Process and catalyst for conversion of methanol to hydrocarbons

Abstract

The present invention relates to an improved porous solid catalyst (C) suitable for the conversion of methanol and its derivatives to low molecular weight hydrocarbons, said porous solid catalyst (C) being based on a zeolite such as ZSM-5 and an inorganic oxide such as ceria wherein the preferred weight ratio of zeolite: inorganic oxide is from 1: 1 to 1: 5. The invention also relates to conversion processes and systems using such catalysts.

Description

Technical Field

[0001] This invention relates to catalysts suitable for converting methanol and methanol derivatives into hydrocarbons. In particular, it relates to improved zeolite catalysts suitable for methanol-to-hydrocarbons (MTH) conversion. The invention also relates to improved methods for converting methanol and methanol derivatives into hydrocarbons. Background Technology

[0002] Zeolites are microporous crystalline aluminosilicates used as catalysts in the conversion of methanol into various products such as gasoline (MTG) and olefins (MTO). In particular, ZSM-5 zeolite has shown good results in the conversion of methanol to hydrocarbons (MTH), as described, for example, in patent US 5367100. Methanol can be obtained from various feedstocks, including biomass, biochar, natural gas, and coal. Methanol conversion represents a promising pathway in current efforts to enhance the value of biomass. Importantly, methanol can be produced from carbon dioxide (CO2) and renewable hydrogen, which is an attractive route to achieving a circular carbon economy and reducing CO2 emissions. However, current MTH heterogeneous catalysts suffer inevitable activity loss during operation, primarily due to coke formation. Catalyst regeneration under harsh conditions is required, which can be costly. The necessary high temperatures above 823 K lead to degradation of active acid sites and microporous structure. Furthermore, some methanol feedstock is trapped in coke, significantly reducing product yield. Some non-zeolite catalyst components can be used to extend the life of zeolite catalysts. For this purpose, impregnation or ion exchange methods can be used. However, introducing ions into zeolites often clogs the active micropore volume and may therefore be detrimental to the activity of the catalyst.

[0003] Therefore, there is room for improvement in the properties of catalysts and related methods used in methanol-to-hydrocarbon conversion. Summary of the Invention

[0004] One object of the present invention is to provide catalysts and methods that overcome the disadvantages and limitations of the prior art.

[0005] In particular, an object of the present invention is to provide catalysts or catalytic compositions suitable for converting methanol and methanol derivatives into hydrocarbons, which have improved lifetimes under the conditions of the conversion process. Specifically, an object of the present invention is to provide catalysts or catalytic compositions with longer lifetimes at lower pressures (e.g., below 30 bar, or 10 bar, or 5 bar, or 2 bar). The lifetimes of the catalysts or catalytic compositions of the present invention are, for example, longer than 150 hours, or 200 hours, or 250 hours, or 300 hours, corresponding to the conversion of more than 10 grams, or 50 grams, 500 grams, or 20,000 grams of methanol per gram of catalyst under typical reaction conditions before a regeneration process is required.

[0006] Another object of the present invention is to provide catalysts or catalytic compositions suitable for improving the selectivity of hydrocarbon production. For example, one object is to maintain or improve selectivity for hydrocarbons (e.g., alkanes, alkenes, alkynes) having fewer than 15 carbon atoms, preferably fewer than 10, or 8, or 5 carbon atoms, more preferably 2 to 4 carbon atoms. Improved selectivity herein refers to greater than 70%, or greater than 80%, or greater than 85%, or greater than 90% or 95% of low molecular weight hydrocarbons. One object is to provide catalysts or catalytic compositions suitable for maintaining or promoting low ratios of high molecular weight hydrocarbons (e.g., polycyclic aromatic hydrocarbons and related compounds) under the conditions of a conversion process. Such a high molecular weight ratio is preferably less than 10%, or less than 5%.

[0007] Another object of the present invention is to provide a catalyst or catalytic composition having increased turn-over or improved throughput capacity, for example, more than 30 g, 50 g, 500 g, 700 g, 900 g, 1000 g, 1500 g, or 20000 g of methanol per gram of catalyst or catalytic composition.

[0008] Another object of the present invention is to provide a catalyst or catalytic composition having improved stability under conversion and / or regeneration conditions.

[0009] Another object of the present invention is to provide a method for converting methanol and methanol derivatives into hydrocarbons, particularly into low molecular weight hydrocarbons. Another object is to provide an improved and less costly method for converting methanol and methanol derivatives into such hydrocarbons.

[0010] According to the invention, these objectives are achieved by the subject matter of the independent claims and are further defined by their dependent claims.

[0011] Compared to what is known in the art, the present invention provides the advantage of more selective and / or more sustainable catalysis for the conversion of methanol and related products. Attached Figure Description

[0012] Exemplary embodiments of the present invention are disclosed in the specification and illustrated by the following drawings:

[0013] Figure 1a The graph shows an enhancement in lifetime of a mixed oxide zeolite (MOZ) catalyst according to an embodiment of the present invention compared to the prior art.

[0014] Figure 1bThe figure shows the extended lifetime of unstable zeolite mixed with inorganic oxides according to one embodiment of the present invention under hydrogen co-feed, compared with the prior art.

[0015] Figure 2 : A diagram showing the regeneration of a catalyst according to an embodiment of the present invention compared to the prior art.

[0016] Figure 3a : This figure shows the improvement of zeolite treatment capacity using CeO2.

[0017] Figure 3b The diagram illustrates the selective distribution of low molecular weight hydrocarbons by a catalyst according to one embodiment of the present invention, compared to the prior art.

[0018] Figure 4a : A graph showing the life enhancement of a bulk mixed oxide zeolite according to an embodiment of the present invention.

[0019] Figure 4b : A graph showing the enhanced lifetime of a zeolite combined with a supported inorganic oxide according to an embodiment of the present invention.

[0020] Figure 5 Comparison of lifetime enhancement of bulk mixed oxide zeolites and zeolites combined with supported inorganic oxides according to the present disclosure.

[0021] Figure 6 : A schematic diagram of a reactor applicable to methanol conversion based on the present disclosure. Detailed Implementation

[0022] According to one aspect, this disclosure relates to acidic zeolite catalysts or catalytic compositions for converting methanol or methanol derivatives into hydrocarbons.

[0023] The term methanol derivative refers to compounds that have similar properties to methanol. Methanol derivatives involve compounds having one carbon atom and a heteroatom selected from oxygen, sulfur, nitrogen, and halogens (e.g., fluorine, chlorine, iodine, and bromine). Methanol derivatives include CH3Cl, CH3Br, CH3F, CH3I, CH3NH2, CH3SH, CH2O, CH2S, CHCl2, CHCl3, CCl4, and related compounds. The term methanol derivative also includes compounds having one carbon atom and a functional group containing a heteroatom and another carbon atom, such as dimethyl ether (CH3OCH3) and dimethylamine ((CH3)2NH).

[0024] Zeolite here refers to a substance based on silicon, aluminum, and oxygen, and containing a variable number of protons (H) that participate in the catalytic reaction. + Microporous crystalline materials. Zeolites are characterized by their composition and porosity. They are also used as molecular sieves. Examples of zeolites include ZSM zeolites, such as ZSM-1, ZSM-4, ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-30, ZSM-34, ZSM-48, ZSM-50, ZSM-57, and ZSM-58, plus Sigma-1 and ITQ-3 zeolites, and SAPO molecular sieves, such as SAPO-5, SAPO-8, SAPO-11, SAPO-14, SAPO-16, SAPO-17, SAPO-18, and SAPO-2. 0. SAPO-31, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-57, SAPO-56, SA PO-59, STA-6, AIPO molecular sieves, such as AIPO-5, AIPO-11, AIPO-18, AIPO-18, AIPO-31, AIPO-34, AIPO-36, AIPO-37, AIPO-46. and less stable zeolites such as ITQ-13, ITQ-33, SUZ-4, MCM-22, EU-1, UZM-9, UZM-12, SAT-7, ZK-5, RHO, RUB-13, UZ M-5, SSZ-13, SSZ-16, SSZ-24, SSZ-39, SSZ-52, SSZ-98, BETA, ZSM-35, FAU, ZSM-22, BEA, USY and MOR.

[0025] According to one embodiment, the catalyst or catalytic composition of the present invention comprises ZSM-5 or ZSM-11 or a combination thereof, more preferably ZSM-5 alone. ZSM-5 includes ZSM-5(25) with a Si / Al ratio of 25 and ZSM-5(40) with a Si / Al ratio of 40. Other Si / Al ratios are conceivable.

[0026] According to another embodiment, the catalyst or catalytic composition of this disclosure comprises SSZ-13, BETA, FAU, ZSM-22, ZSM-35, BEA, USY and MOR or a combination thereof as zeolite.

[0027] The term "catalyst" herein refers to a combination of pure zeolite or a mixture of zeolites with at least one inorganic oxide (e.g., a metal oxide), thereby defining a catalytic composition. Preferably, the catalyst of the present invention is homogeneously prepared, meaning that its structure (including its porosity) and its composition are identical throughout its volume. The catalyst is preferably prepared as beads, powder, or slurry, which may be free or supported on a solid carrier. The catalyst can be in the form of millimeter-sized beads or extrusions, micrometer-sized beads, or powders with a particle size of less than one micrometer. Therefore, the catalyst of the present invention is preferably a microporous solid catalyst.

[0028] Inorganic oxides are derived from the single oxide, dioxide, trioxide, and tetroxide of one of the alkali metals, alkaline earth metals, rare earth metals, and transition metals. Inorganic oxides represent, for example, the single oxides, dioxides, trioxides, or tetroxides of lanthanide elements (e.g., lanthanum, cerium, praseodymium, ytterbium). Inorganic oxides include Sm₂O₃, Y₂O₃, La₂O₃, MgO, CaO, ZrO₂, CeO₂, Ce₂O₃, Mo₂O₃, SrO, BaO, Eu₂O₃, Pr₂O₃, Nd₂O₃, Pm₂O₃, Tb₂O₃, Dy₂O₃, Ho₂O₃, Er₂O₃, SnO₂, ZnO, Mo₂O₃, SiO₂, Al₂O₃, TiO₂, or mixtures thereof, or doped forms thereof, wherein the dopant is one or more alkali metals, alkaline earth metals, transition metals, or rare earth metals.

[0029] It has been found that, under the same or similar conditions, combinations of one or more zeolites according to this disclosure with at least one inorganic oxide can improve the lifetime of a catalyst or catalytic composition. Such combinations, for example, increase lifetime by more than 2, 3, 5, 10, or 20 times compared to the corresponding zeolite without the inorganic oxide. Depending on the nature of the inorganic oxide and / or its ratio to the zeolite, lifetime can be increased by 3 to 56 times, such as 10 to 56 times, compared to the zeolite alone.

[0030] It has been found that, under the same or similar conditions, a combination of one or more zeolites according to this disclosure with at least one inorganic oxide allows for a reduction in the formation of aromatic compounds compared to using zeolites alone. Simultaneously, the selectivity for low molecular weight compounds remains the same or similar to, or is improved, compared to the corresponding values ​​obtained with zeolites alone.

[0031] Further findings indicate that combinations of one or more zeolites, as described herein, with at least one inorganic oxide enhance the rate of coke oxidation under regeneration conditions. For zeolites without inorganic oxides, regeneration conditions typically require temperatures above about 820 K. According to the invention, the regeneration of the catalyst or catalytic composition can occur at temperatures below 820 K, or below 600 K, or below 400 K. In one particular embodiment, the catalyst regeneration temperature can be from 550 K to 770 K. The energy consumed in regeneration is thus reduced. Furthermore, the catalyst or catalytic composition is better protected during the regeneration process and can withstand more regeneration cycles. This further allows for the use of less common zeolites that are not sufficiently stable under other conversion conditions.

[0032] It has also been found that, according to this disclosure, the stability of less stable zeolites, particularly those such as SSZ-13, BETA, ZSM-35, FAU, ZSM-22, BEA, USY, and MOR, can be improved when combined with at least one inorganic oxide. As a result, the lifespan of such zeolites is improved by at least 4 to 56 times compared to zeolites without inorganic oxides. This greater variety of available zeolites provides greater flexibility in the conversion of methanol and methanol derivatives. For example, by making one of these less stable zeolites available, improved selectivity can be obtained for a class of compounds, such as alkenes having 3 to 5 carbon atoms.

[0033] According to one embodiment, zeolite is mixed with one or more inorganic oxides to provide a homogeneous formulation. A suitable amount of zeolite (comprising one or more zeolites) is mixed with a suitable amount of one or more inorganic oxides and treated to provide a homogeneous solid catalyst. The treatment includes mechanical processing, such as crushing, pressing, and sieving the combined materials. Alternatively or additionally, the treatment may include thermal operations, such as heating at a suitable temperature. Alternatively or additionally, the treatment may include chemical treatment, such as washing in water or other solvents (e.g., polar or non-polar solvents). The treatment may also include a crystallization step if necessary. Preferably, the catalyst or catalytic composition does not contain organic additives or organometallic additives. Preferably, the catalyst or catalytic composition is free of phosphorus, phosphorus oxides, and phosphorus derivatives. The resulting catalyst or catalytic composition is a mixed oxide zeolite (MOZ) in which zeolite and inorganic oxides are mixed in bulk.

[0034] Alternatively, one or more inorganic oxides may be supported by a zeolite catalyst, or by a zeolite in the presence of several zeolites, or by another support such as a secondary inorganic oxide.

[0035] According to one implementation scheme, a zeolite is combined with only one inorganic oxide.

[0036] According to another embodiment, a zeolite is combined with several inorganic oxides, including a primary inorganic oxide and a secondary inorganic oxide. The primary inorganic oxide may account for 0.1% to 90% by weight of the inorganic oxides in the catalyst or catalytic composition. Alternatively, the primary inorganic oxide may account for less than 30%, 20%, or 10% by weight of the inorganic oxides.

[0037] The primary inorganic oxide is understood to provide at least one of the aforementioned advantages, particularly improved lifetime, improved conversion rate or processing capacity, improved stability, improved selectivity, and improved regeneration. Preferably, the primary inorganic oxide is selected to provide some or all of the aforementioned advantages in combination.

[0038] Secondary inorganic oxides are understood to be less advantageous than primary inorganic oxides in terms of some or all of the aforementioned benefits when replacing primary inorganic oxides. Secondary inorganic oxides can be selected based on their cost, preferably lower than that of primary inorganic oxides. The ratio between primary and secondary inorganic oxides is chosen such that no loss of properties is observed compared to primary inorganic oxides alone. In particular, it has been observed that, under conversion process conditions, only 10% to 20% by weight of primary inorganic oxide can produce the same advantages as 100% primary inorganic oxide. Therefore, the combination of primary and secondary inorganic oxides allows for the provision of cheaper catalysts without loss or significant loss of benefits.

[0039] According to one implementation, secondary inorganic oxides offer little or no benefit compared to primary inorganic oxides. In this case, secondary inorganic oxides are used as supports or carriers for primary inorganic oxides.

[0040] According to another embodiment, compared to the primary inorganic oxide, the secondary inorganic oxide exhibits some benefits in one or only some of the aforementioned aspects of the conversion process, but limited or no benefits in others. For example, the secondary inorganic oxide allows for improved regeneration processes, while the primary inorganic oxide allows for improvements in several or all of the lifetime, stability, selectivity, and conversion rate of the catalyst or catalytic composition. Therefore, the primary and secondary inorganic oxides have complementary advantages, which provides greater overall benefit.

[0041] According to one implementation, compared to using only the primary inorganic oxide, a combination of the primary and secondary inorganic oxides allows for the improvement of at least one of the aforementioned advantages. Therefore, the combination of the two inorganic oxides provides a synergistic beneficial effect.

[0042] The secondary inorganic oxides can be selected from the cheapest compounds, such as SiO2, Al2O3, TiO2, MgO, CaO, and ZrO2, or from more expensive compounds that have shown some benefits, such as Y2O3, La2O3, or Sm2O3, or other inorganic oxides. Mixtures of secondary inorganic oxides in different ratios can be envisioned to better tune the advantages without loss or significant loss.

[0043] The primary inorganic oxide is preferably selected from CeO2, Y2O3, Sm2O3, or La2O3. CeO2 is more preferred.

[0044] In the catalyst or catalytic composition according to the invention, the ratio of zeolite to inorganic oxide is selected from 100:1 to 1:5 by weight. Therefore, the zeolite / inorganic oxide ratio is 100 / 1, 10 / 1, 1 / 1, 1 / 2, 1 / 3, 1 / 4, 1 / 5, or any intermediate value.

[0045] According to one embodiment, the zeolite is selected from ZSM-5, SSZ-13, BETA, ZSM-35, FAU, ZSM-22, BEA, USY and MOR, or mixtures thereof, and the primary inorganic oxide is CeO2 alone or a combination of secondary inorganic oxides selected from MgO, ZrO2, CaO, Y2O3, Sm2O3 or La2O3 or mixtures thereof with CeO2.

[0046] According to one embodiment, the inorganic oxide comprises CeO2 as the primary inorganic oxide and ZrO2 or MgO as a secondary inorganic oxide in a ratio of 10 / 90, 20 / 80, 70 / 30, 5 / 95, or 1 / 99 by weight.

[0047] The present invention also relates to a method for converting methanol and methanol derivatives into hydrocarbons, particularly low molecular weight hydrocarbons, using a catalyst or catalytic composition according to the present disclosure.

[0048] The conversion method includes the step of filling conversion chamber 1 with a suitable amount of catalyst or catalytic composition C. Figure 6 The catalyst or catalytic composition C is one of the above compositions or a mixture thereof in any suitable ratio. Suitable amounts may range from a few grams to more than 1 kg or more than 10 kg of catalyst, as needed. The weighed catalyst C is arranged in a solid material (as powder or as beads with a diameter of micrometers or millimeters) in the conversion chamber. Preferably, it is arranged on a support that allows good contact between the feed gas and the catalyst C. For example, 1 kg of catalyst or catalytic composition C may be arranged to convert more than 400 kg, or more than 500 kg, or more than 600 kg, or more than 10,000 kg of methanol or methanol derivatives in each conversion cycle. A conversion cycle is defined here as the process between two consecutive regenerations of the catalyst.

[0049] The method includes the step of feeding methanol or a methanol derivative into conversion chamber 1. Feeding is carried out through at least one inlet 10 at a suitable pressure. According to one embodiment, the feeding of methanol or a methanol derivative is carried out at atmospheric pressure. Alternatively, it occurs at a slight overpressure of 1.1 bar to 5 bar, preferably 1.2 bar to 3 bar or 4 bar, preferably less than 2 bar. Inlet 10 is defined herein as any suitable device suitable for feeding methanol. It can be, for example, a nozzle, a syringe, or any equivalent. The feeding of methanol can be carried out at a predetermined temperature, such as room temperature or a temperature of 50 K to 900 K, for example 50 K to 100 K, or 150 K to 300 K, or above 350 K. For this purpose, the method may include the step of preheating the methanol at a suitable temperature before feeding it into the conversion chamber. Alternatively, the methanol or methanol derivative is fed into a heated conversion chamber at room temperature such that it is heated to a suitable temperature immediately or almost immediately during the process. Alternatively, a step of preheating the methanol or methanol derivative at an intermediate temperature before feeding it into conversion chamber 1 is conceivable. Methanol or methanol derivatives can be fed into the conversion chamber 1 through one or more first pipelines L1 suitable for transferring methanol or methanol derivatives from the first storage tank R1 to the conversion chamber 1.

[0050] The method includes the step of co-feeding an inert gas, such as argon or nitrogen, into the conversion chamber 1. According to one embodiment, methanol or a methanol derivative and the inert gas are mixed in an appropriate ratio before being fed into the conversion chamber 1. For this purpose, the necessary pumps and mixing units are provided. Other alternatives are possible.

[0051] The method includes the optional step of co-feeding methanol or a methanol derivative with hydrogen at a suitable flow rate.

[0052] The method includes the step of contacting methanol or a methanol derivative fed into conversion chamber 1 with a catalyst or catalytic composition C to carry out conversion. Contact can be static, wherein the flow of methanol or a methanol derivative passes through a fixed bed of catalyst or catalytic composition C. Contact can also be accomplished using a fluidized bed or a moving bed of catalyst. Alternatively, mechanical stirring can be implemented to improve the reaction. Conversion occurs within conversion chamber 1 at suitable pressure and temperature. Preferably, conversion occurs at a pressure below 5 bar, or 3 bar, or 2 bar. The conversion temperature is, as needed, from 50 K to 900 K, preferably from 450 K to 820 K.

[0053] The method includes the step of collecting hydrocarbon fractions produced by the conversion from conversion chamber 1. Collection of the hydrocarbon fractions can be carried out through one or more outlets. One or more condensation, cooling, and filtration steps can be implemented as needed to collect the final hydrocarbon fractions. According to one embodiment, the collected hydrocarbon fractions represent olefins having 2 to 5, 3 to 5, or 3 to 6 carbon atoms, with a selectivity greater than 70%, 75%, 80%, and up to 90%. The hydrocarbon fractions can be collected into one or more storage tanks R3 through one or more collection lines L3. The hydrocarbons can be analyzed online or offline to determine the conversion profile or changes in the conversion profile.

[0054] According to one implementation scheme, the conversion method is a continuous process, meaning that methanol or methanol derivatives are continuously fed into conversion chamber 1 while suitable hydrocarbon fractions are continuously collected. The temperature and pressure within the conversion chamber are controlled to carry out the conversion.

[0055] During the method, some or all parameters can be predetermined according to the expected results, including conversion pressure, temperature pressure, methanol flow rate, inert gas flow rate, co-feed gas flow rate, methanol to inert gas ratio, and the applicable co-feed gas. These parameters, or some of them, can be adjusted according to the catalyst or catalytic composition C. Alternatively, one or more of these parameters can be automatically adjusted based on corresponding values ​​detected online by suitable sensors according to a predetermined algorithm.

[0056] The method may include a step of regenerating catalyst C after the catalyst or catalytic composition has reached a predetermined cumulative conversion capacity. Alternatively, a regeneration step may be triggered when selective degradation of the desired hydrocarbon fraction or a change in the conversion profile is detected. The regeneration step includes feeding oxygen into conversion chamber 1 at a suitable regeneration temperature. Depending on the catalyst or catalytic composition C used, the regeneration temperature may be from 50 K to 900 K, preferably from 670 K to 850 K. The regeneration step defines the end of a conversion cycle and the beginning of a new conversion cycle. After the regeneration step, the steps of feeding methanol or methanol derivatives, performing conversion, and collecting hydrocarbon fractions as described above may be repeated.

[0057] The method includes the step of replacing the catalyst or catalytic composition C in conversion chamber 1 after partial or complete irreversible loss of activity. According to one embodiment, the catalyst or catalytic composition described herein can participate in more than 10, or more than 15, or more than 20, or more than 30, or more than 50 conversion cycles before being replaced.

[0058] The present invention also relates to a system S comprising a conversion unit and a catalyst or catalytic composition C as described herein. Figure 6System S includes a conversion unit suitable for converting methanol or methanol derivatives into hydrocarbons and a suitable amount of the catalyst or catalytic composition C described herein. The conversion unit includes a conversion chamber 1 provided with at least one inlet 10, 20 suitable for feeding methanol or methanol derivatives into the conversion chamber under suitable temperature and pressure conditions. Methanol or methanol derivatives may be stored in a first tank or reservoir R1 and supplied to the conversion chamber 1 via at least one first pipeline L1 and a necessary first pump P1. The conversion unit includes at least one means for supplying one or more gases (e.g., inert gases or co-feed gases). For this purpose, the conversion unit may include one or more gas tanks or reservoirs R2 and corresponding gas pipelines or conduits L2 suitable for supplying gases to the conversion chamber 1. One or more adapted pumps P2 may be implemented.

[0059] The conversion unit may include one or more intermediate units 40 upstream of the conversion chamber 1, adapted to prepare a feed mixture comprising methanol or a methanol derivative prior to conversion. One or more intermediate units 40 may be adapted to one or more of the following operations:

[0060] - Mix methanol or methanol derivatives with one or more inert gases in a suitable ratio (e.g., MeOH / inert gas = 90 / 10, 80 / 20, or 10 / 90) to provide a premixed gas;

[0061] - Mix the co-feed gas (e.g., hydrogen or hydrocarbon) with methanol or methanol derivatives or with premixed gas in a suitable proportion;

[0062] - Preheat the premixed gas and / or methanol and / or co-feed gas at a suitable temperature;

[0063] - Compress the premixed gas and / or methanol and / or co-feed gas at a suitable pressure;

[0064] - Control the flow rate of methanol and / or premixed gas and / or co-feed gas;

[0065] The conversion unit also includes one or more collection lines L3 downstream of the conversion chamber 1 and corresponding outlets to collect the converted hydrocarbon fractions. The hydrocarbons can be stored in one or more dedicated storage tanks R3.

[0066] The conversion unit may include one or more sensors such as pressure sensors, temperature sensors, liquid or gas detection and analysis devices (e.g., hydrocarbon mass detectors), and any suitable equipment.

[0067] The conversion unit may also include local or remote control devices, including digital devices, computing devices, signal processing devices, data communication devices, and any related equipment.

[0068] Example

[0069] The ZSM-5 catalyst was prepared according to a known procedure. For example, ZSM-5 zeolite with a Si / Al ratio of approximately 45 was prepared using TPAOH. Tetraethyl orthosilicate and Al2(SO4)3x18H2O were used as the silicon and aluminum sources, respectively. The composition of the synthesized gel was as follows: Al2O3:H2SO4:Na2O:TPAOH:SiO2:H2O=1:3:4.6:25:100:1250. The synthesized gel was aged at room temperature for 24 hours, then transferred to a PTFE-lined stainless steel autoclave and hydrothermally crystallized at 443 K under tumbling (30 rpm) for 1 day. The synthesized sample was calcined at 823 K in dry air for 5 hours to remove the structure-directing agent. The calcined zeolite was ion-exchanged three times in a 0.1 M NH4NO3 aqueous solution, and then calcined at 823 K for 5 hours to obtain the protonated form.

[0070] Bulk MOZ catalyst was prepared by mixing 0.2 g of ZSM-5 catalyst with 0.2 g of ZSM-5 catalyst at a Si / Al ratio of 40. The powder was weighed on a balance, transferred to a mixing mortar, and mixed with a pestle for 2 minutes, with powder periodically removed from the wall. Subsequently, the powder was transferred to a mold and pressed at 2 tons for 2 minutes. Finally, the catalyst was pulverized and sieved to the desired particle size.

[0071] For supported oxides, Ce(NO3)3x6H2O (2.52 g) was dissolved in H2O (2 g). The solution was dispersed on TiO2 (10 g). The resulting solid was dried at 373 K under vacuum (50 mbar) for 12 h, and then calcined at 823 K for 5 h. The corresponding MOZs were obtained by following the same procedure as described for bulk MOZs.

[0072] Example 1a: Conversion vs Cumulative Conversion Capacity

[0073] A catalyst based on zeolite ZSM-5(25) with a Si / Al ratio of 25 was mixed with CeO2 or Y2O3 at different ratios to provide mixed oxide zeolite (MOZ). For the compositions in Table 1a below, the conversion (X) as defined in % vs. the number of grams of methanol per gram of catalyst (g) was determined. 甲醇 g 催化剂 -1 The cumulative turnover (CT) is defined as follows. The corresponding values ​​are shown in... Figure 1a middle.

[0074] Lifetime enhancement (LTE) is defined by the ratio between the cumulative conversion (CT) capacity of the mixed oxide zeolite (MOZ) and the cumulative conversion (CT) capacity of the respective individual zeolite.

[0075] Apply the following conditions:

[0076] Methanol flow rate per gram of catalyst (WHSV) = 44 g 甲醇 g 催化剂 -1 Hour -1 ,

[0077] Methanol concentration in argon: CH3OH:Ar = 11:89 mol%

[0078] Temperature T=673 K

[0079] Pressure p = 1.5 bar

[0080] Table 1a

[0081]

[0082] Mixing ZSM-5 zeolite with CeO2 increased the lifetime by approximately 3.2 to approximately 41 times. Compared to Y2O3, the beneficial effects of CeO2 were significantly improved.

[0083] Example 1b: Conversion vs Cumulative Conversion Capacity with Hydrogen Co-Feed

[0084] A catalyst based on zeolite ZSM-5(40) with a Si / Al ratio of 40 was mixed with CeO2 at a given ratio to provide a mixed oxide zeolite (MOZ). For the compositions in Table 1b below, the conversion (X) as defined in % vs. the number of grams of methanol per gram of catalyst was determined under various concentrations of hydrogen (H2). 甲醇 g 催化剂 -1 The cumulative conversion capacity (CT) is defined as follows. The corresponding values ​​are shown in... Figure 1b middle.

[0085] Lifetime enhancement (LTE) is defined as the ratio between the cumulative conversion capacity (CT) of the mixed oxide zeolite (MOZ) under hydrogen co-feed and the cumulative conversion capacity (CT) of the corresponding MOZ in the absence of hydrogen. The corresponding values ​​are shown in... Figure 1b middle.

[0086] Apply the following conditions:

[0087] Methanol flow rate per gram of catalyst (WHSV) = 76 g 甲醇 g 催化剂 -1 Hour -1 ,

[0088] The concentration of methanol in the argon and hydrogen co-feed: CH3OH:Ar:H2 = 20:(80 / 60 / 0):(0 / 20 / 80) mol%

[0089] Temperature T=773 K

[0090] Pressure p = 1.6 bar

[0091] Table 1b

[0092]

[0093] Adding hydrogen as a co-feed to the MOZ catalyst improves catalyst lifetime, even at pressures below 2 bar.

[0094] Example 2: Regeneration of Catalysts

[0095] The catalyst deactivated by methanol-to-hydrocarbon conversion under standard conditions was subjected to a high-temperature regeneration process. The oxidative regeneration of the catalyst based on ZSM-5(25):CeO2 1:5 (composition C3) was tracked by thermogravimetric analysis and compared with the corresponding individual zeolite (composition C1). The corresponding results are provided in... Figure 2 middle.

[0096] Compared to the corresponding individual zeolites, the oxidation of coke in the MOZ catalyst occurs at significantly lower temperatures, above 530 K.

[0097] Example 3a: Lifetime Extension of Different Zeolites with Ce02

[0098] Various zeolite-based catalysts were used in methanol-to-hydrocarbon conversion in the absence of CeO2 and as MOZ when mixed with CeO2 at a zeolite:CeO2 ratio of 1:1. For the compositions in Table 3a below, the conversion (X) as a percentage was determined vs. the number of grams of methanol per gram of catalyst (g). 甲醇 g 催化剂 -1 The cumulative conversion capacity (CT) is defined as follows. The corresponding values ​​are shown in... Figure 3a middle.

[0099] Lifetime enhancement (LTE) is defined by the ratio between the cumulative conversion capacity (CT) of the mixed oxide zeolite (MOZ) and the cumulative conversion capacity (CT) of the corresponding individual zeolite.

[0100] Apply the following conditions:

[0101] Methanol flow rate per gram of catalyst

[0102] WHSV=4.8 g 甲醇 g 催化剂-1 Hour -1 (C10a, C10b, C11a, C11b),

[0103] WHSV=9.6 g 甲醇 g 催化剂 -1 Hour -1 (C12a, C12b, C13a, C13b, C14a, C14b),

[0104] WHSV=19 g 甲醇 g 催化剂 -1 Hour -1 (C9a, C9b).

[0105] The ratio of methanol in argon:

[0106] CH3OH:Ar = 11:89 (C10a, C10b, C11a, C11b, C12a, C12b, C13a, C13b, C14a, C14b) or

[0107] CH3OH:Ar=5.6:94.4 (C9a, C9b) mol%

[0108] temperature

[0109] T = 773 K (C13a, C13b).

[0110] T = 723 K (C12a, C12b).

[0111] T=673 K (C14a, C14b, C12a, C12b, C11a, C11b, C10a, C10b, C9a, C9b)

[0112] Pressure p = 1.6 bar

[0113] Table 3a

[0114]

[0115] When mixed with CeO2, the lifetime of unstable zeolites increases significantly.

[0116] Example 3b: Selectivity of ZSM-35 and ZSM-5 based catalysts for C3 to C5 olefins

[0117] Catalysts ZSM-35(10):CeO2 1:1 (composition C11b) and ZSM-5(40) alone (composition C5) were used in the methanol-to-hydrocarbon conversion process under the same conditions. For both catalysts, C3H6(H1), C4H8(H2), and C5H were tracked. 10(H3) Hydrocarbon conversion (S), defined as a percentage. The corresponding results are shown in... Figure 3b middle.

[0118] Example 4a: Lifetime Enhancement of Bulk Oxide Zeolites

[0119] Under methanol-to-hydrocarbon conversion conditions, the maximum cumulative conversion capacity of a catalyst based on a mixture of ZSM-5(40) and various inorganic oxides in a ZSM-5(40):oxide ratio of 1:1 (except for CaO, where the ratio is 1:0.1) as a bulk mixture was determined.

[0120] Lifetime enhancement (LTE) is defined as the ratio between the cumulative conversion capacity (CT) of the mixed oxide zeolite (MOZ) and the cumulative conversion capacity (CT) of the respective individual zeolite. The corresponding results are provided in Table 4a below. Figure 4a middle:

[0121] Apply the following conditions:

[0122] Methanol flow rate per gram of catalyst (WHSV) = 76 g 甲醇 g 催化剂 -1 Hour -1 ,

[0123] The ratio of methanol in argon gas is: CH3OH:Ar = 20:80 mol%.

[0124] Temperature T=773 K

[0125] Pressure p = 1.6 bar

[0126] Table 4a

[0127]

[0128] While the best lifetime enhancement was achieved with CeO2, several other oxides also exhibited significant lifetime enhancement.

[0129] Example 4b: Lifetime Enhancement of Zeolites with Supported Oxides

[0130] Under methanol-to-hydrocarbon conversion conditions, the maximum cumulative conversion capacity of catalysts based on ZSM-5(40) combined with CeO2 supported on various supports was determined. The ratio of ZSM-5(40):oxides was 1:1, taking into account the total amount of oxides. The amount of CeO2 in the oxides was 10% by weight.

[0131] The conditions are the same as those in Example 4a.

[0132] Lifetime enhancement (LTE) is defined as the ratio between the cumulative conversion capacity (CT) of the zeolite combined with CeO2-loaded zeolite and the cumulative conversion capacity (CT) of the respective individual zeolite. The corresponding results are provided in Table 4b below. Figure 4b middle:

[0133] Table 4b

[0134]

[0135] Even with reduced amounts of loaded main oxide, the lifetime enhancement remains significant.

[0136] Example 5: Lifetime Enhancement Comparison of Zeolites with Supported Oxides

[0137] Under methanol-to-hydrocarbon conversion conditions, the maximum cumulative conversion capacity of the catalyst was determined. Examples C27 and C28 represent catalysts prepared by loading CeO2 onto ZSM-5 at two different loading rates of 1 wt% and 10 wt%.

[0138] Lifetime enhancement (LTE) is defined by the ratio between the cumulative conversion capacity (CT) of catalysts prepared on ZSM-5 with two different loading amounts of CeO2, 1 wt% and 10 wt%. The corresponding results are provided in Table 5 below. Figure 5 middle.

[0139] Apply the following conditions:

[0140] Methanol flow rate per gram of catalyst (WHSV) = 76 g 甲醇 g 催化剂 -1 Hour -1 ,

[0141] Methanol concentration in argon: CH3OH:Ar = 20:80 mol%

[0142] Temperature T=773 K

[0143] Pressure p = 1.6 bar

[0144] Table 5

[0145]

[0146] The hybrid preparation method produces better performance than the conventional method of using CeO2-supported / impregnated zeolite.

Claims

1. A porous solid catalyst or catalytic composition (C) suitable for converting methanol and / or methanol derivatives into low molecular weight hydrocarbons having 2 to 15 carbon atoms, comprising: - Selected from one or more of the following zeolites: ZSM-57, ZSM-58, Sigma-1, ITQ-3, ITQ-13, ITQ-33, SUZ-4, MCM-22, EU-1, UZM-9, UZM-12, SAT-7, ZK-5, RHO, RUB-13, UZM-5, SSZ-16, SSZ-24, SSZ-39, SSZ-52, SSZ-98, ZSM-5, ZSM-11, SSZ-13, BETA, ZSM-35, FAU, ZSM-22, BEA, USY, and MOR, or mixtures thereof. - Selected from at least one inorganic oxide from the following: alkali metals, alkaline earth metals, rare earth metals, and transition metals in monooxide, dioxide, trioxide, and tetroxide forms, such as Sm₂O₃, Y₂O₃, La₂O₃, MgO, CaO, SrO, BaO, ZrO₂, CeO₂, Eu₂O₃, Pr₂O₃, Nd₂O₃, Pm₂O₃, Tb₂O₃, Dy₂O₃, Ho₂O₃, Er₂O₃, SnO₂, ZnO, Mo₂O₃, SiO₂, Al₂O₃, TiO₂, or mixtures thereof, or doped forms thereof, wherein the dopant is one or more alkali metals, alkaline earth metals, transition metals, or rare earth metals. Its features are, The ratio of zeolite to inorganic oxide is 100:1 to 1:50, preferably 1:1 to 1:

5.

2. The porous catalyst or catalytic composition according to claim 1, wherein the inorganic oxide comprises CeO2 alone, or a combination of one or more of SiO2, Al2O3, TiO2, Sm2O3, Y2O3, La2O3, MgO, CaO, ZrO2, Mo2O3 and CeO2.

3. The porous solid catalyst or catalytic composition according to claim 1, wherein the zeolite or mixture thereof is mixed with the inorganic oxide or mixture thereof in bulk to provide mixed oxide zeolite (MOZ).

4. The porous solid catalyst or catalytic composition according to claim 1, wherein the oxide or mixture thereof is combined with the zeolite or mixture thereof as a supported inorganic oxide, and the oxide or mixture thereof comprises a primary inorganic oxide and a secondary inorganic oxide in a ratio of primary inorganic oxide to secondary inorganic oxide of 1 / 99 to 49 / 51, wherein the secondary inorganic oxide is selected from SiO2, Al2O3, TiO2, MgO, ZrO2, CaO, or mixtures thereof, and wherein the primary inorganic oxide is selected from CeO2, Y2O3, Sm2O3 or La2O3, preferably CeO2.

5. The porous solid catalyst or catalytic composition according to claim 4, wherein the supported inorganic oxide comprises 1 wt%, 10 wt%, or 20 wt%, or 50 wt%, or 80 wt% CeO2 and a support, wherein the support is selected from SiO2, Al2O3, TiO2, ZrO2, Nb2O5, Ta2O5, mesoporous and microporous silicates and aluminosilicates, or mixtures thereof.

6. The porous solid catalyst or catalytic composition according to any one of claims 1 to 5, wherein the zeolite is selected from ZSM-5(x), BEA(x), SSZ-13(x), ZSM-35(x), USY(x), ZSM-22(x) and MOR(x), where x defines the Si / Al ratio and is equal to 1, 10, 15, 19, 25, 40, 80, 200 or 1000.

7. The porous solid catalyst or catalytic composition according to claims 1 to 6, wherein the zeolite is selected from ZSM-5 (25), ZSM-5 (40), BEA (19), SSZ-13 (10), SSZ-13 (10), ZSM-35 (10), USY (40), ZSM-22 (40) and MOR (15).

8. The porous solid catalyst or catalytic composition according to claims 1 to 7, wherein the catalyst or catalytic composition is one of the following: 。 9. A method for converting methanol or methanol derivatives into low molecular weight hydrocarbons, comprising the following steps: - (E1) to make a certain amount of methanol or methanol derivative (Q) MeOH ) and a suitable amount of the catalyst or catalytic composition according to any one of claims 1 to 8 (Q) C The methanol or methanol derivative is contacted at a conversion temperature (Tcv) and a conversion pressure (pcv) to convert the methanol or methanol derivative into a hydrocarbon having 2 to 12, preferably 2 to 5, carbon atoms, such as an olefin, during the conversion cycle. - (E2) At the end of the conversion cycle, the appropriate amount of catalyst or catalytic composition (Q) is released. C Regeneration is performed at regeneration temperature (Tr) and regeneration pressure (Pr), and - Repeat steps (E1) and (E2) at least 10, 15, 20, 25, or 30 times.

10. The method of claim 9, wherein the methanol or methanol derivative is combined with an inert gas, such as argon or nitrogen, in a methanol / gas weight ratio of 10 / 90, 20 / 80, 70 / 30, or 99 / 1.

11. The method according to any one of claims 9 and 10, wherein the methanol or methanol derivative is co-fed with hydrogen (H2) and / or additional co-feeds such as water (steam) or hydrocarbons.

12. The method according to any one of claims 9 to 11, wherein the stated amount of methanol or a methanol derivative (Q) is... MeOH ) and the appropriate amount of catalyst or catalytic composition (Q) C The constraint is such that, for the conversion cycle, the weight ratio Q is... MeOH / Q C Greater than 400 / 1, or 500 / 1, or 600 / 1, or 1000 / 1.

13. The method according to any one of claims 9 to 12, wherein the conversion temperature (Tcv) is less than 850 K, or less than 600 K, or less than 400 K, and wherein the conversion pressure (pcv) is less than 30 bar, 10 bar, 5 bar, or 4 bar, or 3 bar, or 2 bar.

14. The method according to any one of claims 9 to 13, wherein the regeneration temperature (Tr) is 50 K to 850 K and the regeneration pressure (pr) is less than 30 bar.

15. A system (S) suitable for converting methanol or methanol derivatives into low molecular weight hydrocarbons, comprising: - Conversion unit, and - Appropriate amount (Q) C (C) is the catalyst or catalytic composition according to any one of claims 1 to 8.

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