Acid condensation catalyst

Abstract

The present specification describes an acid condensation catalyst comprising: a zeolite having a pore size of 10 tetrahedral atoms, a porosity of > = 0.05 mL / g in the range of 20-100, and a silica: alumina ratio (SAR) of 10 to 50; an alumina binder in which the zeolite is dispersed; and at least one metal; wherein the acid condensation catalyst has a porosity of > = 0.06 mL / g in the range of 20-100 measured by physical adsorption using the BJH method. Also described is a method for preparing the catalyst, and a process for acid condensation of a feed stream comprising one or more oxygenates, the process being performed in the presence of the catalyst as described.

Description

Technical Field

[0001] This invention relates to catalysts for acid-catalyzed condensation of oxygen-containing feedstocks to produce aromatic products. Background Technology

[0002] Due to the negative environmental impacts of fossil fuels, there is an urgent need to find alternatives. One approach is to produce fuel from biomass, which, unlike fossil fuels, is renewable. To this end, VirentEnergy Systems Inc. has developed a process for converting biomass into fuel-grade materials (BioForming). TM (Technology). BioForming TM The technology has been widely described, for example, in U.S. Patent No. 7,977,517 (Virent Energy Systems, Inc.) and US2016 / 108330A1 (Virent, Inc.). The process comprises three steps. First, a feedstock containing sugars and / or cellulose biomass is hydrogenated to provide a material containing polyols. Second, the polyol-containing material undergoes hydrodeoxygenation to provide a stream containing unsaturated compounds. Third, the material containing unsaturated compounds undergoes an acid condensation step to produce a variety of products containing aromatic compounds.

[0003] In US7977517B2 and US2016 / 108330A1, the acid condensation step (AC step) is carried out in the presence of a catalyst with acidic sites (AC catalyst). Various catalysts have been proposed, including zeolites, silica-alumina phosphates, aluminum phosphate, amorphous silica-alumina, zirconium oxide, and zirconium sulfate. Examples of zeolite catalysts include La-doped H-mordenite, Ni-doped H-mordenite, Eu-doped H-mordenite, Ga-doped β-zeolite, phosphoric acid-doped SiO2 / Al2O3, Ni-doped Al2O3-bonded ZSM-5, and Ga-doped Al2O3-bonded ZSM-5 (Examples 38-44, all referenced). The catalysts were tested in gas-phase condensation with various oxygen-containing feedstocks.

[0004] Further examples of catalysts for acid condensation steps are described in US9878966B2. In one example, the catalyst comprises 1 wt% Ni (1 / 16” extrusion, 20% Al2O3 binder, ZSM-5 SAT 30, Zeolyst) on a commercially available Al2O3-bonded ZSM-5 support.

[0005] Another example of a process for converting olefins or alkanes into aromatic compounds is described in US2022 / 0203343A11. The catalyst comprises a microporous zeotype material, a binder, and a metal phosphide. The example in this reference was prepared using commercial zeolite CBV3024 from Zeolyst, which has an SAR of 30.

[0006] An undesirable byproduct of the acid condensation step is carbon deposits (also known as coke). The presence of coke hinders feed molecules from entering the acidic sites of the zeolite, thereby reducing catalyst activity. Some degree of coke formation is unavoidable, and coke yield is generally correlated with catalyst productivity. During operation, catalyst regeneration is necessary, in which the carbon accumulated in the catalyst is burned off, requiring reactor shutdown.

[0007] Providing catalysts with reduced coke yield and / or higher activity for a given coke yield would be advantageous, contributing to higher product yields and less regeneration time. This invention provides a solution to this problem. Invention Overview The inventors have now determined that AC catalysts comprising zeolite with pore sizes of 10 tetrahedral atoms and alumina binder are particularly suitable for AC steps. Specifically, the inventors have determined that the activity of the catalyst and the coke yield can be controlled by selecting alumina and zeolite to achieve a specific pore size distribution in the catalyst.

[0009] The following theory, which has been constructed afterward, explains how the porosity of alumina and zeolite affects the coking performance of the catalyst.

[0010] The catalyst of this invention comprises zeolite and a binder matrix. The binder serves to impart strength to the catalyst and prevent it from breaking down in the reactor. Alumina particles constituting the binder surround the zeolite particles and hold the mixture together. Small alumina crystals are desirable compared to the size of the zeolite particles to impart catalyst strength, as the small alumina particles can best fill around the larger zeolite particles.

[0011] Commercial alumina is typically an agglomerate composed of smaller crystals of alumina hydroxide called boehmite or pseudoboehmite (referred to herein as the "alumina binder precursor"). The individual crystals of the alumina binder precursor are on the order of 2 nanometers to tens of nanometers. The agglomerates include micropores and / or mesopores, which contribute to the overall microporosity and mesoporosity of the final catalyst. The alumina binder precursor is acid-gelled before or after combination with zeolite to disperse the individual crystals of the alumina binder precursor and thus allow them to better fill around the zeolite particles. The gelling and binding processes impart properties to the finished catalyst that are related to the properties of the alumina binder precursor and contribute to the porosity of the catalyst.

[0012] Commercial zeolite particles can also be aggregates of smaller zeolite crystals, known as polycrystalline agglomerates, with varying degrees of mesoporosity and macroporosity. Compared to alumina binder precursors, zeolite particles do not exhibit significant decomposition during sol-gelation (described further below).

[0013] The inventors have determined that catalysts with the pore size distribution described herein provide a favorable balance between catalytic activity and coke yield. The pore size distribution of the catalyst is influenced by the pore size distribution of the zeolite material and the alumina. The presence of some mesoporous and macroporous components within the catalyst is thought to allow molecules to approach and exit the channels of the 10-membered ring zeolite particles within the catalyst aggregate. In the absence of sufficient porosity, product molecules are considered less able to exit the catalyst, leading to further reactions and coke accumulation. The zeolite must have a sufficiently high pore volume in the range of 20 Å–100 Å to allow feed molecules to reach the active sites within the zeolite and exit the zeolite once conversion occurs.

[0014] The inventors have also recognized that one factor contributing to catalyst deactivation is the migration of aluminum from the zeolite to the binder. Aluminum provides acidic sites within the zeolite for catalysis to occur. Over time, the migration of aluminum from the zeolite leads to a reduction in the number of active sites, and thus a decrease in activity. Therefore, the zeolite used in this invention has a silica:alumina ratio (SAR) of 10 to 50. This is a lower SAR (higher Al content) than that previously used in comparable catalysts, such as those described in the example of US2016 / 108330A1.

[0015] In a first aspect, the present invention relates to an acid condensation catalyst comprising: Zeolite with a pore size of 10 tetrahedral atoms, a porosity of ≥ 0.05 mL / g in the range of 20 Å to 100 Å, and a silica:alumina ratio (SAR) of 10 to 50. Alumina binder, in which zeolite is dispersed; and At least one metal; The acid condensation catalyst has a porosity of ≥ 0.06 mL / g in the range of 20 Å–100 Å, as measured by physical adsorption using the BJH method.

[0016] In a second aspect, the present invention relates to a method for manufacturing an acid condensation catalyst, the method comprising the following steps: (i) Combining zeolite with an alumina binder precursor, the zeolite having a pore size of 10 tetrahedral atoms, a silica:alumina ratio (SAR) of 10 to 50 and a porosity of ≥ 0.05 mL / g in the range of 20 Å to 100 Å as measured by physical adsorption using the BJH method. The alumina binder precursor is dissolved in acid before or after being combined with zeolite; (ii) Forming the mixture into particles suitable for a fixed-bed process; (iii) Calcination to convert the alumina binder precursor into alumina; and (iv) The product of step (iii) is impregnated with a metal salt; The catalyst is based on the first aspect.

[0017] In a third aspect, the present invention relates to a method for acid condensation of a feed stream, wherein the method is carried out in the presence of a catalyst according to the first aspect. Brief description of the attached diagram Figure 1 The figure illustrates the specific productivity and coke yield of the embodiments and comparative embodiments.

[0019] Detailed Explanation Any subheadings are included for convenience only and should not be construed as limiting the content of this disclosure in any way.

[0020] Acid condensation catalyst As previously mentioned, US2016 / 108330A1 provides examples of Ni-doped Al2O3-bonded ZSM-5 or Ga-doped Al2O3-bonded ZSM-5 (catalysts LL and MM in Table 12) used as catalysts in acid condensation steps. The source of alumina or ZSM-5 is not reported in those examples, although ZSM-5 zeolite was used in Example 52; this ZSM-5 zeolite was material CBV 8014 from Zeolyst International, with a silica to alumina ratio (SAR) of 80.

[0021] Zeolites are typically classified by the number of tetrahedral atoms (Si or Al) defining the pore openings. In this invention, the zeolite is one with 10 tetrahedral atoms in pore size. This pore size has been found to be particularly suitable for the production of fuels and xylene. The zeolite is preferably one with an MFI framework. Most preferably, the zeolite is ZSM-5, as ZSM-5 provides high yields of aromatic products and is resistant to deactivation. In each case, it is preferred that the zeolite is in hydrogen form.

[0022] Zeolites have a framework that can be balanced by cations such as ammonium cations and / or protons. Preferably, the zeolite is in the form of hydrogen.

[0023] To ensure that the catalyst does not deactivate too quickly, the zeolite has an SAR of 10 to 50. Preferably, the zeolite has an SAR in the range of 10 to 40, more preferably in the range of 20 to 40.

[0024] The inventors have determined that the pore size distribution of a catalyst plays a crucial role in providing a favorable balance between productivity and coke yield. The porosity in the catalyst originates from the mixing of porosities associated with the zeolite and alumina binders.

[0025] A pore size of 20 Å–100 Å corresponds to small mesopores (mesopores are defined as pores with a diameter of 20 Å–500 Å). Zeolites with a porosity ≥ 0.05 mL / g in the 20 Å–100 Å range have sufficient pore size to allow feed molecules to approach and exit the active sites without molecule entrapment and coking. Preferably, the zeolite has a porosity of 0.05 mL / g in the 20 Å–100 Å range. 沸石 Up to 0.15 mL / g 沸石 Preferably 0.05 mL / g 沸石 Up to 0.10 mL / g 沸石 Such as 0.05 mL / g 沸石 Up to 0.08 mL / g 沸石 Porosity.

[0026] Porosity can be measured using the BJH method with N2 or Ar as the adsorbent. Similar values ​​for pore volume are obtained regardless of the gas used. Preferably, porosity is measured using the BJH method via Ar physisorption.

[0027] Zeolites may also include porosity related to pore sizes ranging from 100 Å to 1000 Å, encompassing both mesopores and macropores. Preferably, the zeolite has a porosity of 0.05 mL / g in the range of 100 Å to 1000 Å. 沸石 Up to 1.0 mL / g 沸石 Preferably 0.05 mL / g 沸石Up to 0.50 mL / g 沸石 Preferably 0.05 mL / g 沸石 Up to 0.40 mL / g 沸石 Porosity.

[0028] Various zeolites with different pore size distributions are commercially available. The pore size distribution can be a result of the methods used to manufacture the zeolite. Alternatively, zeolites can be modified to introduce porosity by methods known to those skilled in the art, such as treatment with an alkaline solution or hydrothermal aging with steam at elevated temperatures.

[0029] Based on the total weight of the catalyst, the zeolite content is preferably 60 wt% to 95 wt%, more preferably 60 wt% to 90 wt%, with 70 wt% to 85 wt% being the most preferred.

[0030] The alumina content in the catalyst is preferably 5 wt% to 40 wt%, more preferably 10 wt% to 40 wt%, with 10 wt% to 30 wt% being the most preferred. In a preferred embodiment, the alumina is γ-alumina.

[0031] The weight ratio of zeolite to alumina in the catalyst is preferably 60:40 to 95:5, more preferably 60:40 to 90:10, and the ratio of 70:30 to 90:10 is the most preferred.

[0032] The catalyst is doped with one or more metals. Preferred metals are transition metals and lanthanides. Particularly preferred is that the catalyst is doped with nickel. Preferably, the metal, preferably nickel, is present in an amount sufficient to associate with acidic sites on the zeolite, but not in an amount exceeding that. The preferred nickel content is 0.1 wt% to 5 wt%, preferably 0.5 wt% to 2 wt%, based on the total weight of the catalyst. Unlike the metal phosphide-containing catalysts described in US2022 / 203343A1, it is preferred that the metal is not present as a metal phosphide.

[0033] The porosity derived from zeolite and alumina contributes to the overall porosity of the catalyst. The acid condensation catalyst exhibits a porosity ≥ 0.06 mL / g in the range of 20 Å–100 Å. 催化剂 Preferably ≥ 0.09 mL / g 催化剂 The porosity is preferably 0.06 mL / g in the range of 20 Å to 100 Å. 催化剂 Up to 0.30 mL / g 催化剂 Preferably 0.06 mL / g 催化剂 Up to 0.20 mL / g 催化剂 Such as 0.06 mL / g催化剂 Up to 0.15 mL / g 催化剂 The porosity is particularly preferred. The acid condensation catalyst has a porosity of 0.09 mL / g in the range of 20 Å to 100 Å. 催化剂 Up to 0.30 mL / g 催化剂 Preferably 0.09 mL / g 催化剂 Up to 0.20 mL / g 催化剂 Such as 0.09 mL / g 催化剂 Up to 0.15 mL / g 催化剂 Porosity.

[0034] The catalyst may also include a porosity in the range of 100 Å to 1000 Å, encompassing both mesopores and macropores. Preferably, the catalyst has a porosity of 0.05 mL / g in the range of 100 Å to 1000 Å. 催化剂 Up to 1.0 mL / g 催化剂 Such as 0.05 mL / g 催化剂 Up to 0.50 mL / g 催化剂 The porosity is [value missing]. Higher porosities within this range appear to be associated with increased productivity (see Example 1), therefore, a catalyst having a porosity such as 0.20 mL / g is preferred. 催化剂 Up to 0.50 mL / g 催化剂 Porosity.

[0035] Catalyst manufacturing The first step in the manufacture of the catalyst (step (i)) involves combining the zeolite with an alumina binder precursor. The properties of the zeolite used as an input material to form the catalyst are described under the heading “Acid Condensation Catalysts.” The alumina binder precursor is referred to herein as “precursor” because it is soluble before or after combination with the zeolite to break down the alumina into smaller alumina crystals and thus allow it to bind more effectively with the zeolite. Solubilization is preferably achieved by treating the alumina with an aqueous acid, preferably an aqueous monocarboxylic acid. Preferred acids include nitric acid, formic acid, and acetic acid. While the alumina binder precursor may comprise any suitable form of alumina, boehmite is preferred.

[0036] In a preferred embodiment, the zeolite and alumina binder precursor are combined by kneading. Kneading helps achieve uniform dispersion of the zeolite in the alumina. Kneading is preferably carried out in the presence of an aqueous phase to aid mixing, and in the case of the use of an aqueous acid, to additionally pectinate the alumina. A binder (not to be confused with the alumina binder precursor) may also be added during kneading to provide particles with a certain strength. The binder can act as a rheologist to aid extrusion. The binder can be an organic binder that is burned off in a subsequent calcination step. The binder is preferably cellulose, preferably hydroxyethyl cellulose. Alternatively, the binder can be an inorganic binder, such as silica, aluminum hydroxychloride, or kaolin phosphate. Kneading can be carried out at low or elevated temperatures, such as above 50°C, typically above 80°C, such as above 100°C.

[0037] The porosity of the zeolite and alumina binder precursors contributes to the porosity of the catalyst. Therefore, alumina binder precursors can be used to introduce additional porosity in the range of 20 Å–100 Å and / or 100 Å–1000 Å. In some embodiments, a single alumina binder precursor can be used. In alternative embodiments, two or more different alumina binder precursors can be used. Given knowledge of the target pore size distribution in the final catalyst and the pore size distribution of the zeolite, those skilled in the art will be able to select a suitable alumina binder precursor.

[0038] The mixture of zeolite, alumina, and optionally a binder is then formed into particles suitable for a fixed-bed process (step (ii)). The product of this step may be referred to as a green compact. Preferred particle types include microspheres, microparticles, or extrudates. Suitable forming techniques will be known to those skilled in the art. In a preferred embodiment, the forming step involves extruding the mixture to form an extrudate, preferably producing a cylindrical or multi-lobed extrudate. The particle diameter and shape can be adjusted based on the reactor size and pressure drop requirements.

[0039] The green body is then calcined (step (iii)). Calcination removes any residual water in the green body, burns off any binders already included, and sintersects the alumina particles, which provides strength to the catalyst particles. Calcination conditions will be readily determined by those skilled in the art. Typical conditions are a temperature of at least 500°C for at least 1 hour. Calcination at about 600°C for about 2 hours is generally suitable. Calcination can also induce a phase transformation of alumina, for example, by converting boehmite to γ-alumina.

[0040] The product of step (iii) is then impregnated with one or more metals (step (iv)). Preferred metals include transition metals and lanthanides. Particularly preferred is that the particles are doped with nickel. Doping of the particles can be achieved using an aqueous solution containing a salt of the desired metal, for example by initial wet impregnation or by ion exchange. Particularly preferred is the use of a solution containing a nickel salt, preferably by initial wet impregnation or by ion exchange, to dope the particles with nickel.

[0041] Following the doping of particles, a drying step and, optionally, a further calcination step are typically required. Suitable conditions will be readily determined by those skilled in the art.

[0042] Applications of catalysts The catalyst described in this article has been found to be particularly effective as a catalyst for converting a feed stream containing oxygen-containing hydrocarbons ("oxygenated compounds") into products with a higher number of carbon atoms per molecule.

[0043] As used herein, the term "oxygen-containing compound" refers to a hydrocarbon having one or more carbon atoms and at least one oxygen atom (referred to herein as C2). 1+ O 1+ Hydrocarbons). Preferably, it contains... n Oxygen compounds containing one carbon atom include one and n The oxygen atoms between the C atoms n O 1-n In a preferred embodiment, the oxygen-containing compound comprises 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. In a preferred embodiment, the oxygen-containing hydrocarbon has a carbon atom:oxygen atom ratio of 0.5:1.0 to 1.5:1.0, such as 0.75:1.0 to 0.75-1.5:1.0, such as 0.75:1.0 to 1.25:1.0.

[0044] Exemplary oxygenated compounds and process conditions applicable to AC reactions are those described in US2016 / 0108330A (Virent Inc.), the disclosure of which is incorporated herein by reference.

[0045] Preferred non-limiting examples of oxygen-containing compounds include monosaccharides, disaccharides, polysaccharides, ethers, sugars, sugar alcohols, alditols, ethylene glycol, ethylene glycol, acetic acid, propanol, propylene glycol, propionic acid, glycerol, glyceraldehyde, dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, butanediol, butyric acid, butyrose, tartaric acid, pentaldehyde, hexaldehyde, methyl ethyl ketone, pentaldehyde, hexose, alditols, hemicellulose, cellulose derivatives, lignocellulose derivatives, starch, and polyols. As described in US2016 / 0108330A, particularly in paragraphs

[0093] -

[0102] , it is sometimes preferable to convert an oxygen-containing hydrocarbon into another oxygen-containing hydrocarbon that can be more readily processed by an AC catalyst, particularly via hydrogenation.

[0046] Preferred oxygen-containing compounds as substrates for AC reactions include alcohols, ketones, aldehydes, furans, glycols, triols, hydroxycarboxylic acids, or carboxylic acids. Particularly preferred substrates include those selected from the group consisting of: methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, cyclopentanol, cyclohexanol, 2-methylcyclopentanol, hydroxy ketones, cyclic ketones, acetone, propanone, butanone, pentanone, hexanone, 2-methyl-cyclopentanone, ethylene glycol, 1,3-propanediol, propylene glycol, butanediol, pentanediol, hexanediol, methylglyoxal, butanedione, pentanedione, diketonehexane, hydroxy aldehydes, acetaldehyde, propionaldehyde, butyraldehyde, pentanol, hexanol, formic acid, acetic acid, propionic acid, butyric acid, valerate, hexanol, etc. Acids, lactic acid, glycerol, furan, tetrahydrofuran, dihydrofuran, 2-furanethanol, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-ethyl-tetrahydrofuran, 2-methylfuran, 2,5-dimethylfuran, 2-ethylfuran, hydroxymethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 5-hydroxymethyl-2(5H)-furanone, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furonic acid, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol, 1-(2-furanyl)ethanol and hydroxymethyltetrahydrofurfural, their isomers or combinations thereof. In yet another exemplary embodiment, the oxygen-containing compound further comprises recycled C 1+ O 1-3 hydrocarbon.

[0047] The product of the AC reaction contains 4 or more carbon atoms (C). 4+ The product is a compound of C. 4+ alcohols, C 4+ Ketones, C 4+ Alkanes, C 4+ Olefins, C 5+ Cycloalkanes, C 5+Cycloolefins, aryl compounds, fused aryl compounds, or mixtures thereof.

[0048] Example The invention will now be described through the following non-limiting embodiments.

[0049] Test methods BJH Measurement Full isotherms at 77 K were measured on catalyst and zeolite samples with pressure p / p0 ranging from approximately 0.000001 to 0.995 (using Ar or N2). Barrett-Joyner-Halenda (BJH) pore size and volume analysis were performed using the analytical software package MicroActive version 5.01 from Micromeritics. The thickness curve model was chosen as Harkins and Jura, and the adsorption branch of the isotherm was generally used to avoid data interruptions caused by the hysteresis loop closure at p / p0 = 0.42.

[0050] General procedures for manufacturing catalysts Alumina was placed in the mixing bowl of a paddle mixer with a slightly excess of DI water, and the solids were mixed for approximately 5 minutes. Zeolite was added to the wetted solids, and the mixture was mixed for another 5 minutes. The wetted solids were transferred to a commercial kneader with a jacketed bowl. An organic binder (hydroxyethyl cellulose) was added, and the solids were mixed for a short period. The heater supplying oil to the jacketed kneader bowl was turned on and set to a temperature of 125°C. After the solids were combined, an aqueous nitric acid solution (approximately 0.1 mol HNO3 per mol Al2O3) was added to the mixer. The solids were mixed, and DI water was added as needed. The slurry was mixed until a consistency representative of the extrudable material was obtained. The solids were extruded in a 2” OD plunger extruder equipped with four 1.8 mm diameter openings. The resulting green body was calcined at 600°C for a period of 2 hours.

[0051] The following describes a nickel-doped, calcined material. Liquid water absorption was measured on a small sample on a dry support to determine the water absorption (g). 水 / g 载体 An aqueous solution of nickel nitrate, with a volume equal to the water absorption volume of the catalyst support, is added to the support in a mixed manner. The solid is then dried and calcined at 400°C. The amount of nickel nitrate in the solution is chosen such that the Ni content after drying and calcination is equal to 1.0 wt% of the catalyst.

[0052] Material A variety of ZSM-5 samples were tested, and the ZSM-5 samples have the properties listed in Table 1. Prepare Z1 as follows: Dissolve sodium aluminate (175 g) and NaOH (225 g) in 4 L of water. Separately, dissolve tetrapropylammonium bromide (1085 g) in 4 L of water. Combine the solutions and allow them to mix. Add LUDOX. TM 6398 g of silica was placed in an autoclave, and the combined solutions were transferred to the autoclave with stirring. The autoclave was pressurized with N2 (20-25 psi) and then heated to 170 °C over 90 min, held at 170 °C for 14 h, and then allowed to cool. The material was removed from the autoclave and washed until the conductivity of the wash water was <500 µS. The filter cake was dried overnight in an oven and then crushed into a fine powder using a pestle and mortar. The powder was then calcined (incremented at 2 °C / min to 110 °C, then at 5 °C / min to 450 °C, held for 16 h, then at 5 °C / min to 550 °C, held for 16 h). After crystallization, the zeolite was washed and ion-exchanged to remove sodium.

[0053] Z2 was prepared as follows: Approximately 42 kg of water was added to a tank, followed by 280 g of tetrapropylammonium bromide as a template. To a tank containing water and TPABr, 72 kg of water glass (28.9 wt% SiO2, 8.9 wt% Na2O), 12.5 kg of aluminum sulfate (8.2% Al2O3), and 4.45 kg of sulfuric acid (93%) were added simultaneously, maintaining the pH at approximately 9.5. After adding all raw materials, the gel was transferred to a reactor and hydrothermally crystallized at a high temperature (~160°C) until the relative crystallinity of the zeolite reached 95% or higher. After crystallization, the zeolite was washed and ion-exchanged to remove sodium.

[0054] Z3 is a commercial PTF material from Hejia Chemical.

[0055] Z4 is a commercial material CBV 3024E from Zeolyst International.

[0056] Various alumina samples were tested, and the alumina samples had the properties listed in Table 2. Alumina 1 is CATAPAL A from Sasol.

[0057] Alumina 2 is from UOP's Veral TM Alumina V-250.

[0058] Alumina 3 is from Sasol's PURAL 200.

[0059] The catalyst was prepared according to a standard procedure and possesses the properties described in Table 3. Figure 1 The figure shows the relative coke yields of catalysts C1 through C10 relative to specific catalysts. There are limits to the coke × productivity performance line, which indicates that at least some of the coke is due to molecules inherent in the feed. The goal is to have catalysts that are as close as possible to the coke × productivity line and have the highest possible productivity. Catalysts C1, C3, C4, C5, C9, and C10 are close to the coke × productivity performance line.

[0060] Catalysts C6, C7, and C8 exhibit low porosity (≤ 0.06 mL / g) in the range of 20 Å–100 Å, deviating from the coke x-productivity line. It is assumed that the low mesoporosity in these materials indicates that feed molecules are trapped and converted into coke.

[0061] Although C2 has a comparable overall porosity in the 20 Å–100 Å range compared to catalysts located on the coke x-productivity line, the zeolite (Z2) used in this catalyst has a porosity of 0.03 mL / g in the 20 Å–100 Å range. This indicates that the zeolite itself must have a sufficiently high porosity in the 20 Å–100 Å range to allow feed molecules to enter and exit.

Claims

1. An acid condensation catalyst, comprising: Zeolite, with a pore size of 10 tetrahedral atoms and a concentration ≥ 0.05 mL / g in the range of 20 Å–100 Å. 沸石 The porosity and silica:alumina ratio (SAR) of 10 to 50; An alumina binder, wherein the zeolite is dispersed in the alumina binder; as well as At least one metal; The acid condensation catalyst described herein has a concentration of ≥ 0.06 mL / g in the range of 20 Å–100 Å, as measured by physical adsorption using the BJH method. 催化剂 Porosity.

2. The catalyst according to claim 1, wherein the catalyst has a concentration of 0.06 mL / g in the range of 20 Å to 100 Å. 催化剂 Up to 0.30 mL / g 催化剂 Porosity.

3. The catalyst according to claim 1, wherein the catalyst has a concentration of ≥ 0.09 mL / g in the range of 20 Å–100 Å, as measured by physical adsorption using the BJH method. 催化剂 Porosity.

4. The catalyst according to claim 3, wherein the catalyst has a concentration of 0.09 mL / g in the range of 20 Å–100 Å, as measured by physical adsorption using the BJH method. 催化剂 Up to 0.30 mL / g 催化剂 Porosity.

5. The catalyst according to any one of claims 1 to 4, wherein the catalyst has a concentration of 0.05 mL / g in the range of 100 Å to 1000 Å. 催化剂 Up to 1.0 mL / g 催化剂 Porosity.

6. The catalyst according to any one of claims 1 to 4, wherein the catalyst has a concentration of 0.20 mL / g in the range of 100 Å to 1000 Å. 催化剂 Up to 0.50 mL / g 催化剂 Porosity.

7. The catalyst according to any one of claims 1 to 6, wherein the catalyst is in the form of microspheres, microparticles or extrusions.

8. The catalyst according to any one of claims 1 to 7, wherein the zeolite has an SAR in the range of 20 to 40.

9. The catalyst according to any one of claims 1 to 8, wherein the zeolite has a ZSM-5 framework.

10. The catalyst according to any one of claims 1 to 9, wherein the alumina content is from 5 wt% to 40 wt% based on the total weight of the catalyst.

11. The catalyst according to any one of claims 1 to 10, wherein the zeolite content is from 60 wt% to 95 wt% based on the total weight of the catalyst.

12. The catalyst according to any one of claims 1 to 11, wherein the metal is nickel.

13. The catalyst according to claim 10, wherein the nickel content is 0.1 wt% to 5 wt% based on the total weight of the catalyst.

14. The catalyst according to claim 10, wherein the nickel content is 0.5 wt% to 2 wt% based on the total weight of the catalyst.

15. The catalyst according to any one of claims 1 to 14, wherein the metal is not present as a metal phosphide.

16. The catalyst according to any one of claims 1 to 15, wherein the catalyst comprises: Zeolite with a ZSM-5 framework and ≥ 0.05 mL / g in the range of 20 Å–100 Å. 沸石 The porosity and silica:alumina ratio (SAR) of the catalyst are 10 to 50, and the amount of the zeolite is equivalent to 60 wt%-95 wt% based on the total weight of the catalyst. An alumina binder, wherein the zeolite is dispersed in the alumina binder, the amount of the alumina binder being equivalent to 5 wt%-40 wt% based on the total weight of the catalyst; as well as The catalyst contains 0.1 wt%–5 wt% nickel based on its total weight; and the acid condensation catalyst has a concentration of ≥ 0.06 mL / g in the range of 20 Å–100 Å, as measured by physical adsorption using the BJH method. 催化剂 Porosity.

17. A method for manufacturing an acid condensation catalyst, comprising the following steps: (i) Combining zeolite with an alumina binder precursor, the zeolite having a pore size of 10 tetrahedral atoms, a silica:alumina ratio (SAR) of 10 to 50 and a porosity of ≥ 0.05 mL / g in the range of 20 Å to 100 Å as measured by physical adsorption using the BJH method. The alumina binder precursor is acid-gelled before or after being combined with the zeolite; (ii) Forming the mixture into particles suitable for a fixed-bed process; (iii) Calcination to convert the alumina binder precursor into alumina; as well as (iv) The product of step (iii) is impregnated with a metal salt; The catalyst is defined according to any one of claims 1 to 16.

18. The method of claim 17, wherein the zeolite has a porosity of 0.05 mL / g to 0.15 mL / g in the range of 20 Å to 100 Å.

19. The method of claim 17 or claim 18, wherein the alumina adhesive is a monobasic acid sol.

20. The method according to any one of claims 17 to 19, wherein the metal salt is a transition metal salt or a lanthanide metal salt.

21. The method according to any one of claims 17 to 20, wherein the metal salt is a nickel salt.

22. The method according to any one of claims 17 to 21, wherein the particles are in the form of microspheres, microparticles or extrusions.

23. A process for acid condensation of a feed stream containing one or more oxygen-containing compounds, wherein the method is carried out in the presence of a catalyst according to any one of claims 1 to 16.

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