Enhanced Conversion of Oxygenates to Hydrocarbons by Adsorption

Abstract

The present invention relates to a process for converting an oxide to a hydrocarbon in the presence of a sorbent material having the ability to adsorb water. Further, the present invention relates to a fluidized bed reactor or a fixed bed reactor for converting an oxide to a hydrocarbon, comprising a catalyst and a sorbent material having the ability to adsorb water. The present invention also relates to the use of a sorbent material having the ability to adsorb water for increasing the conversion of an oxide to a hydrocarbon.

Description

Technical Field

[0001] There is a growing interest in renewable sources for the production of chemical building blocks: hydrocarbons such as olefins, alkanes, and aromatics. By selecting renewable sources instead of petroleum and natural gas, the environmental impact of these chemical building blocks is significantly reduced. Oxygenates such as methanol and dimethyl ether (DME) are typical intermediates obtained in carbon capture and utilization processes or in the bioconversion of organic waste streams. These oxygenates can subsequently be converted into the target hydrocarbons.

Background Art

[0002] The conversion of oxygenates to hydrocarbons is known in the art. Water is split off from the oxygenate and the ether and / or alcohol groups are removed to form hydrocarbons. The reaction is exothermic. The specific mix of hydrocarbons formed depends on the reaction conditions such as the pressure and temperature selected and the catalyst (Gunawardena et al., Journal of Thermodynamics, vol. 2012, p1 - 7). There is a vast amount of literature available regarding the selection of reaction conditions and catalysts. The hydrocarbons formed are olefins, alkanes, and / or aromatics. The process is typically carried out at a high temperature so that a sufficiently high conversion is obtained. The corresponding rapid catalyst coking typically occurs within 50 - 100 minutes but is eliminated by incorporating a continuous decoking step into the process. The optimal temperature depends on the catalyst, the target hydrocarbon, and the oxygenate provided. Typically, methanol is reacted at a temperature of about 450 °C, while dimethyl ether, for example, is reacted at about 350 °C.

[0003] Li et al. (ACS Catal. 2021, 11, 7780 - 7819) provided an overview of the conversion of methanol to aromatics (MTA), and Tian et al. (ACS Catal. 2015, 5, 1922 - 1938) and also Topchiev et al. (Catalysts 2019, 9(5), 485) provided an overview of the conversion of methanol to olefins (MTO), while Sanz - Martinez et al. (Catalysts 2022, 12, 134) provided the state - of - the - art technology regarding the conversion of methanol to alkanes (MTG). Magomedova et al. (Catalysts, 2019, 9, 485) described the conversion of dimethyl ether to olefins.

[0004] WO 9955650 A1 pamphlet discloses the conversion of methanol to olefins (MTO) in the presence of a catalyst. To eliminate rapid catalyst coking, the catalyst is regenerated using a gas containing oxygen at elevated temperature. Water is removed from the product stream by a quenching step where the quenching medium is water. US 2019001311 specification describes an MTO process using an acidic zeolite catalyst containing ZSM - 5 and bentonite clay. Bentonite clay binds to ZSM - 5 particles to impart catalyst structural integrity. In US 2015119617 A1 specification, water is removed from the product stream. The removal of water is carried out by a quenching step of the olefin stream, and then this stream is contacted with a molecular sieve containing zeolite 3A and / or 4A to remove water from the quenched olefin stream. The regeneration of the catalyst is carried out using a gas containing oxygen / oxidant at a temperature of 200 - 1500 °C. WO 2006 / 104757 pamphlet describes a process with reduced catalyst deactivation. The coked catalyst is regenerated using a regeneration gas with a regeneration temperature of 600 °C or less. Prior to regenerating the coked catalyst, the regeneration gas can be compressed to condense the water portion and can be contacted with a water adsorbent.

Summary of the Invention

Means for Solving the Problem

[0005] The inventors have surprisingly found that the conversion process from oxides to hydrocarbons can be increased by introducing a sorbent material having the ability to adsorb water. In Example 1, surprisingly, the conversion of DME in the presence of a sorbent material having the ability to adsorb water is much higher than when the sorbent material is water-saturated so that the effect of the sorbent material is canceled. The inventors have not only found that the conversion to hydrocarbons is increased, but also found that the absolute concentration of the reactant can be higher to increase the reaction rate. Therefore, since a lower reaction temperature can be selected through this adsorption-based enhancement, the energy efficiency is improved and the capital investment required for the heating device and heat-resistant materials is reduced. In addition, since the operating window of the process design of the process for converting oxides to hydrocarbons is expanded, the possibility of a new reaction product mix can be opened. The reaction window is expanded to lower temperatures and possibly higher pressures.

[0006] In addition, the inventors have surprisingly found that coking-induced catalyst deactivation is reduced or even prevented. In Example 3, the reactor was operated cyclically in consecutive steps of oxide reaction and sorbent material regeneration. After 50 cycles, no catalyst deterioration was observed. Without being bound by theory, the inventors believe that the shift to lower reaction temperatures and gas compositions contributes to this surprising improvement. Since catalyst deactivation is reduced or even prevented, catalyst decoking is not required or is not required very often, and accordingly the efficiency of the whole process is improved. A specific catalyst decoking step may not be required or may not be required very frequently.

[0007] In a preferred embodiment, the process includes two or more reactors that include a catalyst and a sorbent material capable of adsorbing water. Such a combination of reactors is operable by a pressure swing method, a temperature swing method, and / or a concentration swing method, wherein at least one of the reactors is in a reaction mode. At the same time, one or more of the other reactors are in a sorbent regeneration mode. Thus, it is possible to continuously carry out the entire process. In such an operation, as another advantage, if some catalyst coking still occurs, one of the reactors can be put into a decoking mode. There is no need for another decoking reactor, and the flexibility of the reactor design is higher. This is because the transport of the catalyst to a specific decoking reactor generally limits its design. During decoking, typically the sorbent is also regenerated.

Brief Description of the Drawings

[0008]

Figure 1a

Figure 1b

DETAILED DESCRIPTION OF THE INVENTION

[0009] In a first aspect, the present invention relates to: a) contacting a catalyst and an oxidant in the presence of a sorbent material capable of adsorbing water in a reactor to form hydrocarbons, and subsequently b) regenerating the sorbent material in the same reactor by contacting the sorbent material with a purge gas, A process for converting an oxidant to a hydrocarbon, comprising, wherein the catalyst and the sorbent material are not the same.

[0010] Furthermore, the present invention relates to a fluidized bed reactor or a fixed bed reactor for converting an oxidant to a hydrocarbon, comprising a catalyst for converting an oxidant to a hydrocarbon and a sorbent material capable of adsorbing water, wherein the catalyst and the sorbent material are not the same.

[0011] The present invention also relates to the use of a sorbent material capable of adsorbing water for converting an oxidant to a hydrocarbon in the presence of a catalyst for converting an oxidant to a hydrocarbon, wherein the catalyst and the sorbent material are not the same, and preferably for use: - The conversion is increased compared to when the sorbent material is absent, - The lifetime of the catalyst is extended compared to when the sorbent material is absent, - The deactivation of the catalyst is reduced as compared to when no sorbent material is present, - The reaction rate is increased as compared to when no sorbent material is present, and - The need for catalyst decoking is reduced, preferably prevented, as compared to when no sorbent material is present, involving one or more of the following in use.

[0012] The embodiments disclosed in this document apply to all aspects of the present invention, namely, the conversion process from oxides to hydrocarbons, the fluidized bed reactor or fixed bed reactor for the conversion from oxides to hydrocarbons, and the use of a sorbent material capable of adsorbing water for the conversion from oxides to hydrocarbons in the presence of a catalyst.

[0013] Conversion The present invention relates to the conversion from oxides to hydrocarbons. In this case, one or more oxide compounds undergo a chemical reaction to form one or more hydrocarbon compounds. Such chemical reactions are known in the art and typically require the presence of a catalyst. Based on common knowledge, a person skilled in the art can select a combination of an oxide, a catalyst, and reaction conditions such as pressure and temperature to direct the reaction to a desired mix of specific hydrocarbons. In a preferred embodiment, at least 50 mol%, more preferably at least 70 mol%, most preferably at least 90 mol% based on the total number of moles of reaction products excluding water are hydrocarbons.

[0014] Preferably, the conversion rate of the conversion from oxides to hydrocarbons is at least 80%, more preferably at least 90%, even more preferably at least 95%, most preferably at least 98%. The conversion rate can be calculated by the following: [(number of moles of supplied oxides - number of moles of oxides at the end of the reaction) / (number of moles of supplied oxides)], and is expressed in %. Preferably, the reaction products of the conversion from oxides to hydrocarbons contain less than 20 mol%, more preferably less than 10 mol%, most preferably less than 5 mol% of oxides based on the total number of moles of supplied oxides.

[0015] In a preferred embodiment, at least 50 mol%, more preferably at least 70 mol%, and most preferably at least 90 mol% based on the total number of moles of reaction products excluding water are olefins. More preferably, at least 50 mol%, more preferably at least 70 mol%, and most preferably at least 90 mol% based on the total number of moles of reaction products excluding water are the sum of ethylene, propylene, 1-butene, 2-butene, and isobutylene. Even more preferably, at least 50 mol%, more preferably at least 70 mol%, and most preferably at least 90 mol% based on the total number of moles of reaction products excluding water are the sum of ethylene and propylene. In this embodiment, preferably, the oxygenate is methanol or dimethyl ether.

[0016] In another preferred embodiment, at least 50 mol%, more preferably at least 70 mol%, and most preferably at least 90 mol% based on the total number of moles of reaction products excluding water are alkanes. More preferably, at least 50 mol%, more preferably at least 70 mol%, and most preferably at least 90 mol% based on the total number of moles of reaction products excluding water are the sum of alkanes containing 2 to 18 carbon atoms. Even more preferably, at least 50 mol%, more preferably at least 70 mol%, and most preferably at least 90 mol% based on the total number of moles of reaction products excluding water are the sum of ethane, propane, butane, isobutane, pentane, isopentane, and neopentane. In this embodiment, preferably, the oxygenate is methanol or dimethyl ether.

[0017] In yet another preferred embodiment, at least 50 mol%, more preferably at least 70 mol%, and most preferably at least 90 mol% of the total moles of reaction products excluding water are aromatic substances. More preferably, based on the total moles of reaction products excluding water, at least 50 mol%, more preferably at least 70 mol%, and most preferably at least 90 mol% is the sum of benzene, toluene, and xylene. In this embodiment, preferably, the oxygenate is methanol or dimethyl ether.

[0018] In all of these embodiments, the total moles of reaction products excluding water means the total moles of reaction products minus the amount of water in the reaction products expressed in molar units.

[0019] Oxygenate An oxygenate is a molecule composed of carbon (C), hydrogen (H), and oxygen (O) atoms. In the present invention, the oxygenate is typically an ether or alcohol containing 1 to 6 carbon atoms. Preferably, the oxygenate consists of hydrogen, carbon, and oxygen atoms. Preferably, the oxygenate does not contain a double bond. In a preferred embodiment of the present invention, the oxygenate is one or more of methanol (MeOH), ethanol (EtOH), isopropyl alcohol (IPA), n-butanol (BuOH), gasoline grade tert-butanol (GTBA), methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), tert-hexyl methyl ether (THEME), ethyl tert-butyl ether (ETBE), tert-amyl ethyl ether (TAEE), dimethyl ether (DME), or diisopropyl ether (DIPE). More preferably, the oxygenate is methanol and / or dimethyl ether. Even more preferably, the oxygenate is methanol. Even more preferably, the oxygenate is dimethyl ether.

[0020] Hydrocarbon Hydrocarbons are molecules consisting of carbon (C) and hydrogen (H) atoms. In a preferred embodiment of the present invention, the hydrocarbon contains at most 20 carbon atoms, more preferably 2 to 18 carbon atoms. In a preferred embodiment, the hydrocarbon is selected from the list consisting of olefins, alkanes, and aromatics. More preferably, the hydrocarbon is selected from the list consisting of olefins, alkanes, and aromatics, and the hydrocarbon contains at most 20 carbon atoms, more preferably 2 to 18 carbon atoms. Even more preferably, the hydrocarbon is selected from the list consisting of olefins, alkanes, and aromatics, in which case the olefin contains 2 to 5 carbon atoms, the alkane contains 2 to 18 carbon atoms, and the aromatic contains 6 to 8 carbon atoms.

[0021] In a preferred embodiment, the hydrocarbon is an olefin. In a preferred embodiment, the hydrocarbon is an alkane. In a preferred embodiment, the hydrocarbon is an aromatic.

[0022] In a preferred embodiment, the oxygenate is methanol and / or dimethyl ether, and the hydrocarbon is an olefin. In a preferred embodiment, the oxygenate is methanol and / or dimethyl ether, and the hydrocarbon is an alkane. In a preferred embodiment, the oxygenate is methanol and / or dimethyl ether, and the hydrocarbon is an aromatic.

[0023] Olefin An olefin is an acyclic hydrocarbon having one double bond. Olefins are also referred to as alkenes. In a preferred embodiment of the present invention, the olefin is one or more of ethylene, propylene, 1-butene, 2-butene, and isobutylene. Olefins are typical building blocks for other chemicals such as polymers.

[0024] Alkane Alkanes are acyclic hydrocarbons that do not contain double or triple bonds. Alkanes are also referred to as paraffins. Typically, alkanes are used as fuels. In a preferred embodiment of the present invention, the alkane contains 2 to 18 carbon atoms, more preferably 3 to 18 carbon atoms. Depending on the application, different amounts of carbon atoms are preferred. For synthetic LPG, preferably the alkane contains 3 to 4 carbon atoms, for naphtha, preferably the alkane contains 5 to 7 carbon atoms, for gasoline, preferably the alkane contains 4 to 12 carbon atoms, for kerosene, preferably the alkane contains 11 to 15 carbon atoms, and for diesel, preferably the alkane contains 14 to 18 carbon atoms.

[0025] Aromatics Aromatics are hydrocarbon compounds containing an aromatic ring. In a preferred embodiment, the aromatic contains a phenyl ring. In a preferred embodiment of the present invention, the aromatic is one or more of benzene, toluene, and xylene.

[0026] Catalyst A vast amount of literature has been published on catalysts for the conversion of oxygenates to hydrocarbons. For example, Li et al. (ACS Catal. 2021, 11, 7780 - 7819) provided an overview of catalysts for the conversion to aromatics (MTA), Tian et al. (ACS Catal. 2015, 5, 1922 - 1938) and also Topchiev et al. (Catalysts 2019, 9(5), 485) provided an overview of catalysts for the conversion to olefins (MTO), and Sanz - Martinez et al. (Catalysts 2022, 12, 134) provided the state of the art of technologies related to catalysts for the conversion to alkanes (MTG). Typically, catalysts containing acidic sites are prepared for that purpose.

[0027] In a preferred embodiment, the catalyst is selected from the list consisting of H-beta, ZSM-5, ZSM-22, MCM-22, mordenite, UZM-9, SAPO (e.g., SAPO-17, -18, -34, -35, -44, -56), and AlPO, and more preferably the catalyst is ZSM-5 or SAPO-34. The catalyst can be fixed to a carrier material and / or bound to a binder material. In the present invention, a catalyst fixed to a carrier material and / or bound to a binder material is regarded as a catalyst.

[0028] In some catalysts, their core structure is also known as a water adsorbent (e.g., zeolite), but the modification that makes such a core structure suitable for catalysis has a significant adverse effect on the water-binding affinity. Typically, the active catalyst sites created on the core structure are acidic and are created, for example, by increasing the silicon (Si) to aluminum (Al) ratio or by introducing phosphorus (P) by contacting with phosphoric acid. Such modifications typically eliminate any water adsorption capacity of the catalyst. Conversely, a water adsorbent has the same core structure as the catalyst but has no catalytic activity at all. Catalyst sites are not introduced into the water adsorbent at all. Moreover, water adsorption is affected by temperature, and although some catalysts may have some residual water adsorption capacity at ambient temperature, this capacity does not exist at higher temperatures. When the catalyst is fixed on a carrier or combined with a binder material, the carrier or binder has some water adsorption capacity, but this catalyst will not have a water adsorption capacity. This is because the carrier or binder is present in a relatively small amount.

[0029] In a preferred embodiment, the catalyst has a maximum water adsorption capacity of less than 0.10 grams of water per gram of catalyst at the temperature and pressure of step a), more preferably less than 0.04 grams of water per gram of catalyst at the temperature and pressure of step a), even more preferably less than 0.02 grams of water per gram of catalyst at the temperature and pressure of step a), and most preferably less than 0.01 grams of water per gram of catalyst at the temperature and pressure of step a).

[0030] Preferably, the water adsorption capacity is measured via breakthrough analysis or via thermogravimetric analysis (TGA), preferably via TGA. Both of these methods are described in Van Kampen et al. (Adsorption 27, 577-589 (2021)) and Ruthven (Ruthven, D.M. (1984). Principles of adsorption and adsorption processes. John Wiley & Sons.).

[0031] In breakthrough analysis, first, the catalyst sample is dried at 400 °C in an atmosphere free of water vapor, and subsequently, at the temperature and pressure of step a), the catalyst is exposed to a gas mixture containing 40 mol% water and an inert tracer until equilibrium is reached, in which case the amount of adsorbed water is obtained by time integration of the measured outlet composition. It is possible to derive the water adsorption capacity in units of grams of water per gram of catalyst by dividing the amount of adsorbed water expressed in weight units by the weight of the catalyst sample.

[0032] In thermogravimetric analysis, first, the catalyst sample is dried at a temperature of 400 °C in an atmosphere free of water vapor, and subsequently, at the temperature and pressure of step a), the catalyst is exposed to a gas mixture containing 40 mol% water for at least 1000 seconds, and the weight increase of the dried catalyst between before and after exposure to the gas mixture containing 40 mol% water is measured. The water adsorption capacity is the weight increase divided by the weight of the dried catalyst sample.

[0033] The form of the catalyst depends on the size and type of the reactor. In a preferred embodiment, the catalyst is a particulate material, preferably with a particle size of 0.10 millimeters to 10 centimeters, more preferably 0.30 millimeters to 5.0 centimeters, and even more preferably 1.0 centimeter to 5.0 centimeters. Typically, the optimal particle size for a fluidized bed reactor is smaller compared to a fixed bed reactor. Typically, the optimal particle size for an industrial scale reactor is larger than that of a laboratory reactor. One skilled in the art can select the optimal particle size for a specific reactor design.

[0034] A sorbent material capable of adsorbing water Sorbent materials capable of adsorbing water are known in the art. Preferably, the sorbent material capable of adsorbing water is a molecular sieve, more preferably a zeolite, and even more preferably an LTA zeolite. A molecular sieve is a material containing pores of uniform size. A zeolite is an aluminosilicate mineral containing pores of uniform size. LTA zeolite is Linde type A zeolite. Preferably, the sorbent material capable of adsorbing water is a molecular sieve having a pore diameter in the range of 1 to 10 angstroms (Å), more preferably in the range of 2 to 5 Å, even more preferably in the range of 3 to 5 Å, and most preferably in the range of 3 to 4 Å. More preferably, the sorbent material capable of adsorbing water is a zeolite having a pore diameter in the range of 1 to 10 Å, more preferably in the range of 2 to 5 Å, even more preferably in the range of 3 to 5 Å, and most preferably in the range of 3 to 4 Å. Even more preferably, the sorbent material capable of adsorbing water is an LTA zeolite having a pore diameter in the range of 1 to 10 Å, more preferably in the range of 2 to 5 Å, even more preferably in the range of 3 to 5 Å, and most preferably in the range of 3 to 4 Å.

[0035] In a preferred embodiment, the sorbent material capable of adsorbing water has a molar ratio of Al to Si of 0.3:1.0 to 10.0:3.0, more preferably 0.5:1.0 to 2.0:1.0, and most preferably 0.8:1.0 to 1.2:1.0. Equal amounts of Si to Al exhibit a lower acidic structure that is sufficiently capable of adsorbing water. Preferably, the sorbent material capable of adsorbing water has a water adsorption capacity of at least 0.04 grams of water per gram of sorbent material at the temperature and pressure of step a), more preferably at least 0.06 grams of water per gram of sorbent material at the temperature and pressure of step a), even more preferably at least 0.08 grams of water per gram of sorbent material at the temperature and pressure of step a), and most preferably at least 0.10 grams of water per gram of sorbent material at the temperature and pressure of step a).

[0036] As far as the catalyst is concerned, preferably, the water adsorption capacity is measured via breakthrough analysis or via thermogravimetric analysis (TGA), preferably via TGA. Both of these methods are described in Van Kampen et al. (Adsorption 27, 577-589 (2021)) and Ruthven (Ruthven, D.M. (1984). Principles of adsorption and adsorption processes. John Wiley & Sons.).

[0037] In breakthrough analysis, first, a sample of the sorbent material capable of adsorbing water is dried at 400 °C in an atmosphere free of water vapor, and subsequently, at the temperature and pressure of step a), the sorbent material capable of adsorbing water is exposed to a gas mixture containing 40 mol% water and an inert tracer until equilibrium is reached, in which case the amount of adsorbed water is obtained by time integration of the measured outlet composition. The water adsorption capacity can be derived in units of grams of water per gram of the sorbent material capable of adsorbing water by dividing the amount of adsorbed water expressed in weight units by the weight of the sorbent material sample capable of adsorbing water.

[0038] In thermogravimetric analysis, first, a sample of the sorbent material capable of adsorbing water is dried at a temperature of 400 °C in an atmosphere free of water vapor, and subsequently, at the temperature and pressure of step a), the sorbent material capable of adsorbing water is exposed to a gas mixture containing 40 mol% water for at least 1000 seconds, and the weight increase of the dry sorbent material capable of adsorbing water between before and after exposure to the gas mixture containing 40 mol% water is measured. The water adsorption capacity is the weight increase divided by the original weight of the dry sorbent material sample capable of adsorbing water.

[0039] In a preferred embodiment, the catalyst and the sorbent material capable of adsorbing water are not bonded to each other. Bonding may reduce the catalytic activity of the catalyst and / or the water adsorption capacity of the sorbent material. Moreover, bonding is costly and leads to a reduction in the degree of freedom in selecting the ratio of the catalyst to the sorbent material capable of adsorbing water.

[0040] In a preferred embodiment, the weight ratio of the catalyst to the sorbent material capable of adsorbing water is from 1.0:10.0 to 10.0:1.0, more preferably from 1.0:10.0 to 5.0:1.0, even more preferably from 1.0:10.0 to 2.0:1.0, and most preferably from 1.0:5.0 to 1.0:1.0. Within these ratio ranges, a good water adsorption capacity can be obtained at a sufficient reaction rate.

[0041] The form of the sorbent material capable of adsorbing water depends on the size and type of the reactor. In a preferred embodiment, the sorbent material capable of adsorbing water is a particulate material, preferably with a particle size of from 0.10 millimeters to 10 millimeters, more preferably from 0.30 millimeters to 5.0 millimeters, and even more preferably from 1.0 centimeter to 5.0 centimeters. Typically, the optimal particle size for a fluidized bed reactor is smaller compared to a fixed bed reactor. Typically, the optimal particle size for an industrial scale reactor is larger than that of a laboratory reactor. Those skilled in the art can select the optimal particle size for a specific reactor design.

[0042] In a preferred embodiment, at the start of step a), the sorbent material capable of adsorbing water contains less than 0.10 grams of water per gram of the sorbent material at the temperature and pressure of step a), even more preferably less than 0.04 grams of water per gram of the sorbent material at the temperature and pressure of step a), even more preferably less than 0.02 grams of water per gram of the sorbent material at the temperature and pressure of step a), and most preferably less than 0.01 grams of water per gram of the sorbent material at the temperature and pressure of step a).

[0043] Purge gas In a preferred embodiment, the purge gas is air, nitrogen, hydrogen, or a hydrocarbon gas, more preferably air. Preferably, the purge gas contains less than 5.0 mol% of water, preferably less than 1.0 mol% of water, and most preferably less than 0.5 mol% of water based on the total purge gas.

[0044] Process One aspect of the present invention relates to a process for the conversion of oxides to hydrocarbons. The process includes a reaction step a) in which reaction products are formed and a regeneration step b) in which a sorbent material capable of adsorbing water is regenerated. The regeneration of the sorbent material capable of adsorbing water relates to the desorption of water from the sorbent material. Thus, the sorbent material is capable of immediately adsorbing water in its next reaction step a). In reaction step a), following the formation of the reaction products, further water is adsorbed by the sorbent material capable of adsorbing water.

[0045] The present invention relates to contact in a reactor. In a preferred embodiment, the contact is by providing a feed, more preferably by providing a continuous feed. In a preferred embodiment, the contact is by providing a feed, and the feed is a feed gas.

[0046] In a preferred embodiment, the temperature of step a) is 200°C to 500°C, more preferably 200°C to 400°C, even more preferably 200°C to 350°C, and most preferably 225°C to 275°C. This temperature is lower than that of conventional processes. The inventors have surprisingly found that excellent conversion can be achieved even at such lower temperatures. Moreover, the lower temperature provides a slower coke formation or even no coke formation at all. Typically, the catalyst is deactivated due to coke formation. In a preferred embodiment, the oxide is DME and the temperature of step a) is 200°C to 500°C, more preferably 200°C to 400°C, even more preferably 200°C to 350°C, and most preferably 225°C to 275°C, or the oxide is methanol and the temperature of step a) is 200°C to 500°C, more preferably 275°C to 400°C, even more preferably 300°C to 400°C, and most preferably 300°C to 350°C.

[0047] In a preferred embodiment, the pressure in step a) is from 1.0 to 30 bara, more preferably from 1.0 to 20 bara, even more preferably from 2.0 to 10 bara, and most preferably from 4.0 to 8.0 bara. The selection of the pressure in step a) is related to several aspects. A higher pressure in step a) enables a greater pressure difference between steps a) and b), which is beneficial for the water desorption in step b) when the pressure is selected as the driving force for water desorption. Such a pressure swing operation is generally an efficient way to operate the process according to the present invention. This is because the pressure drop can be caused within a short time and relatively little energy is used. Although this does not apply to conventional processes, since water is removed in the reaction step, the increase in pressure tends to affect the conversion, albeit not significantly. In some cases, it has been reported that the pressure affects the selectivity. In the art, the conversion process from oxides to hydrocarbons is typically operated at ambient pressure, although operating pressures up to 30 bara have been reported.

[0048] The conditions of the reactor between step a) and step b) are different in terms of temperature, pressure, and / or feed gas composition. This is typical of a swing process. The water holding capacity of the sorbent is dependent on temperature and pressure. In the regeneration step b), the reactor undergoes a change in temperature, pressure, and / or feed gas composition to efficiently desorb water from the sorbent material. The purge gas in step b) carries away the water. In a preferred embodiment, the temperature in step b) is at least 100 °C higher than the temperature in step a), and / or the pressure in step b) is at least 0.9 bar lower than the pressure in step a). More preferably, the temperature in step b) is at least 150 °C higher than the temperature in step a), and / or the pressure in step b) is at least 3.0 bar lower than the pressure in step a). Even more preferably, the temperature in step b) is at least 200 °C higher than the temperature in step a), and / or the pressure in step b) is at least 5.0 bar lower than the pressure in step a). In a preferred embodiment, the temperature in step b) is at least 100 °C higher than the temperature in step a). More preferably, the temperature in step b) is at least 200 °C higher than the temperature in step a). Even more preferably, the temperature in step b) is at least 150 °C higher than the temperature in step a). In a preferred embodiment, the pressure in step b) is at least 0.9 bar lower than the pressure in step a). More preferably, the pressure in step b) is at least 5.0 bar lower than the pressure in step a). Even more preferably, the pressure in step b) is at least 3.0 bar lower than the pressure in step a).

[0049] In a preferred embodiment, the temperature in step b) is from 200 °C to 500 °C, more preferably from 200 °C to 400 °C, even more preferably from 200 °C to 350 °C, and most preferably from 225 °C to 275 °C. When the process includes a temperature swing, preferably, the temperature in step b) is from 300 °C to 700 °C, more preferably from 400 °C to 600 °C, even more preferably from 400 °C to 500 °C. In a preferred embodiment, the pressure in step b) is from 1.0 to 30 bara, more preferably from 1.0 to 20 bara, even more preferably from 2.0 to 10 bara, and most preferably from 4.0 to 8.0 bara. When the process includes a pressure swing, preferably, the pressure in step b) is from 2.0 to 20 bara, more preferably from 1.0 to 10 bara, even more preferably from 0.5 to 5 bara, and most preferably from 0.1 to 2 bara.

[0050] In a preferred embodiment, the process is operated cyclically, in which case step a) is performed again following step b). Thus, the reactor of the process is switched between mode a) and mode b), optionally in combination with another mode. Considering the production plant, a continuous process is preferred, and the process preferably includes two or more reactors, more preferably three or more reactors, including a catalyst and a sorbent material capable of adsorbing water. In this embodiment, preferably, at least one of the two or more or three or more reactors is in mode a). By having two or more reactors, it is possible to set one reactor in reaction mode a) while setting other reactors in regeneration mode b). When the sorbent material capable of adsorbing water in the reactor in reaction mode a) is saturated with water, it is possible to switch the feed flow to the reactor that was in regeneration mode b), and since the reaction can continue in this reactor, this reactor enters the reaction mode. Meanwhile, the reactor containing the water-saturated sorbent material can enter regeneration mode b). Thus, it is possible to maintain a continuous feed flow and product flow. In some situations, modes a) and b) are not of equal length. Therefore, in a preferred embodiment, the process includes step c) an idle mode. During the idle mode, no gas is supplied to the reactor.

[0051] The inventors have found that in the process of the present invention, there is little or no tendency for catalyst coking to occur. This can reduce or even eliminate the need for catalyst decoking. Without being bound by theory, the inventors believe that lower temperature and / or water removal during the reaction and / or intermittent sorbent regeneration have a positive effect on coke formation. Nevertheless, situations may still arise where catalyst decoking is necessary. During catalyst decoking, coke is removed by contacting the catalyst with a gas containing oxygen at a temperature above 400°C, preferably above 500°C, more preferably above 600°C. In a preferred embodiment, the process of the present invention includes step d) of decoking the catalyst by contacting it with an oxygen-containing gas at a temperature above 400°C, preferably above 500°C, more preferably above 600°C. In a preferred embodiment, the catalyst is decoked in a reactor containing a sorbent material capable of adsorbing water with the catalyst. Thus, catalyst decoking and sorbent regeneration are carried out simultaneously. In this embodiment, preferably the reactor is a fixed bed reactor. Preferably the process is operated cyclically, in which case step a) is carried out following step b), and step d) is carried out at most once every 3 cycles, more preferably at most once every 6 cycles, most preferably at most once every 9 cycles.

[0052] In a preferred alternative embodiment, the catalyst is decoked in a separate decoking reactor. In this embodiment, preferably the reactor is a fluidized bed reactor.

[0053] Reactor The present invention further relates to a fluidized bed reactor or a fixed bed reactor for the conversion of oxygenates to hydrocarbons, comprising a catalyst for the conversion of oxygenates to hydrocarbons and a sorbent material capable of adsorbing water, wherein the catalyst and the sorbent material are not the same. In a preferred embodiment, the present invention relates to two or more such reactors. Preferably the reactor is a fixed bed reactor.

[0054] In a preferred embodiment, the catalyst is selected from the list consisting of H-beta, ZSM-5, ZSM-22, MCM-22, mordenite, UZM-9, SAPO (e.g., SAPO-17, -18, -34, -35, -44, -56), and AlPO, and preferably the catalyst is ZSM-5 or SAPO-34. In a preferred embodiment, the sorbent material capable of adsorbing water is a molecular sieve having a pore diameter in the range of 2 to 5 Å, more preferably a zeolite having a pore diameter in the range of 2 to 5 Å, and even more preferably an LTA zeolite having a pore diameter in the range of 2 to 5 Å.

[0055] In a preferred embodiment, the weight ratio of the catalyst to the sorbent material capable of adsorbing water is 1.0:10.0 to 10:1.0, preferably 1.0:10.0 to 5.0:1.0. In a preferred embodiment, the sorbent material capable of adsorbing water has a water adsorption capacity of at least 0.04 grams of water per gram of sorbent material at the temperature and pressure of step a), preferably at least 0.06 grams of water per gram of sorbent material at the temperature and pressure of step a), more preferably at least 0.08 grams of water per gram of sorbent material at the temperature and pressure of step a), and most preferably at least 0.10 grams of water per gram of sorbent material at the temperature and pressure of step a).

[0056] In a preferred embodiment, the catalyst has a water adsorption capacity of less than 0.10 grams of water per gram of catalyst at the temperature and pressure of step a), preferably less than 0.04 grams of water per gram of catalyst at the temperature and pressure of step a). In a preferred embodiment, the catalyst and the sorbent material capable of adsorbing water are not bonded to each other.

[0057] In a preferred embodiment, the oxygenate is one or more of methanol (MeOH), ethanol (EtOH), isopropyl alcohol (IPA), n-butanol (BuOH), gasoline-grade tert-butanol (GTBA), methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), tert-hexyl methyl ether (THEME), ethyl tert-butyl ether (ETBE), tert-amyl ethyl ether (TAEE), dimethyl ether (DME), or diisopropyl ether (DIPE). Preferably, the oxygenate is methanol and / or dimethyl ether, and more preferably the oxygenate is methanol. In a preferred embodiment, the hydrocarbon is selected from the group consisting of olefins, alkanes, aromatics, and any combination thereof, where preferably, the olefin is one or more of ethylene, propylene, 1-butene, 2-butene, and isobutylene, the alkane is one or more of alkanes containing 2 to 18 carbon atoms, and the aromatic is one or more of benzene, toluene, and xylene.

[0058] Use The present invention also relates to the use of a sorbent material capable of adsorbing water for converting an oxygenate to a hydrocarbon in the presence of a catalyst for converting the oxygenate to the hydrocarbon, wherein the catalyst and the sorbent material are not the same, and preferably for use, the following: - The conversion is increased compared to when the sorbent material is absent. - The lifetime of the catalyst is extended compared to when the sorbent material is absent. - The deactivation of the catalyst is reduced compared to when the sorbent material is absent. - The reaction rate is increased compared to when the sorbent material is absent, and - The need for catalyst decoking is reduced, preferably prevented, compared to when the sorbent material is absent. relates to the use, involving one or more of the above. Preferably, the increase, extension, and / or reduction are compared to when no sorbent material is present and the same amount of catalyst is present.

[0059] Thus, in one embodiment, the present invention relates to the use of a sorbent material capable of adsorbing water for increasing the conversion of an oxide to a hydrocarbon in the presence of a catalyst for the conversion of an oxide to a hydrocarbon, wherein the catalyst and the sorbent material are not the same, and the increase is compared to when the sorbent material is absent.

[0060] In another embodiment, the present invention relates to the use of a sorbent material capable of adsorbing water for increasing the lifespan of a catalyst in a process of converting an oxide to a hydrocarbon in the presence of a catalyst for the conversion of an oxide to a hydrocarbon, wherein the catalyst and the sorbent material are not the same, and the increase is compared to when the sorbent material is absent.

[0061] In yet another embodiment, the present invention relates to the use of a sorbent material capable of adsorbing water for reducing the deactivation of a catalyst in a process of converting an oxide to a hydrocarbon in the presence of a catalyst for the conversion of an oxide to a hydrocarbon, wherein the catalyst and the sorbent material are not the same, and the reduction is compared to when the sorbent material is absent.

[0062] In yet another embodiment, the present invention relates to the use of a sorbent material capable of adsorbing water for increasing the reaction rate in a process of converting an oxide to a hydrocarbon in the presence of a catalyst for the conversion of an oxide to a hydrocarbon, wherein the catalyst and the sorbent material are not the same, and the increase is compared to when the sorbent material is absent.

[0063] In yet another embodiment, the present invention relates to the use of a sorbent material capable of adsorbing water for reducing the need for catalyst decoking in a process of converting an oxide to a hydrocarbon in the presence of a catalyst for the conversion of an oxide to a hydrocarbon, wherein the catalyst and the sorbent material are not the same, and the reduction is compared to when the sorbent material is absent.

[0064] In a preferred embodiment, the catalyst is selected from the list consisting of H-beta, ZSM-5, ZSM-22, MCM-22, mordenite, UZM-9, SAPO (e.g., SAPO-17, -18, -34, -35, -44, -56), and AlPO, and preferably the catalyst is ZSM-5 or SAPO-34. In a preferred embodiment, the sorbent material capable of adsorbing water is a molecular sieve having a pore diameter in the range of 2 to 5 Å, more preferably a zeolite having a pore diameter in the range of 2 to 5 Å, and even more preferably an LTA zeolite having a pore diameter in the range of 2 to 5 Å.

[0065] In a preferred embodiment, the weight ratio of the catalyst to the sorbent material capable of adsorbing water is 1.0:10.0 to 10:1.0, preferably 1.0:10.0 to 5.0:1.0. In a preferred embodiment, the sorbent material capable of adsorbing water has a water adsorption capacity of at least 0.04 grams of water per gram of sorbent material at the temperature and pressure of step a), preferably at least 0.06 grams of water per gram of sorbent material at the temperature and pressure of step a), more preferably at least 0.08 grams of water per gram of sorbent material at the temperature and pressure of step a), and most preferably at least 0.10 grams of water per gram of sorbent material at the temperature and pressure of step a).

[0066] In a preferred embodiment, the catalyst has a water adsorption capacity of less than 0.10 grams of water per gram of catalyst at the temperature and pressure of step a), preferably less than 0.04 grams of water per gram of catalyst at the temperature and pressure of step a). In a preferred embodiment, the catalyst and the sorbent material capable of adsorbing water are not bonded to each other.

[0067] In a preferred embodiment, the oxygenate is one or more of methanol (MeOH), ethanol (EtOH), isopropyl alcohol (IPA), n-butanol (BuOH), gasoline-grade tert-butanol (GTBA), methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), tert-hexyl methyl ether (THEME), ethyl tert-butyl ether (ETBE), tert-amyl ethyl ether (TAEE), dimethyl ether (DME), or diisopropyl ether (DIPE). Preferably, the oxygenate is methanol and / or dimethyl ether, and more preferably, the oxygenate is methanol. In a preferred embodiment, the hydrocarbon is selected from the group consisting of olefins, alkanes, aromatics, and any combination thereof. In that case, preferably, the olefin is one or more of ethylene, propylene, 1-butene, 2-butene, and isobutylene, the alkane is one or more of alkanes containing 2 to 18 carbon atoms, and the aromatic is one or more of benzene, toluene, and xylene.

[0068] In a preferred embodiment, the use is in a fluidized bed reactor or a fixed bed reactor, preferably in a fixed bed reactor. In a preferred embodiment, the use is at a temperature of 200°C to 500°C, preferably 200°C to 400°C, even more preferably 200°C to 350°C, and most preferably 225°C to 275°C. In a preferred embodiment, the use is at a pressure of 1.0 to 30 bara, preferably 1.0 to 20 bara.

[0069] General definition In this specification and the claims, the term "to comprise" is used in its non-limiting sense, meaning that it includes the items following the word but does not exclude items not specifically listed. Additionally, a reference to "an element" by the indefinite article "a" or "an" does not exclude the possibility of more than one element existing, unless it is clearly required by the context that only one element exists. Therefore, the indefinite article "a" or "an" typically means "at least one". When used in connection with a numerical value, the words "about" or "approximately" (e.g., about 10) preferably mean that the given value can be a value that is 1% larger or smaller than that value.

[0070] The present invention has been described above with reference to several exemplary embodiments. Modifications and alternative implementations of some parts or elements are possible and are included within the scope of protection defined by the appended claims. All citations of documents and patent documents are hereby incorporated by reference in this application.

[0071] bara is an abbreviation of bar absolute and relates to pressure with a perfect vacuum as the zero reference. 1 bar is 100,000 N / m 2 and is. 1 bar is 100,000 pascals. In the context of the present invention, particularly in relation to "the use of a sorbent material capable of adsorbing water for converting an oxide to a hydrocarbon in the presence of a catalyst for the conversion of an oxide to a hydrocarbon", "in the presence of" means that the catalyst and the sorbent material are present in the same reactor.

Examples

[0072] Example 1 - Oxide conversion Method A quartz reactor with an inner diameter of 16 mm was filled with 2.5 grams of catalyst and 6.0 grams of water adsorbent to a bed height of approximately 70 mm. During adsorption, at 250 °C and 1 bara, 92 Nml·min -1It was fed into the reactor. The gas mixture contained 5 mol% DME, 5 mol% He as a tracer, and the balance Ar. Regeneration was carried out by switching the gas flow to 100 mol% Ar and raising the temperature to 400 °C for 60 minutes. The reactor outlet gas analysis was continuously carried out by a Pfeiffer Thermostar mass spectrometer.

[0073] Regarding the materials, a mixture consisting of an adsorbent and either the catalyst SAPO or HZSM-5 was used. The materials used are as follows. Water adsorbent: Molecular sieve 3A, ASGE Catalyst 1: SAPO-34, Zeolyst Catalyst 2: Zeolite HZSM-5, PQ Chemicals

[0074] In the experiment, a particle size of 0.212 - 0.425 mm was used. The adsorbent (3A) is available in the form of small pellets. The appropriate particle size is obtained by crushing and sieving. Both of these catalysts are available as fine powders. To obtain the appropriate particle size, these powders are first pelletized using a manual press. Subsequently, the tablets are crushed and sieved again. 6.0 g of adsorbent particles are thoroughly mixed with either 2.5 grams of SAPO-34 or HZSM-5. After mixing, it is filled into a quartz reactor with an inner diameter of 16 mm to achieve a typical bed height of approximately 70 mm.

[0075] Results Mass spectrometry of the product mixture was carried out, and the peak assignments were made according to Wallace, W.E. (2018). Mass spectra. NIST Chemistry WebBook, NIST Standard Reference Database, (69). Table 1 shows an overview of the analyzed species with their corresponding m / z values. Table 2 summarizes the values of each m / z before and after breakthrough at the specifically indicated times.

[0076] [Table 1]

[0077]

Table 2

[0078] Investigation and Conclusions Both of these experiments relate to DME dehydration experiments on SAPO and HZSM5 catalysts, and they are carried out in much the same way as conventionally. The reaction temperature is relatively low. The difference is that it is in the presence of a water adsorbent that affects reactor performance and causes a transient response.

[0079] Essentially, the experiment can be divided into the period before breakthrough and the period after breakthrough. The period before breakthrough starts at t = 0 and ends when the water signal begins to increase. This increase indicates that water has started to pass through the reactor and the 3A water adsorbent, i.e., the adsorbent has become saturated. The period after breakthrough consists of two phases. First, the water concentration in the reaction product increases logarithmically until it reaches the plateau phase. In Experiment 1, the period before breakthrough ends at about 28 minutes and reaches the plateau phase at about 65 minutes. In Experiment 2, the period before breakthrough ends at about 4 minutes and reaches the plateau phase at about 33 minutes.

[0080] Before water breakthrough, the concept of adsorption enhancement is applied. That is, water is removed from the gas phase in the reactor by adsorption, causing a shift or enhancement of DME conversion. As demonstrated in Table 2, in both Experiments 1 and 2, the amounts of oxygenates DME and methanol released from the reactor are very low.

[0081] The plateau phase corresponds to the "conventional" response since the action of the adsorbent is effectively canceled. The mass spectrometer signals are not quantitative, but they are comparable in their mutual relationships. In Experiments 1 and 2, the responses clearly show a significantly enhanced DME (and methanol) conversion before breakthrough compared to after breakthrough. During the pre-breakthrough period, Experiment 1 shows a high response, for example, at m / z values of 41 and 55 that are indicators of the hydrocarbons (olefins and / or paraffins) formed. Experiment 2 shows this effect even more markedly, where the pre-breakthrough m / z values of 41, 43, and 55 are higher than their respective post-breakthrough responses. In all cases, after water breakthrough, the DME response increases strongly, suggesting that the DME conversion decreases significantly. The low conversion of the conventional process without adsorption is not unexpected, since the temperature of 250 °C is somewhat low for DME (and methanol) dehydration experiments.

[0082] In conclusion, Experiments 1 and 2 demonstrate the effect of enhanced sorption. Before breakthrough, a nearly complete DME conversion can be achieved and hydrocarbon products are formed. The post-breakthrough state shows an incomplete conversion and a somewhat modified product spectrum. Thus, enhanced sorption significantly increases the conversion and allows for a lower reaction temperature.

[0083] Example 2 - Absence of water adsorption with the SAPO34 catalyst The SAPO34 catalyst of Example 1 was tested with respect to water adsorption. 0.5 grams of the SAPO34 catalyst (212 - 425 μm sieve fraction) was placed in a reactor with a diameter of 6 mm and the temperature was set to 250 °C. The pressure in the reactor was 1 bara. A gas stream containing 10 mol% water (92 Nml·min -1)(0) was provided to the reactor, and the gas flow coming from the reactor was analyzed in the same manner as in Example 1. The breakthrough of the water front was instantaneous, and since the delivery stream reached a constant water concentration in less than 1 minute, it was suggested that no water adsorption occurred. The steady-state flow was maintained for about 22 minutes, after which the temperature was increased to 400 °C and a gas flow containing no water was provided. The subsequent decrease in the water concentration in the delivery stream was instantaneous, and since no typical water peak of the water adsorbent material was observed, it was suggested again that the SAPO34 catalyst did not adsorb water.

[0084] Example 3 - Absence of catalyst deactivation due to coke formation Method In Example 3, the water adsorbent combination of Experiment 1 (zeolite HZSM-5, PQ Chemicals, and molecular sieve 3A type, ASGE, both in the sieve fraction of 212 - 425 μm) was used. A quartz reactor with an inner diameter of 10 mm was filled with 0.5 grams of catalyst and 2.5 grams of water adsorbent to a bed height of about 58 mm. However, the reactor was operated alternately in the reaction mode and the sorbent regeneration mode without monitoring one cycle. The reaction mode was at a temperature of 250 °C and a pressure of 1 bara as described in Example 1. The sorbent regeneration mode was at 400 °C and 1 bara. As in the case of Example 1, during adsorption, 92 Nml·min -1 was supplied to the reactor. The gas mixture contained 5 mol% DME, 5 mol% He as a tracer, and the balance Ar. The purge gas was Ar. The reaction time was 15 minutes and the regeneration time was 45 minutes. The reactor outlet gas analysis was continuously performed by a Pfeiffer Thermostar mass spectrometer. At the start of the reaction mode, after the sorbent regeneration mode, DME was supplied to the reactor and the helium inlet concentration was increased (step change). At the outlet of the reactor, the concentrations of the reaction products and the unconverted feed gas are on a time scale. For clarity, only the outlet concentrations of helium, DME, and water are plotted.

[0085] Results and conclusions The goal of this experiment was to investigate the effect of the method of the present invention on catalyst deactivation. In Figure 1a, the outlet concentrations of DME (m / z 45), He (m / z 4), and water (m / z 18) are plotted as a function of time for the third cycle, and in Figure 1b for the 50th cycle.

[0086] Assess the system performance with respect to DME conversion. As seen in Examples 1 and 2, after the breakthrough of the increased helium concentration, a period follows during which all of the DME is converted until DME also breaks through, after which water breakthrough follows. The local peak of DME observable immediately after DME breakthrough and the breakthrough time difference between DME and water are both not further investigated but are tentatively attributed to a dynamic “roll-up” effect (as discussed, for example, in Yang, R.T. (1997). Gas separation by adsorption processes (Vol. 1). World Scientific.).

[0087] In cycle 3, the He signal is steady and increases at t = 295.7 minutes, suggesting the end of the regeneration mode and the start of the reaction mode. The breakthrough of DME is at 296.2 minutes, 0.42 minutes after the start of the reaction mode. In cycle 50, the He signal is steady and increases at t = 4681.8 minutes, suggesting the end of the regeneration mode and the start of the reaction mode. The breakthrough of DME is at 4682.2 minutes, 0.43 minutes after the start of the reaction mode.

[0088] Essentially, the DME conversion resulting from the breakthrough time difference between the helium step change and the DME signal surprisingly remains invariant between cycle 3 and cycle 50. Therefore, no measurable degradation of DME conversion can be observed for more than 70 hours of repeated cycling, from which it can be concluded that the catalyst activity remains constant.

[0089] Example 4 - Effect of adsorption enhancement on SAPO - 34 stability and conversion Method The reaction was carried out in a quartz reactor connected to a Pfeiffer Thermostar mass spectrometer (MS) for the analysis of the reactor outlet gas. The measurement setup was the same as in Examples 1 to 3. Three experiments were conducted. In the first and second experiments, the quartz reactor with an inner diameter of 13 mm was filled only with the catalyst, while in the third experiment, the quartz reactor with an inner diameter of 18 mm was filled with a mixture of the catalyst and a water adsorbent. The materials used are described below. Water adsorbent: Molecular sieve 3A type, ASGE Catalyst: SAPO-34, Zeolyst

[0090] In all experiments, the particle sizes of the catalyst and the adsorbent were 0.212 - 0.425 mm. The adsorbent (3A) was available in the form of small pellets. Appropriate particle sizes were obtained by crushing and sieving. The catalyst was available as a fine powder. To obtain the appropriate particle size, the powder was first pelletized using a manual press. Subsequently, the tablets were crushed and sieved again. In the first experiment, a quartz reactor with an inner diameter of 13 mm was filled with 2.54 g of the SAPO-34 catalyst to obtain a bed height of 37 mm. Similarly, in the second experiment, a quartz reactor with an inner diameter of 13 mm was filled with 2.501 g of the SAPO-34 catalyst to obtain a bed height of 39 mm. In the third experiment, 6.035 g of adsorbent particles and 2.507 grams of the SAPO-34 catalyst were thoroughly mixed. After mixing, it was filled into a quartz reactor with an inner diameter of 18 mm to obtain a bed height of 54 mm.

[0091] During adsorption, 91.6 Nml / min -1 was supplied to the reactor in all experiments. The gas mixture contained 5 mol% DME, 5 mol% He as a tracer, and the balance Ar in all three experiments. Experiments 1 and 2 (reactor beds consisting only of the SAPO-34 catalyst) were conducted at two temperatures of 450 °C and 250 °C. Experiment 3 (reactor bed consisting of a mixture of the SAPO-34 catalyst and the zeolite 3A water adsorbent) was conducted at 250 °C.

[0092] Experiment 3 was conducted in cyclic mode, and regeneration was carried out by switching the gas flow to 90 mol% Ar and 10 mol% He and increasing the temperature to 400 °C. The reaction time for each cycle was 60 minutes. In all experiments, the composition of the gas released from the reactor was measured in the same manner as in Example 1. Thus, the water, MDE, and hydrocarbon concentrations could be tracked over time.

[0093] Results and Discussion The difference between Experiment 1 and Experiment 2 was the operating temperature. In Experiment 1 at 450 °C, the conversion gradually decreased in the first 30 hours, which was recognizable by the gradual decrease in the hydrocarbon concentration in the outlet stream (about 20%). After about 30 hours, the reaction suddenly stopped, which was manifested by a sharp increase in the DME signal and a decrease of the olefin concentration to zero. This corresponded to the complete deactivation of the catalyst. The conversion seemed to be stable in the first 30 hours, but catalyst deactivation also occurred. However, due to the excessive amount of catalyst, this could not be established in the outlet stream.

[0094] In Experiment 2 at 250 °C, almost instantaneous loss of activity was observed. Immediately after the start of the DME feed, incomplete conversion was suggested because a significant amount of DME was present in the reaction product (about 30% of the feed rate). Olefins were formed. After about 20 hours, the DME concentration increased gradually with time and the olefin concentration decreased gradually until the DME concentration reached a plateau at the input concentration and the hydrocarbon concentration became zero. This corresponded to the complete deactivation of the catalyst. The relatively low initial conversion was not unexpected because the temperature of 250 °C was somewhat low for DME (and methanol) dehydration experiments. Both of these experiments demonstrate the relatively rapid and complete deactivation of the catalyst.

[0095] The main difference between the first two experiments and the third experiment is the presence of the water adsorbent that affects the reactor performance and causes a transient response. When the water signal starts to increase significantly, it suggests that water has started to pass through the reactor and the water adsorbent has become saturated. At the same time, since the DME response increases strongly, it is suggested that the DME conversion has decreased. Before water breakthrough, the concept of enhanced adsorption is applied. The adsorbent removes water from the gas phase, causing a shift or enhancement of DME conversion.

[0096] In the third experiment at 250 °C in the presence of the water adsorbent, the conversion of DME is significantly higher than when only the catalyst is present (i.e., Experiment 2). In the initial 12 cycles, after switching to the DME feed, it is recognizable that all of the DME is converted to hydrocarbons as there is no DME present in the outlet stream. Even after 30 cycles (about 90 hours), the DME conversion is still about 50%. After 65 cycles (about 190 hours), the DME conversion drops to about 25% and then stabilizes at this 25% level (measured up to 125 cycles).

[0097] Therefore, comparing the second and third experiments, it is possible to conclude that the method of the present invention provides higher conversion and considerably long catalyst stability. In addition, we notice that the third experiment has not been optimized yet. The regeneration of the adsorbent may not be complete and may result in a decrease in the adsorption capacity and thus a decrease in DME conversion over time. Moreover, since the cycle time is longer than the time required to saturate the adsorbent, the reaction continues after the adsorbent is saturated (recognizable by the gradual increase in the water concentration in the outlet stream), which may lead to catalyst deactivation.

[0098] In conclusion, it is demonstrated from the experiments that when the sorbent is present, the catalyst activity is maintained longer even at a lower temperature (250 °C vs. 450 °C). In addition, equally importantly, by introducing the adsorbent into the conversion process from oxides to hydrocarbons, the conversion is considerably improved.

Claims

1. a) Contacting a catalyst and an oxygenated substance in a reactor in the presence of an sorbent material capable of adsorbing water to form a hydrocarbon, and subsequently b) Regenerating the sorbent material in the same reactor by bringing the sorbent material into contact with the purge gas, A process for converting oxygenated materials to hydrocarbons, wherein the catalyst and the sorbent material are not the same.

2. The process according to claim 1, wherein the process is operated cyclically, and step a) follows step b).

3. The process according to claim 1, wherein the temperature in step a) is 200°C to 500°C, preferably 200°C to 400°C, more preferably 200°C to 350°C, and most preferably 225°C to 275°C.

4. The process according to claim 1, wherein the pressure in step a) is 1.0 to 30 bar, preferably 1.0 to 20 bar.

5. The process according to claim 1, wherein the temperature in step b) is at least 100°C higher than the temperature in step a), and / or the pressure in step b) is at least 0.9 bar lower than the pressure in step a), preferably, the temperature in step b) is at least 150°C higher than the temperature in step a), and / or the pressure in step b) is at least 3.0 bar lower than the pressure in step a).

6. The process according to claim 1, comprising two or more reactors containing the catalyst and the sorbent material having the ability to adsorb water, preferably, at least one of the two or more reactors carrying out step a).

7. The process according to claim 1, wherein the catalyst is selected from the list consisting of H-beta, ZSM-5, ZSM-22, MCM-22, mordenite, UZM-9, SAPO (e.g., SAPO-17, -18, -34, -35, -44, -56), and AlPO, and preferably the catalyst is ZSM-5 or SAPO-34.

8. The process according to claim 1, wherein the adsorbent material having the ability to adsorb water is a molecular sieve having a pore diameter in the range of 2 to 5 Å, more preferably a zeolite having a pore diameter in the range of 2 to 5 Å, and even more preferably an LTA zeolite having a pore diameter in the range of 2 to 5 Å.

9. The process according to claim 1, wherein the weight ratio of the catalyst to the sorbent material capable of adsorbing water is 1.0:10.0 to 10.0:1.0, preferably 1.0:10.0 to 5.0:1.

0.

10. The process according to claim 1, wherein the adsorbent material having the ability to adsorb water has a water adsorption capacity of at least 0.04 grams of water per gram of adsorbent material at the temperature and pressure of step a), preferably at least 0.06 grams of water per gram of adsorbent material at the temperature and pressure of step a), more preferably at least 0.08 grams of water per gram of adsorbent material at the temperature and pressure of step a), and most preferably at least 0.10 grams of water per gram of adsorbent material at the temperature and pressure of step a).

11. The process according to claim 1, wherein the catalyst has a water adsorption capacity of less than 0.10 grams of water per gram of catalyst at the temperature and pressure of step a), preferably less than 0.04 grams of water per gram of catalyst at the temperature and pressure of step a).

12. The process according to claim 1, wherein the oxygenated substance is one or more of methanol (MeOH), ethanol (EtOH), isopropyl alcohol (IPA), n-butanol (BuOH), gasoline-grade tert-butanol (GTBA), methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), tert-hexyl methyl ether (THEME), ethyl tert-butyl ether (ETBE), tert-amyl ethyl ether (TAEE), dimethyl ether (DME), or diisopropyl ether (DIPE), preferably the oxygenated substance is methanol and / or dimethyl ether, and more preferably the oxygenated substance is methanol.

13. The process according to claim 1, wherein the hydrocarbon is selected from the group consisting of olefins, alkanes, aromatics, and any combination thereof, preferably the olefin is one or more of ethylene, propylene, 1-butene, 2-butene, and isobutylene, the alkane is one or more of alkanes containing 2 to 18 carbon atoms, and the aromatic is one or more of benzene, toluene, and xylene.

14. A fluidized bed reactor or fixed bed reactor for the conversion of oxygenated materials to hydrocarbons, comprising a catalyst for the conversion of oxygenated materials to hydrocarbons and an sorbent material capable of adsorbing water, wherein the catalyst and the sorbent material are not the same.

15. The use of a water-adsorbing sorbent material to increase the conversion of oxygenated materials to hydrocarbons, wherein the conversion is increased compared to when the sorbent material is absent, and the conversion from oxygenated materials to hydrocarbons occurs in the presence of a catalyst for the conversion from oxygenated materials to hydrocarbons, wherein the catalyst and the sorbent material are not identical.

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