for lubricant products in recent years. In particular, the quality of raw materials has deteriorated recently due to rising oil prices, while the development of automotive engine technology demands higher quality lubricants. In this regard, the hydroisomerization reaction of orthoparaffin with a C15 content or higher can be applied to the manufacturing process of high-viscosity index advanced lubricants.

[0004] The aforementioned hydroisomerization reaction is known to primarily proceed via a bi-functional catalyst, which typically consists of a metal component with hydrogenation / dehydrogenation capabilities and a support with acidic sites for skeletal isomerization. Various materials are known as supports with acidic sites, including silica-alumina, clay, and zeolites. Zeolites, in particular, not only maintain a stable structure even under harsh reaction conditions but also possess a large specific surface area and multiple acidic sites, making them suitable for isomerization reactions.

[0005] In order to maximize the hydroisomerization reaction and suppress the cracking of hydrocarbons as the target of treatment, research has been conducted on zeolite materials with excellent shape selectivity. It has been reported that zeolite materials with a unidimensional 10-ring microporous structure (such as ZSM-22, ZSM-23, EU-2, ZSM-48, etc.) have excellent selectivity for the hydroisomerization reaction.

[0006] According to the International Zeolite Association (IZA) catalog, EU-2, along with ZSM-48, ZBM-30, and EU-11, belongs to the ZSM-48 family. The ZSM-48 family has been assigned a three-letter skeleton structure code by the Structure Commission of the International Zeolite. MREs. They have similar XRD patterns, i.e., similar crystal structures.

[0007] Patent No. 10-2161426 discloses a process for hydroisomerization of hydrocarbon oil using zeolites belonging to the ZSM-48 family as catalysts, as well as the specific specifications of the zeolite catalysts used therein.

[0008] In addition, U.S. Patent No. 5,961,951 discloses a series of processes for manufacturing zeolite catalysts having this ZSM-48 structure by mixing silica, trivalent metal oxides, alkali metal oxides, ethylenediamine and water, as well as the specifications of the zeolite catalysts manufactured by said processes.

[0009] However, the patent document discloses catalysts suitable for the hydroisomerization of orthoparaffin with 10 or more carbon atoms, but does not specifically mention the specifications of the catalyst required as a hydroisomerization catalyst for orthoparaffin with 22 or more carbon atoms, which has a carbon number far exceeding 10. Summary of the Invention

[0010] Technical issues

[0011] The purpose of this invention is to provide a zeolite catalyst having an MRE structure for hydroisomerization of hydrocarbons with 22 or more carbon atoms that are difficult to reach the interior of the zeolite catalyst due to the long length of the carbon chain.

[0012] Technical solution

[0013] According to one aspect of the invention, a zeolite catalyst having an MRE structure for a hydroisomerization reaction is provided, wherein the zeolite catalyst employs dimethylpyridine (Lutidine) and trimethylpyridine (Collidine) as adsorbents, and the adsorption ratio of dimethylpyridine to trimethylpyridine, as measured by FTIR, can be greater than 3 and less than 10.

[0014] According to a specific example of the present invention, the zeolite catalyst having the MRE structure can be any one of EU2, ZSM-48 and ZBM-30 zeolites.

[0015] According to a specific example of the present invention, the zeolite catalyst is used with dimethylpyridine and trimethylpyridine as adsorbents, and the adsorption ratio of dimethylpyridine to trimethylpyridine measured by FTIR can be 8 or less.

[0016] According to a specific example of the invention, the zeolite catalyst may have a silica-alumina ratio (SAR) of 100 to 250.

[0017] According to a specific example of the invention, the zeolite catalyst may have an SAR of 120 to 200.

[0018] According to a specific example of the invention, the zeolite catalyst may have an SAR of 150 to 170.

[0019] According to a specific example of the present invention, the zeolite catalyst may have a pore volume of less than 0.1 cc / g with a diameter of more than 50 nm.

[0020] According to a specific example of the present invention, the zeolite catalyst may have a pore volume of less than 0.2 cc / g with a diameter of 2 nm to 50 nm.

[0021] According to a specific example of the invention, the zeolite catalyst may have a morphology selected from a group consisting of granular, needle, and rod morphologies.

[0022] According to a specific embodiment of the invention, the zeolite catalyst may have a concentration of 250 m. 2 / g or more 300m 2 BET surface area below / g.

[0023] According to one aspect of the present invention, a method for hydroisomerization of a feedstock is provided, comprising: in the presence of a zeolite catalyst according to the above aspect, at a temperature of 200 to 500°C, a hydrogen pressure of 1 to 200 atmospheres, and a flow rate of 1.0 to 10.0 hr... -1 Liquid space velocity (LHSV) and 45 to 1780 Nm 3 / m 3 The step of carrying out a hydroisomerization reaction of the feedstock under conditions of hydrogen / feedstock ratio.

[0024] According to a specific example of the present invention, the number of carbons in the hydrocarbons in the supplied raw material may be at least 22.

[0025] Technical effect

[0026] The zeolite catalyst of the present invention can maximize the prevention of cracking of hydrocarbon feedstocks used in the manufacture of lubricating base oils while increasing the yield of hydroisomerization. Furthermore, the hydroisomerization reaction of feedstocks using the zeolite catalyst of the present invention can be carried out at a lower reaction temperature compared to the case using conventional zeolites. Attached Figure Description

[0027] Figure 1 It is equivalent to the chemical structures of dimethylpyridine and trimethylpyridine used to measure the acidic sites of the zeolite catalyst with MRE structure of the present invention.

[0028] Figure 2 This is a simplified schematic diagram showing the adsorption sites of dimethylpyridine and trimethylpyridine used as adsorbents for measuring the acidic sites of the zeolite catalyst with MRE structure of the present invention.

[0029] Figure 3 These are SEM images used to observe the morphology of zeolite catalysts with MRE structures in Examples A to D;

[0030] Figure 4 The FTIR peak data for dimethylpyridine and trimethylpyridine according to embodiments of the present invention are shown. Detailed Implementation

[0031] Zeolite catalysts for hydroisomerization

[0032] According to one aspect of the invention, a zeolite catalyst having an MRE structure for a hydroisomerization reaction is provided, wherein the zeolite catalyst employs dimethylpyridine and trimethylpyridine as adsorbents, and the adsorption ratio of dimethylpyridine to trimethylpyridine, as measured by FTIR, can be greater than 3 and less than 10.

[0033] The adsorption ratio of dimethylpyridine to trimethylpyridine can be greater than 3 and less than 10, greater than 3 and less than 9, greater than 3 and less than 8, greater than 3 and less than 8, greater than 3 and less than 7, greater than 3 and less than 6, greater than 3 and less than 5, greater than 3 and less than 4, greater than 4 and less than 10, greater than 4 and less than 9, greater than 4 and less than 8, greater than 4 and less than 7, greater than 4 and less than 6, greater than 4 and less than 5, greater than 5 and less than 10, greater than 5 and less than 9, greater than 5 and less than 8, greater than 5 and less than 7, greater than 5 and less than 6, greater than 6 and less than 10, greater than 6 and less than 9, greater than 6 and less than 8, greater than 6 and less than 7, greater than 7 and less than 10, greater than 7 and less than 9, greater than 7 and less than 8.

[0034] like Figure 1As shown, dimethylpyridine, which has a pyridine chemical structure with two methyl groups, is smaller in molecular size than trimethylpyridine, which has three methyl groups. Therefore, it can penetrate deeper into the pores present on the MRE zeolite catalyst. However, the absolute molecular size of dimethylpyridine and trimethylpyridine makes it difficult for them to penetrate into the deep interior of the MRE zeolite catalyst through the pores.

[0035] That is, dimethylpyridine can enter the pore mouth located slightly inside the pores of the MRE zeolite catalyst, while trimethylpyridine can exist near the pore inlet located outside the pore mouth.

[0036] In this invention, to observe the distribution of acidic sites in the MRE zeolite catalyst, Fourier transform infrared spectroscopy (FTIR) was used with dimethylpyridine and trimethylpyridine as adsorbents. As mentioned above, dimethylpyridine can penetrate deeper into the pores than trimethylpyridine. According to the FTIR peak measurement results, a ratio of dimethylpyridine to trimethylpyridine adsorption exceeding 3 indicates that the acidic sites of the MRE zeolite catalyst are mainly located near the pore openings, rather than on the outside of the pores. Figure 2 As shown, when the adsorption ratio of dimethylpyridine to trimethylpyridine is less than 3, the acidic sites are mainly located on the outside of the pores. Therefore, the cracking reaction is more dominant than the hydroisomerization reaction, which may be unfavorable in terms of reaction yield. Conversely, when the adsorption ratio of dimethylpyridine to trimethylpyridine exceeds 10, the acidic sites of the MRE zeolite catalyst are located further inside than at the pore openings. Therefore, when the metal is supported by the MRE zeolite support, the metal cannot be smoothly dispersed, which may lead to a decrease in catalyst performance.

[0037] More specifically, the MRE zeolite catalyst can support metals such as platinum in the zeolite to impart binary functional catalyst properties. Here, the metal precursor is supported on the zeolite in a solution dissolved in water. The size of the metal precursor is larger than the micropores of the MRE zeolite, thus preventing it from entering the micropores and instead remaining on the outer surface. The external acidic sites of the zeolite serve to uniformly disperse the metal remaining on the outer surface of the zeolite, such as preventing sintering during the reaction. When the adsorption ratio of dimethylpyridine to trimethylpyridine exceeds 10, the acidic sites that help disperse the metal are located more internally, resulting in insufficient acidic sites on the surface, which may prevent the metal from dispersing smoothly.

[0038] In one implementation example, the zeolite catalyst can be any one of EU2, ZSM-48, and ZBM-30 zeolites. As mentioned above, MRE is a three-letter framework structure code assigned by the International Zeolite Structure Committee to the ZSM-48 family. The type of zeolite catalyst with the MRE structure is not limited as long as it belongs to the ZSM-48 family.

[0039] In one implementation, the zeolite catalyst may have an SAR of 100 to 250. SAR refers to the molar ratio of SiO2 to Al2O3 constituting the zeolite catalyst. The zeolite catalyst with the MRE structure may have an SAR of 100 to 250, 100 to 200, 100 to 180, 120 to 250, 120 to 200, 120 to 180, 150 to 250, 150 to 200, 150 to 180, or 150 to 170. In the zeolite catalyst, a portion of the Si present in SiO2 can be replaced by Al. The substituted Al has a 3+ charge, unlike the 4+ charge of Si. Therefore, this substitution induces a charge imbalance. To maintain charge neutrality under this charge imbalance, H is introduced. + This H + The more Al₂O₃ constitutes the zeolite catalyst, the more acidic sites exist within it. A lower SAR (Specific Acidity Range) is more advantageous in terms of catalyst yield. More specifically, when the SAR exceeds 250, the amount of Al in the entire zeolite catalyst is low, thus reducing the number of acidic sites where conversion reactions occur. Therefore, to achieve the same level of reaction as zeolites with more acidic sites, and to ensure more conversion reactions occur at a single acidic site, the reaction temperature needs to be increased. However, in this case, as the reaction temperature increases, decomposition reactions can also be promoted simultaneously. Furthermore, when the SAR is less than 100, the EU-1 structure is primarily synthesized, rather than the EU-2 structure desired in this invention. The EU-1 structure is less advantageous in terms of isomerization yield compared to the EU-2 structure.

[0040] In one implementation, the zeolite catalyst may not contain pores with a diameter greater than 50 nm.

[0041] According to the IUPAC classification of pore size, pores with a width (diameter) of less than 2 nm are classified as micropores, pores with a width of 2 nm to 50 nm are classified as mesopores, and pores with a width of more than 50 nm are classified as macropores. According to the classification, the zeolite catalyst with MRE structure of the present invention may not contain macropores.

[0042] The pore size and volume of the zeolite catalyst were measured using a BET apparatus (e.g., Micromeritics' ASAP2020), which, based on BET theory, measures the amount of gas adsorbed on the solid surface by measuring the pressure change in a vacuum chamber during a process of changing gas pressure at a certain temperature. For example, N2 can be adsorbed after a three-hour pretreatment at 350°C under vacuum, and the amount of adsorbed N2 gas can be measured and calculated from the BET adsorption isotherm.

[0043] More specifically, the volume of macropores in the zeolite catalyst is less than 0.3 cc / g, preferably less than 0.2 cc / g, more preferably less than 0.1 cc / g. Most preferably, the zeolite catalyst does not contain macropores.

[0044] In one implementation, the zeolite catalyst may not contain mesopores. More specifically, the zeolite catalyst may have a pore volume of less than 0.2 cc / g with a diameter of 2 nm to 50 nm. Preferably, the zeolite catalyst may have a pore volume of less than 0.1 cc / g with a diameter of 2 nm to 50 nm, and more preferably, the zeolite catalyst may not contain pores with a diameter of 2 nm to 50 nm. When the mesopore volume of the zeolite catalyst exceeds 0.2 cc / g, C22+ hydrocarbons can easily penetrate into the deeper interior of the catalyst, which is both a hydroisomerization reaction site and a cracking reaction site, thus cleaving the orthoparaffin chain through undesirable cracking as a side reaction.

[0045] Furthermore, the preparation methods for zeolite catalysts including macroporous and mesoporous materials include methods such as first preparing the zeolite catalyst and then etching the pores, and methods such as directly synthesizing zeolite including macroporous and mesoporous materials using surfactants. For the former, some zeolite is lost through the etching process, thus increasing the manufacturing cost per unit weight. For the latter, special surfactants are required, which have high raw material costs. Moreover, the process of treating the foam remaining in the mother liquor after zeolite filtration in the post-synthesis zeolite recovery step is also costly, thus contributing to the high manufacturing cost. The zeolite catalyst of the present invention, as described above, does not substantially contain macroporous and mesoporous materials, thus offering advantages in terms of manufacturing cost.

[0046] As described above, the zeolite catalyst according to the present invention preferably does not contain macropores or mesopores, and may only include fine pores (micropores) with a diameter of less than 2 nm. Since C22+ orthoparaffin does not easily enter the interior of the zeolite catalyst through these fine pores, the cracking reaction of C22+ orthoparaffin at the acidic sites inside the zeolite is prevented. Furthermore, as described above, the acidic sites of the zeolite catalyst are located at the pore openings, thus allowing C22+ orthoparaffin to isomerize into isoparaffin through the desired hydroisomerization reaction without approaching the interior of the catalyst.

[0047] In one implementation, the zeolite catalyst may have a morphology selected from a group consisting of particulate, needle-like, and rod-like morphologies. The morphology is achieved through, for example... Figure 3 The SEM image shown indicates that, in terms of improving the yield of the hydroisomerization reaction of hydrocarbon feedstock and reducing the weighted average bed temperature (WABT), the zeolite catalyst preferably has a particulate morphology.

[0048] In one implementation example, the zeolite catalyst may have a concentration of 250 m. 2 / g or more 300m 2 The specific surface area of ​​the zeolite catalyst is less than / g. The specific surface area is measured using a BET apparatus (e.g., Micromeritics' ASAP 2020), which, based on BET theory, measures the amount of gas adsorbed on the solid surface by measuring the pressure change in a vacuum chamber during a process of changing gas pressure at a certain temperature. For example, after pretreatment at 350°C under vacuum for three hours to allow N2 adsorption, the amount of adsorbed N2 gas is measured and calculated based on the BET adsorption isotherm.

[0049] More specifically, the zeolite catalyst may have a concentration of 250m. 2 / g or more 300m 2 / g or less, 250m 2 / g or more 290m 2 / g or less, 250m 2 / g or more 280m 2 / g or less, 250m 2 / g or more 270m 2 / g or less, 250m 2 / g or more 260m 2 / g or less, 260m 2 / g or more 300m 2 / g or less, 260m 2 / g or more 290m 2 / g or less, 260m 2 / g or more 280m 2 / g or less, 260m 2 / g or more 270m 2 / g or less, 270m 2 / g or more 300m 2 / g or less, 270m 2 / g or more 290m 2 / g or less, 270m 2 / g or more 280m 2 / g or less, 280m 2 / g or more 300m 2 / g or less, 280m 2 / g or more 290m 2 / g or less or 290m 2 / g or more 300m 2The BET surface area is below / g. The zeolite catalyst of the present invention, as described above, substantially does not contain the aforementioned macropores and mesopores, but rather micropores, thus exhibiting a high BET surface area, which is approximately 220 m², compared to the typical MRE structure of zeolites. 2 The / g level increases. Under otherwise identical conditions, a low BET surface area indicates that the zeolite structure has not grown normally, and this generally results in low catalyst activity.

[0050] Hydroisomerization process using zeolite catalysts

[0051] According to one aspect of the invention, a process is provided for isomerizing a feedstock containing orthoparaffin (including mineral-based, synthetic, and / or biomass-based feedstocks) to isoparaffin while supplying hydrogen, in the presence of the aforementioned zeolite catalyst. This feedstock typically contains at least about 15% by weight of orthoparaffin, specifically at least about 40% by weight.

[0052] As a specific example of the supplied raw material, it may be a hydrocarbon oil fraction having a boiling point range of at least about 150 to 580°C (measurable by ASTM D-86 or ASTM D-2887), specifically a hydrocarbon oil fraction within the range of lubricating base oils.

[0053] In particular, the pores of the aforementioned zeolite catalyst are micropores with a diameter of less than 2 nm, thus making it effective for hydrocarbon oil fractions with a carbon number of about 22 or more within the boiling point range of about 360 to 580 °C for lubricating base oils. More specifically, the zeolite catalyst with the aforementioned micropores is effective for the hydroisomerization of hydrocarbon oil fractions with carbon numbers of 22 to 35, 22 to 30, 22 to 25, 25 to 35, 25 to 30, 27 to 35, or 27 to 30.

[0054] In one implementation, the hydrocarbon supply feedstock may contain about 15% by weight of orthoparaffin (wax component), specifically at least about 40% by weight. Furthermore, the supply feedstock may, for example, contain less than about 10 ppm (wt) of nitrogen (specifically, less than about 5 ppm (wt)) and / or less than about 10 ppm (wt) (specifically, less than about 5 ppm (wt)) of sulfur.

[0055] The hydroisomerization process supplies hydrocarbon feedstock at, for example, a temperature of about 200 to 500°C (specifically about 220 to 450°C, more specifically about 240 to 400°C), a hydrogen pressure of about 1 to 200 atmospheres (specifically about 100 to 180 atmospheres, more specifically about 130 to 150 atmospheres), and a hydrogen pressure of about 0.1 to 10 h⁻¹. -1 (Specifically, about 0.5 to 5 hours) -1 More specifically, about 1 to 2 hours -1The space velocity (LHSV) is approximately 45 to 1780 Nm. 3 / m 3 (Specifically, approximately 200 to 100 Nm) 3 / m 3 More specifically, approximately 480 to 530 Nm 3 / m 3 It is executed under the condition of hydrogen / feed supply ratio.

[0056] After the above-described hydroisomerization process, the pour point of the hydrocarbon oil fraction used as the feedstock can be reduced by at least -12°C, specifically by at least -18°C. Furthermore, when the feedstock is a hydrocarbon oil fraction within the boiling point range of a lubricating base oil, the viscosity coefficient can be, for example, at least about 60, specifically about 70 to 160, more specifically about 80 to 150, and particularly specifically in the range of about 120 to 140.

[0057] The following preferred embodiments are disclosed to aid in understanding the present invention, but these embodiments are provided merely for the purpose of making the present invention easier to understand, and the present invention is not limited thereto.

[0058] Preparation Example

[0059] According to a specific example of the present invention, the zeolite catalyst is prepared by the following process, and the reagents used in the preparation example and the comparative preparation example are shown in Table 1 below.

[0060] Table 1

[0061]

[0062] Preparation of Sample A

[0063] Solution A1 was prepared by completely dissolving 1121.49g of sodium hydroxide and 44.73g of bead (>98.0%) in distilled water. Solution A2 was prepared by adding 5.06g of aluminum hydroxide to solution A1 and dissolving it completely. Solution A3 was then prepared by adding 37.49g of hexamethonium chloride dihydrate (>99.0%) to solution A2 and dissolving it completely. Subsequently, while rapidly stirring solution A3 at room temperature, 780.30g of LUDOX HS-40 colloidal silica was added dropwise for approximately 1 hour to form a gel. The prepared gel was poured into a 2L Hastelloy autoclave and rotated at 600 rpm. It was then aged at room temperature and pressure for 24 hours, followed by heating to 165°C for 85 minutes, and hydrothermally synthesized at 165°C for 48 hours.

[0064] Afterwards, the zeolite was thoroughly washed with DI water until the pH reached neutral, and then dried overnight in a 50°C oven. The organic matter in this synthesized zeolite was completely removed during the muffle furnace process at 450°C for 1 hour at 3°C / min and 550°C for 6 hours at 1°C / min. The zeolite after this series of washing and calcination processes is called Na-EU2.

[0065] In order to contain Na in Na-EU2 + The ion is replaced by NH4 + The Na-EU2 was subjected to two ion exchanges using a 1M NH4NO3 solution at room temperature. The zeolite resulting from the ion exchange was referred to as NH4-EU2.

[0066] Subsequently, 42g of NH4-EU2 and 18g of Pural pseudoboehmite were thoroughly mixed, and the mixture was initially impregnated in a solution of 36g of 1% Pt(NH3)4(NO3)2 + 1.32g of 60% nitric acid using an impregnation method. After thorough drying at room temperature, the impregnated zeolite was calcined in a muffle furnace at 120℃ for 3 hours × 2℃ / min and at 500℃ for 3 hours × 2℃ / min to obtain the final zeolite catalyst sample A.

[0067] Comparative preparation examples

[0068] Samples B to D were prepared using the same reagents as in the preparation example described below via the following process.

[0069] Sample B

[0070] Zeolite catalyst sample B was prepared using the same process as sample A, except that the rotation speed was 400 rpm during the step of rotating it after gel formation, and it was not aged at room temperature and pressure for 24 hours thereafter.

[0071] Sample C

[0072] Solution C1 was prepared by adding 4.59 g of CATAPAL A to 223.65 g of 20 wt% NaOH solution and dissolving it completely. Solution C2 was prepared by adding 942.57 g of distilled water (DI) to solution C1 and dissolving it completely. Solution C3 was prepared by adding 37.49 g of hexamethonium chloride dihydrate (>99.0%) to solution C2 and dissolving it completely. Then, while rapidly stirring solution C3 at room temperature, 780.30 g of LUDOX HS-40 colloidal silica was added dropwise for about 1 hour to form a gel. The prepared gel was then poured into a 2 L Hastelloy autoclave and rotated at 600 rpm. The temperature was raised to 165 °C at room temperature and pressure for 5 hours, and then hydrothermally synthesized at 165 °C for 48 hours.

[0073] Subsequently, zeolite catalyst sample C was prepared by the same cleaning, drying, calcination and ion exchange steps as sample A.

[0074] Sample D

[0075] Solution D1 was prepared by completely dissolving 204.56 g of 20 wt% NaOH solution in 811.15 g of distilled water (DI). Solution D2 was prepared by adding 5.17 g of aluminum hydroxide to solution D1 and dissolving it completely. Solution D3 was then prepared by adding 20.55 g of hexamethonium chloride dihydrate (>99.0%) to solution D2 and dissolving it completely. Finally, solution D4 was prepared by adding 60.40 g of cetyltrimethylammonium chloride solution (25 wt% in H2O) to solution D3 and dissolving it completely. While rapidly stirring the prepared solution D4 at room temperature, 798.13 g of LUDOX HS-40 colloidal silica was added dropwise for about 1 hour to form coagulation. The prepared gel was poured into a 2L Hastelloy autoclave and rotated at about 400-600 rpm. After aging at room temperature and pressure for 24 hours, the temperature was raised to 165°C for 85 minutes and then hydrothermally synthesized at 165°C for 48 hours.

[0076] Subsequently, zeolite catalyst sample D was prepared by the same cleaning, drying, calcination and ion exchange steps as sample A.

[0077] Example

[0078] 1. Measurement of the distribution of acidic sites in zeolites

[0079] FTIR measurements were performed to determine the distribution of acidic sites in samples A through D. The measurements were conducted in the following order.

[0080] 1) Preparation of 15mg self-supporting zeolite wafers with a diameter of 1.3cm.

[0081] 2) Zeolite wafers carried in high-temperature / high-voltage battery cells

[0082] 3) At 1.0×10 -8 Under TORG pressure, the temperature is increased to 550°C at a rate of 10°C / min, followed by evacuation for 2 hours.

[0083] 4) At 1.0×10 -8 Cooled to 150°C under Torr pressure.

[0084] 5) Repeatedly inject dimethylpyridine or trimethylpyridine under vacuum and at 150°C until the adsorption peak area no longer increases.

[0085] 6) At 1.0×10 -8 Removal of physically adsorbed dimethylpyridine or trimethylpyridine by applying pressure and temperature of 200°C for 2 hours

[0086] 7) At 1.0×10 -8 Under Torr pressure, the adsorption area was measured after cooling to 150℃.

[0087] The FTIR peaks of trimethylpyridine and dimethylpyridine obtained by the aforementioned FTIR measurement method are as follows: Figure 4 As shown, the FTIR adsorption areas for dimethylpyridine and trimethylpyridine are integraled to 1600 cm⁻¹. -1 Up to 1700cm -1 The wavenumber range was obtained. The specific peak areas for each sample are shown in Table 3 below.

[0088] 2. Measure the yield and reaction temperature of the hydroisomerization reaction of zeolite.

[0089] The supplied raw materials, possessing the physical properties shown in Table 2 below, are supplied at a hydrogen pressure of approximately 160 atmospheres and a working time of approximately 1.7 hours. -1 Liquid space velocity (LHSV), approximately 500 Nm 3 / m 3 The hydrogen / feed ratio and reaction temperature (target flow point -18°C) were introduced into the hydroisomerization reaction in the presence of zeolite catalysts from samples A to D.

[0090] Table 2

[0091]

[0092] The SAR, BET surface area, mesopore volume fraction, peak area of ​​dimethylpyridine and trimethylpyridine, peak area ratio of dimethylpyridine / trimethylpyridine, weighted average bed temperature (WABT), and yield of the hydroisomerization reaction of samples A to D according to the embodiments are shown in Table 3 below.

[0093] Table 3

[0094]

[0095] As shown in Table 3, the highest yield of 92.5% was achieved when using the zeolite catalyst of Sample A, which simultaneously met the requirements of SAR above 150, BET surface area above 250, and dimethylpyridine / trimethylpyridine peak area ratio above 3 and below 10, to carry out the hydroisomerization reaction. This confirms that such a high yield can be achieved at a low reaction temperature (WABT).

[0096] Furthermore, regarding the morphology of samples A through D, see [link to relevant documentation]. Figure 3 It can be seen that sample A exhibits a granular type, sample B exhibits an amorphous type with incomplete crystal growth, sample C exhibits a needle type, and sample D exhibits a rod type morphology. Due to this morphology, the surface area of ​​sample B, which is amorphous in Table 3, is significantly lower than that of samples A, C, and DBET, which have other types of morphology.

Claims

1. A zeolite catalyst having an MRE structure for hydroisomerization reactions, wherein dimethylpyridine and trimethylpyridine are used as adsorbents, and the adsorption ratio of dimethylpyridine to trimethylpyridine, as measured by Fourier transform infrared spectroscopy, is greater than 3 and less than 10. in, Zeolite catalysts with the MRE structure have a silica-alumina ratio of 100 to 200. Among them, the zeolite catalyst with the MRE structure has 250m 2 / g or more 300m 2 BET surface area below / g The zeolite catalyst having the MRE structure does not contain pores with a diameter exceeding 50 nm, and In the zeolite catalyst with the MRE structure, the volume of pores with a diameter of 2 nm to 50 nm is less than 0.2 cc / g. The zeolite catalyst is used for the hydroisomerization of the feedstock, wherein the hydrocarbon in the feedstock has 22 or more carbon atoms.

2. The zeolite catalyst having an MRE structure for hydroisomerization reaction according to claim 1, wherein: The zeolite catalyst having the MRE structure is any one of EU2, SM-48 and ZBM-30 zeolite.

3. The zeolite catalyst having an MRE structure for hydroisomerization reaction according to claim 1, wherein: Using dimethylpyridine and trimethylpyridine as adsorbents and measuring the adsorption ratio of dimethylpyridine to trimethylpyridine by Fourier transform infrared spectroscopy, the adsorption amount was less than 8.

4. The zeolite catalyst having an MRE structure for hydroisomerization reaction according to claim 1, wherein: Zeolite catalysts having the MRE structure have morphology selected from groups consisting of particulate, needle-like, and rod-like morphologies.

5. The zeolite catalyst having an MRE structure for hydroisomerization reaction according to claim 4, wherein: Zeolite catalysts with the MRE structure have a particulate morphology.

6. A method for hydroisomerization of feedstock, comprising: In the presence of a zeolite catalyst having an MRE structure for hydroisomerization reaction as described in claim 1, Maintain the supply of raw materials at a temperature of 200 to 500°C, a hydrogen pressure of 1 to 200 atmospheres, and a working time of 1.0 to 10.0 hours. -1 The velocity in the liquid space and 45 to 1780 Nm 3 / m 3 The steps of the hydroisomerization reaction under the condition of hydrogen / feed feed ratio. The hydrocarbon in the supplied raw material has at least 22 carbon atoms.

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