Process enhanced production of decarburized olefins

Abstract

A mixed metal oxide selective oxygen carrier (SOC) suitable for selective oxidation of hydrogen, the SOC comprising bismuth oxide, a rare earth oxide, and Ti, Zr, and Hf dopants, can be characterized by high levels of oxygen carrying capacity, selectivity, and stability. The SOC can be synthesized by adopting a sol-gel process, a co-precipitation salt or an initial wet method. The invention includes a method of dehydrogenating paraffin on SOC. The SOC may also be used to catalytically crack hydrocarbons.

Description

[0001] Related applications

[0002] This application claims priority benefit of U.S. Provisional Patent Application Serial No. 63 / 434,463, filed on December 21, 2022.

[0003] Preface

[0004] Process intensification (PI) is a technique designed to modify conventional chemical processes into more cost-effective, higher-yielding, environmentally friendly, and safer ones. It offers opportunities to address some of the challenges encountered in mitigating the impact of greenhouse gas (GHG) emissions. PI technology is characterized by equipment size reduction through enhanced and targeted mixing and mass / heat transfer, resulting in improved selectivity, increased energy efficiency, lower capital costs, and reduced waste. The smaller processing volumes handled in intensified systems have the potential to reduce material costs and improve safety.

[0005] The production of light olefins (ethylene and propylene) is a particularly attractive target for process intensification, with combined production of these two chemicals exceeding 200 million tonnes in 2010, resulting in emissions of 220 million tonnes of CO2 equivalent (18% of the industry total).1 Recent reports indicate substantial growth in both markets (global production of at least 165 million tonnes of ethylene and 110 million tonnes of propylene in 2017, or annual demand growth rates exceeding 4% for each), and industry sources suggest that process emissions are growing at a corresponding rate.2 Ethylene (C2H4) and propylene (C3H6) are often described as integral to the chemical industry, serving as direct precursors to polyethylene and polypropylene (each accounting for approximately two-thirds of the demand for the respective monomers), with demand for these materials projected to grow by nearly 70% by 2050.[4] The highly endothermic cracking reactions, high operating temperatures (600–900°C), feed heating requirements, and complex downstream separations contribute to the high energy and CO2 emission intensities of these chemicals.6

[0006] To overcome the limitations of thermodynamic equilibrium, many research groups have investigated the oxygen dehydrogenation (ODH) of propane. However, no breakthrough has been achieved in finding catalysts that can provide the propylene yields required for commercial applications. As an alternative to ODH, different approaches based on the combination of dehydrogenation (DH) with selective hydrogen combustion (SHC) have been proposed. Selective hydrogen combustion (SHC) can be considered as an extension technology of catalytic hydrogen combustion, by which hydrogen can be selectively burned among a group of combustible components. The concept of SHC was proposed as early as the 1980s to improve DH.

[0007] The selective removal of hydrogen from dehydrogenation and other endothermic, equilibrium-limited H2-producing processes can increase the yield of these olefins. The main impact of this new technology is its significant GHG and energy saving potential. The current PDH process produces more than 1.5 tons of CO2 for every ton of propylene produced7. The main source of GHG emissions from PDH plants is the fuel burned to provide the reaction endotherm, which is about 3000MJ / ton of propylene. The oxidation of the hydrogen produced during the reaction can provide most of this endotherm. Since the PDH reaction is equilibrium-limited, removing hydrogen can achieve higher conversions at lower temperatures. In addition, compared with oxidative dehydrogenation (ODH), CL-ODH uses active lattice oxygen to achieve H2 removal, which (i) allows over-oxidation of the product to CO X and (ii) performing a reactive separation of O2 and N2.

[0008] SHC technology has been successfully integrated with the DH process for ethylbenzene to produce styrene using modified Pt, Pd, or Rh catalysts for SHC and Fe catalysts for DH [8,9] (Lummus / UOP SMART SM process). However, combining SHC with DH processes to produce light olefins from alkanes such as ethane, propane, and butane has not yet been commercialized. These processes face several challenges, such as low hydrogen combustion selectivity due to the combustion of hydrocarbon molecules and poor stability of the SHC catalyst.

[0009] In recent years, due to the increasing commercial demand for light olefins, especially propylene, many efforts have been made to improve the selectivity of hydrogen combustion and apply this technology to improve the production efficiency of light alkane dehydrogenation. For example, Lin et al. developed a new catalyst SiCuHZSM-5 and applied it to the selective combustion of hydrogen in the dehydrogenation of isobutane

[10] . They reported that a mixture of hydrogen, isobutane and air in a volume ratio of 2 / 2 / 96 at 550 ° C and 1 atm had high selectivity for hydrogen combustion. Grasselli's group tested various metal oxides as SHC catalysts for propane dehydrogenation using C3H8 / C3H6 / H2 in a ratio of 80 / 20 / 20, while co-feeding oxygen in a ratio of O2 / H2 = 10 / 20

[11] . Their results showed that the In2O3 / SiO2 catalyst had the best SHC activity and selectivity for hydrogen combustion (99.7%) compared with other catalysts. However, Blekkan et al. observed that the SHC selectivity of In2O3 / SiO2 catalysts decreased when the concentration of oxygen or propylene increased

[13] . Several other research reports have shown that Pt-based catalysts are reported to be effective for both SHC and DH reactions. Blekkan et al. reported that below a certain oxygen concentration, tin-doped Pt / SiO2 catalysts can burn hydrogen with a selectivity of about 90% at 500°C. In comparison, the selectivity of undoped Pt catalysts under the same conditions is relatively low (about 80%)

[14] . These results are supported by the work of Kaneko and co-workers, who studied supported PtSn catalysts for the combined propane dehydrogenation and SHC reactions at 500°C

[15] . They showed that when the O2 / H2 feed ratio was less than 1 / 2, the PtSn / ZnAlO catalyst could achieve stable propane conversions above the equilibrium conversion.

[0010] In contrast to the co-feed mode used to carry out the SHC reaction (where oxygen or air fluid is introduced along with the hydrocarbon), there is another approach for selective hydrogen combustion, known as the redox mode

[16] . In this mode, the SHC is operated in the absence of gaseous oxygen, and the solid oxygen carrier (SOC) is the only oxidant used to burn the hydrogen produced by the dehydrogenation reaction. The SOC thus acts as an oxygen reservoir, requiring oxygen replenishment, thereby separating the reaction and regeneration cycles, similar to chemical looping.

[0011] Various oxides have been proposed as SOCs for redox mode, such as Bi2O3 / SiO2

[16] , Ce 0.90 Bi 0.10O2

[18] , PbCrO4

[19] and Na2WO4 / CaMnO3

[20] . Grasselli et al.

[16] first explored the redox process mode of propane dehydrogenation, using Pt-Sn / HZSM-5 catalyst and Bi2O3 / SiO2 redox catalyst for selective oxidation of hydrogen. The selectivity of these systems was later obtained. et al.

[13] . Rothenberg’s group claimed that at 400℃, bismuth-doped cerium dioxide Ce 0.90 Bi 0.10 O2 catalysts not only exhibit high activity but also high selectivity for the oxidative dehydrogenation of propane, as 90% of the hydrogen feed can be converted with a selectivity of 98%

[18] . Rothenberg et al. published a comprehensive study on the selective hydrogen combustion using doped and promoted CeO2 in the dehydrogenation of ethane and propane, including a fixed-bed reactor study that employed a 1D transport modeling component to demonstrate an integrated process scheme for combined dehydrogenation and H2 oxidation [22–30]. Recent literature reports indicate that some progress has been made in identifying low-cost and low-toxicity redox catalysts with high H2 combustion selectivity - for example, Rothenberg and co-workers examined doped perovskite oxides LaFeO3 and LaMnO3 prepared from relatively abundant lanthanum oxides and transition metal oxides and found that they exhibited high selectivity (93%) for H2 combustion and satisfactory cycling stability in the presence of propane and propylene

[31] . Li and co-workers reported that the Na2WO4 / CaMnO3 catalyst showed 89% H2 conversion and 88% selectivity in a mixture of hydrogen and ethane at 850 °C, and it also provided stable SHC performance for more than 50 redox cycles

[20] . Agaskar et al. described an OC-based system involving two independently operated catalysts, one for propane dehydrogenation and one for selective hydrogen combustion32. Agaskar et al.

[32] also suggested mixed metal oxides containing Bi, Sb, or Te for SOC functionality and reported increased propylene production after the introduction of SOC catalysts.

[0012] US Patent No. 5,430,209 states that certain metal oxides are reduced more easily and faster by hydrogen than by hydrocarbons, and thus exhibit excellent selective hydrogen combustion (SHC) characteristics. 12 、In2Mo3O 12 、Bi2O3、Fe2Mo3O 12 、Ce2Mo3O 12Examples of metal oxides claimed to have excellent SHC properties are shown in the patent. The patent claims that when 42% Bi2O3 on silica is contacted with a 1:1 mixture of hydrogen and propylene at 550°C in helium for 140 seconds, hydrogen conversion is 85%, while propylene conversion is less than 0.5%. The patent also states that Bi2O3 is selective for hydrogen combustion in the presence of propane and co-feed gaseous oxygen. At 500°C, propane conversion to CO2 is less than 2%, while hydrogen conversion exceeds 990%. The patent claims that when propane is reacted at 540°C over physically mixed Pt-Sn-ZSM5 and Bi2O3 / silica, propane conversion and propylene yield increase from 24% and 22% to 47% and 42%, respectively, compared to Pt-Sn-ZSM5 alone. However, COx yield also increases from 0.6% to 3%.

[0013] Patent US2021 / 0213424A1 describes the synthesis of a redox catalyst for chemical chaining oxidative ethane dehydrogenation (CL-ODH). The redox catalyst consists of a core oxygen carrier region having an outer surface, a shell / surface layer comprising a promoter material. The patent describes a method for chemical chaining-oxidative cracking (CL-oxygen cracking) and chemical chaining-oxidative ethane dehydrogenation (CL-oxygen-ODH) using a redox catalyst. CL-oxygen cracking includes the use of a structured oxygen carrier that combines a low-temperature oxygen carrier with a surface modification, which inhibits the deep oxidation of hydrocarbons while allowing easy combustion or selective oxidative hydrogenation of hydrogen. In CL-oxygen cracking, alkanes are thermally or catalytically dehydrogenated, and the hydrogen produced is selectively burned by the oxygen carrier. In a separate regeneration step, the reduced oxygen carrier is then regenerated with air, CO2, or steam. Similarly, in CL-ODH, ethane is converted to ethylene, the hydrogen produced is selectively burned by the oxygen carrier, and the reduced oxygen carrier is then regenerated by air / CO2 or steam. The patent compares pure Pr6O11 with Pr6O 11 The 0.1 wt% Na2WO4 catalyst on Pr6O11 was reported to have ethane CL_ODH at 700°C, and it was claimed that 0.1% Na2WO4 on Pr6O11 achieved 20% ethane conversion and 25% and 17% ethylene yield, respectively, compared to pure Pr6O11. The SHC performance of Mg6MnO8 showed an SHC selectivity of 89% at 550°C, while the SHC selectivity of Mg6MnO8 with 20% Na2WO4 was 100%. Similar results were reported for SrMnO3 and CaMnO3 with and without 20% Na2WO4.

[0014] Patent 2004 / 0167013A1 discloses a catalyst system and process for combined cracking and selective hydrogen combustion. The feed stream may comprise hydrocarbon oils with a boiling point ranging from 221°C to 566°C, such as cracked gas oil, residue and gas oil, heavy and reduced petroleum crude oil, atmospheric distillation bottoms, heating oil, asphalt, tar, etc. The catalyst system consists of a solid acid component, a metal-based component composed of one or more elements from Group 3 and Groups 4-15 of the Periodic Table of the Elements, and at least one of oxygen and sulfur, wherein the Group 3 element, Group 4-15 element, and oxygen or sulfur are chemically bonded to a support. The patent claims that when using only a conventional zeolite catalyst, distilled at 700°C for 2 hours and reacted at 540°C without the addition of a selective hydrogen combustion (SHC) catalyst, the hydrogen yield is 0.23% by weight, the C1-C4 hydrocarbon yield is 33% by weight, and the light naphtha conversion is 39%. However, the patent claims that with the addition of the SHC catalyst, the hydrogen production is significantly reduced to 0.021 wt%, the hydrogen conversion is calculated to be 53%, the COx production is 0.055 wt%, and the H2 selectivity is 81%. The patent reports that better SHC depends on the preparation and synthesis of the SHC catalyst so that it can selectively burn hydrogen in the product while minimizing non-selective hydrocarbon oxidation. Therefore, LaMn is synthesized as follows 0.4 Ni 0.4 Al 0.2 O3 catalyst: A solution of lanthanum nitrate, manganese chloride, nickel nitrate, and aluminum nitrate in DI water was slowly poured into a separate solution of sodium bicarbonate and tetraethylammonium hydroxide in DI water to form a precipitate, and the suspension was then aged for one hour. The precipitate was recovered by centrifugation and washed with isopropyl alcohol to remove water impurities, cations, and anions. The washing step was repeated to completely remove impurities, followed by drying and calcination in air at 800°C for 2 hours.

[0015] Despite these and other efforts, the high operating costs due to low oxygen-carrying capacity, low hydrogen combustion selectivity leading to frequent switching, and the stability degradation of SHC catalysts due to repeated regeneration are probably the main reasons hindering the commercialization of redox-based SHC technology. Summary of the Invention

[0016] To be an effective candidate as an O2 carrier for selective hydrogen combustion, a metal oxide should be reducible under the dehydrogenation (DH) reaction conditions, thereby providing an oxygen source to burn H2. Furthermore, it should provide oxygen in a selective manner, thereby selectively converting H2 into H2O without oxidizing the bulk hydrocarbons present in the reactor (propane and propylene in our case). In general, a suitable SOC needs to (i) have a sufficiently high oxygen carrying capacity, (ii) be highly selective for hydrogen combustion, and (iii) be highly stable to repeated redox cycles.

[0017] Oxygen Support Selection: Reducible oxides of a few metals - Bi, In, Sb, Zn, Ti, Pb, and Te - are selective for SHC. This disclosure describes novel bismuth-based solid oxygen supports that, when combined with dehydrogenation catalysts, can be used as catalysts for selective hydrogen combustion.

[0018] 1. Oxygen-Carrying Capacity: The amount of oxygen a SOC can provide—its oxygen-carrying capacity—determines how frequently it should be replenished. Therefore, it is a crucial aspect of the SOC. Bismuth oxide has an oxygen-carrying capacity in the range of approximately 24 kg of oxygen per ton of carrier. The capacity of the SOC can be enhanced through judicious selection of the active oxygen-carrying material, its loading level, and the support material.

[0019] Although the active components of the catalyst are mainly responsible for the catalytic performance, the supports and / or modifiers also play an important role in the catalyst, affecting the dispersion and oxygen carrying capacity of the primary SOC. For example, Grasselli et al. ( 18 ) It was found that ZrO2 outperformed SiO2, TiO2, and Al2O3 supporting In2O3 for the SOC reaction. Similarly, the addition of Ce and Zr has been shown to increase the oxygen carrying capacity of bismuth oxide.

[0020] 2. Selectivity: In the context of SOC alkane dehydrogenation (DH), selectivity is defined as the lattice oxygen distribution between hydrogen combustion and hydrocarbon combustion. Combining oxidative dehydrogenation (ODH) with SOC is challenging for alkanes because selective H2 combustion is more difficult at higher temperatures due to the higher reactivity of the resulting olefin molecules. Consequently, propane ODH reactions operate at temperatures of 550°C or lower. In contrast, ethane ODH has been successfully performed above 600°C due to the lower reactivity of ethylene molecules.

[0021] However, studies have shown that the selectivity of redox catalysts is time-dependent and depends on the exact extent of oxidation or reduction of the SOC at a given time. In many cases, the activity and selectivity of redox catalysts are inversely proportional. 2- The redox catalyst of the species will favor complete oxidation rather than partial oxidation (22) This means that H2 selectivity changes with production time. (23-25) showed that selectivity, activity, and stability can be tuned by doping the oxide lattice with different cations. Cocatalysts and supports can be used to modify the activity and / or selectivity of redox oxides. For example, Kaneko et al. (23) It was observed that the addition of Zn to Al2O3 could improve the selectivity and stability of Pt / Al2O3 catalyst for the combined DH and SOC process at 500 °C.

[0022] 3. Stability: Catalysts with the highest selectivity for H2 combustion in redox mode typically contain oxides of In, Pb, and Bi, as well as transition metals such as Cr and Cu. In several studies, the same elements have been doped into ceria. (6-14) However, the stability and performance of these redox catalysts at temperatures above 550°C (e.g., 650-700°C for propane ODH and 800-850°C for ethane ODH) generally decrease over time.

[0023] Specifically, bismuth oxide and metallic bismuth have lower melting points (817°C and 272°C, respectively). Therefore, the activity of bismuth oxide as a SOC decreases over time. Bismuth can be stabilized by adding additional components, but if it does not form an active phase, this may reduce the available oxygen carrying capacity. Many candidates have been studied with positive results as dopants or supports to Bi, such as W, Ce or Zr. The stabilizer used in the present invention is typically a rare earth oxide present in an amount of about 10 mol% to about 40 mol%. Although the preferred rare earth oxide is yttrium oxide, it is believed that oxides of the entire lanthanide series can be used in the present invention.

[0024] We have found that adding small amounts of zirconium oxide or titanium dioxide to yttria-doped bismuth oxide can significantly improve the stability of bismuth oxide. A typical bismuth oxide-yttria composition is 75% bismuth oxide and 25% yttria. Incorporating zirconium oxide or titanium dioxide in amounts up to approximately 10 wt% improves the stability of yttria-doped bismuth oxide by several orders of magnitude.

[0025] In one aspect, the present invention provides a mixed metal oxide selective oxygen carrier (SOC) suitable for selective oxidation of hydrogen at elevated temperatures in the presence of hydrocarbons and steam, having the general formula (AC)(ST)(DP), wherein a) the active support (AC) represents an oxide of bismuth, b) the active support stabilizer (ST) represents an oxide of a rare earth metal selected from the group consisting of cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), terbium (Tb), ytterbium (Yb) and yttrium (Y) or mixtures thereof, and c) the dopant (DP) represents a Group 4 metal titanium (Ti), zirconium (Zr), hafnium (Hf) or mixtures thereof; and characterized in that the OC has an oxygen carrying capacity >20 kg O2 / ton of support, selectivity parameter ≤ 0.1 and stability parameter ≤ 0.0025, using the following test: SOC is loaded in a fixed bed reactor such that 50> dT / dP> 10 (ratio of tube diameter to SOC particle diameter), 200> L / dP> 50 (ratio of SOC bed length to SOC particle diameter) and 2> dP> 0.5 mm, at a temperature of 550°C, a pressure of 0.05 atm and a temperature of 0.5 hr -1The reactor was exposed to a feed flow of a 1:1 molar mixture of propylene and hydrogen at a feed rate of 100 wt hourly space velocity (WHSV) for 20 cycles, each cycle consisting of a 9 minute reaction followed by a 9 minute air regeneration with a 5 minute nitrogen purge between the reaction and air regeneration.

[0026] Since SOC cannot be fully distinguished from the prior art based solely on its elemental composition, the above measurements are needed to uniquely characterize the catalyst. In various embodiments, SOC can be further characterized by any of the compositional or physical properties described herein.

[0027] The present invention includes a method for dehydrogenating a paraffin wax, the method comprising contacting the paraffin wax with a SOC (as described herein) and a dehydrogenation catalyst in a reaction chamber under conditions sufficient to dehydrogenate the paraffin wax and produce olefins. Sufficient conditions are conventional conditions for dehydrogenation or can be determined by only routine experimentation.

[0028] In another aspect, the present invention provides a method for synthesizing SOC using a sol-gel procedure, wherein an organic alkoxide or mixture of supports is first dissolved in an organic solvent, the solution is hydrolyzed using a mineral acid or base, and the resulting sol-gel mixture is dried and calcined to produce the SOC.

[0029] In another aspect, the present invention provides a method for synthesizing SOC using a coprecipitation procedure, wherein a salt or mixture of SOC is first dissolved in water, and then the salt is coprecipitated from the solution using a precipitant. Finally, the resulting precipitate is dried and calcined to produce SOC.

[0030] A binder such as alumina, silica or titania may be added to the SOC and then calcined to form a final particle with a BET surface area greater than 30 m 2 / g, and the particle size of the mixed metal oxide SOC is between 30-3000 microns (μm).

[0031] In another aspect, the present invention provides a method for synthesizing SOC using the incipient wetness method. A SOC support such as silica, alumina, or titania is impregnated with a salt solution of the SOC metal, followed by drying and finally calcination to produce the final form of the SOC.

[0032] Another aspect of the present invention provides a continuous process for dehydrogenating paraffin wax having 2 to 8 carbon atoms using SOC and a suitable dehydrogenation catalyst, wherein the process is carried out at a reaction temperature of 500 to 800° C. and a reaction time of 0.1 to 1 hour. 1The process is carried out under a space velocity of 0.01-0.2 MPa, a pressure of 0.01-0.2 MPa and an SOC to dehydrogenation catalyst ratio of 0.1 to 10 wt / wt (SOC mass / dehydrogenation catalyst mass). The paraffin feedstock is contacted with the catalyst under dehydrogenation conditions for a reaction period in the range of about 0.05 seconds to 10 minutes. After the reaction period, the catalyst is regenerated by contacting the catalyst with air. Catalyst regeneration is carried out at a reaction temperature of 500-800° C., a pressure of 0.01-0.2 MPa and a regeneration period in the range of about 1 minute to 10 minutes. The process can be carried out in a fluidized bed reactor or a fixed bed swing reactor. Preferably, the method comprises 2-10,000 cycles or 2-1000 or 2-100 cycles, wherein preferably no more than 5% or 2% or no more than 1% by mass of fresh catalyst (on average) is added in each cycle.

[0033] Another aspect of the present invention provides a continuous process for catalytically cracking hydrocarbons, the process being carried out by contacting hydrocarbons having 4 to 40 carbon atoms with SOC and a suitable cracking catalyst in a reaction chamber under conditions sufficient to crack the hydrocarbons into smaller molecules, the reaction temperature of the hydrocarbons with the SOC and the suitable cracking catalyst being 500 to 800° C. for 0.1 to 60 hours. -1 The method comprises contacting the SOC and the cracking catalyst with an oxygen-containing gas at a space velocity of 100-200° C. and a pressure of 0.01-0.2 MPa, a steam concentration of 0-30 wt % and a SOC to cracking catalyst ratio of 0.1 to 10 wt / wt for a reaction period in the range of 0.05 seconds to 10 minutes; regenerating the SOC and the cracking catalyst with an oxygen-containing gas, wherein the regeneration is carried out at a reaction temperature of 500-800° C., a pressure of 0.01-0.2 MPa and a regeneration period in the range of 0.05 seconds to 10 minutes.

[0034] In any of its aspects, the present invention may also be characterized by one or any combination of the following: wherein the AC (active carrier) species constitutes 1 wt% to 75 wt% of the total weight of the SOC, wherein the weight includes the transition metal and the associated oxygen required to balance the oxidation state of the transition metal; wherein the active carrier (AC) species constitutes 1 wt% to 50 wt% of the total weight of the SOC; wherein the active carrier (AC) species constitutes 1 wt% to 40 wt% of the total weight of the SOC; wherein the DP (dopant) constitutes 1 wt% to 15 wt% of the total weight of the SOC; wherein the DP (dopant) 1 wt% to 10 wt% of the total weight of the SOC; wherein DP (dopant) accounts for 1 wt% to 5 wt% of the total weight of the SOC; wherein ST (SOC stabilizer) accounts for 1 wt% to 50 wt% of the total weight of the SOC; wherein ST (SOC stabilizer) accounts for 1 wt% to 35 wt% of the total weight of the SOC; wherein ST (SOC stabilizer) accounts for 1 wt% to 15 wt% of the total weight of the SOC; wherein the SOC composition has less than 2 wt% of copper (Cu) or manganese (Mn) or magnesium (Mg); wherein the BET surface area is >30 m2 / g; wherein SOC is synthesized using inorganic salts, comprising the steps of: a) dissolving appropriate salts of AC, ST and DP or a mixture thereof in water, b) co-precipitating the salts using a precipitant such as ammonium hydroxide, c) drying and calcining the resulting precipitate to produce SOC, and d) adding a carrier support CS to the SOC to form particles; wherein SOC is synthesized using a sol-gel procedure, comprising the steps of: a) dissolving an organic alkoxide, an acetate of AC, ST and DP or a mixture thereof in an organic solvent, b) hydrolyzing the organic alkoxide, acetate solution, preferably in the presence of an acid or base catalyst, to produce a gel, c) drying and calcining the resulting gel to produce SOC, and d) adding a carrier support CS to the SOC to form particles; wherein SOC and the support are mixed in an oxygen-containing atmosphere , preferably calcined in air at 500-1100°C, preferably 550-800°C, and most preferably 550-650°C for 2-6 hours; wherein the SOC is synthesized using an inorganic salt, comprising the steps of: a) dissolving an appropriate salt of AC, ST, and DP, or a mixture thereof, in water, b) impregnating a carrier support CS with the salt solution, c) drying and calcining the resulting precipitate in an oxygen-containing atmosphere, preferably air, preferably at 550-800°C, and most preferably 550-650°C, for 2-6 hours to produce SOC particles; wherein the volume average particle size of the mixed metal oxide SOC is 30-3000 microns (μm); wherein the paraffin is carried out in a fluidized bed reactor or a fixed bed rocking reactor; and / or wherein the contacting is carried out in a fluidized bed reactor or a fixed bed rocking reactor. In these descriptions, the "weight" or "mass" of the metal includes the associated oxygen atoms.

[0035] The present invention is further illustrated in the following examples. In any of its aspects, the invention may also be characterized by any description selected from the examples, for example, within ±20% (or within ±10%) of any value in any of the examples, tables or figures; however, the scope of the invention, in its broader aspects, is not intended to be limited by these examples.

[0036] The present invention can provide advantages such as: the product of catalyst activity and catalyst selectivity exceeds 0.1 tons of product / hour / ton of catalyst; and the overall catalyst consumption does not exceed 1 kg catalyst / ton of product. None of the existing technologies meet these three characteristics simultaneously.

[0037] Glossary

[0038] Oxygen Carrying Capacity - The oxygen carrying capacity (OCC) of a solid oxygen carrier (SOC) is defined as the amount of lattice oxygen available for oxidation. The OCC is typically calculated by assuming that the mass change of the SOC during reduction is primarily due to the loss of lattice oxygen from the carrier. OCC is measured in kg oxygen / ton SOC, and an effective SOC will have an OCC > 20 kg oxygen / ton SOC.

[0039] Selectivity Parameter - Since SOCs can burn both hydrogen and hydrocarbons, a method is needed to compare the selectivities achieved by different SOCs, as well as PDH catalysts, at different conversions. The selectivity parameter is calculated from the ratio of the rate constant for the hydrocarbon oxidation reaction to the rate constant for the alkane dehydrogenation reaction and remains constant regardless of alkane conversion. It can be quantified by the COx / olefin ratio (wt / wt) at the reactor outlet. Catalysts that produce olefins with high selectivity will have a selectivity parameter of <0.1.

[0040] SOC stability parameter - The loss of SOC with repeated reaction-regeneration cycles is quantified by measuring the rate of change of SOC capacity with cycle number. The stability parameter is measured as follows: Stability parameter = [1 – x 20 / x1] / 19, where x1 and x 20 It refers to the hydrogen conversion rate of the 1st and 20th cycles. The stability parameter value of the SOC with high stability will be ≤ 0.0025. The stability parameter of US Patent 5,430,209 is about 0.006.

[0041] Calcination Temperature - The term "calcination temperature" refers to the maximum temperature used as an intermediate step in a catalyst synthesis procedure to convert metal salts to their oxide forms.

[0042] Regeneration Temperature - The catalyst can be regenerated at elevated temperatures under flowing air in order to remove heavier hydrocarbons (coke) from the active catalyst structure. The maximum temperature used in this step is referred to as the "regeneration temperature."

[0043] Conversion - The term "conversion of a reactant" refers to the change in moles or mass of a reactant between the material flowing into the reactor and the material flowing out of the reactor divided by the moles or mass of the reactant in the material flowing into the reactor.

[0044] Pore ​​size - Pore size refers to the size of molecules or atoms that can penetrate the pores of a material. As used herein, the term "pore size" of zeolites and similar catalyst compositions refers to the Norman radius adjusted pore size, which is well known to those skilled in the art. The determination of Norman radius adjusted pore size is described, for example, in Cook, M.; Conner, W.C., "How big are the pores of zeolites?" Proceedings of the International Zeolite Conference, 12th, Baltimore, July 5-10, 1998; (1999), 1, pp. 409-414.

[0045] "Particle size" is the number average particle size and, for non-spherical particles, is based on the largest dimension.

[0046] One of ordinary skill in the art will understand how to determine the pore size (e.g., minimum pore size, average of minimum pore size) in the catalyst. For example, x-ray diffraction (XRD) can be used to determine atomic coordinates. XRD techniques for determining pore size are described, for example, in Pecharsky, VK et al., "Fundamentals of Powder Diffraction and Structural Characterization of Materials", Springer Science+Business Media, Inc., New York, 2005. Other techniques that can be used to determine pore size (e.g., zeolite pore size) include, for example, helium pycnometry or low-pressure argon adsorption techniques. These and other techniques are described in Magee, JS et al., "Fluid Catalytic Cracking: Science and Technology", Elsevier Publishing Company, July 1, 1993, pp. 185-195. The pore size of the mesoporous catalyst can be determined, for example, by nitrogen adsorption techniques as described in Gregg, SJ et al., “Adsorption, Surface Area and Porosity”, 2nd ed., Academic Press Inc., New York, 1982 and Rouquerol, F. et al., “Adsorption by powders and porous materials. Principles, Methodology and Applications”, Academic Press Inc., New York, 1998.

[0047] Residence Time - Residence time is the time a substance spends in a reaction vessel. It can be defined as the volume of the reactor divided by the flow rate (volume per second) of the gas entering the reactor.

[0048] Selectivity - The term "selectivity" refers to the percentage of a particular product (or products) produced relative to all products produced in a reaction. For example, if 100 grams of product are produced in a reaction and 80 grams of olefin are found among these products, the selectivity for olefin over all products is 80 / 100 = 80%. Selectivity can be calculated on a mass basis, as in the aforementioned examples, or it can be calculated on a molar basis, where the selectivity is calculated by dividing the number of moles of a particular product by the number of moles of all products. Unless otherwise indicated, selectivity is based on mass.

[0049] Yield - The term "yield" is used herein to refer to the amount of product exiting a reactor divided by the amount of reactants flowing into the reactor, typically expressed as a percentage or fraction. Mass yield is the mass of a specific product divided by the weight of the feed used to produce that product. Unless otherwise specified, "%" refers to mass %, which is synonymous with weight %. Ideal gas behavior is assumed so that mole % in the gas phase is the same as volume %.

[0050] In accordance with standard patent terminology, the term "comprising" means "including" and does not exclude additional components. Any inventive aspect described in conjunction with the term "comprising" also includes narrower embodiments in which the term "comprising" is replaced by the narrower terms "consisting essentially of" or "consisting of." As used in this specification, the terms "includes" or "including" should not be construed as limiting the invention, but rather as listing exemplary components. In accordance with standard terminology, a "system" includes devices and materials (e.g., reactants and products) as well as conditions within the devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 The effect of bismuth loading on SOC capacity using yttrium oxide as a support is shown. Estimates based on gas flow rates indicate that Bi2O3-based SOCs have available oxygen carrying capacities between 20-90 kg oxygen / ton SOC. Our studies demonstrate that both the support and bismuth loading influence SOC capacity.

[0052] Figure 2 Selective hydrogen combustion using a combined PDH of Zr-YDB SOC. Hydrogen conversion and propylene selectivity are shown as a function of propane conversion. Example

[0053] Example 1

[0054] A solid oxygen carrier (SOC) was prepared by dispersing 6 ml of a 15% bismuth nitrate solution on 17 gm of zirconium oxide by the incipient wetness technique, followed by drying at 120° C. overnight and calcining at 450° C. for 4 hours. This SOC was designated SOC A.

[0055] Example 2

[0056] The SOC used was the same as in Example 1, the only difference being that the support was silica instead of zirconia. This SOC was designated SOC B.

[0057] Example 3

[0058] The SOC used was the same as in Example 1, the only difference being that the support was titania instead of zirconia. This SOC was designated SOC C.

[0059] Example 4

[0060] The SOC used was the same as in Example 1, the only difference being that the support was ceria instead of zirconia. This SOC was designated SOC D.

[0061] Example 5

[0062] A SOC was prepared by dispersing an alumina binder in the form of acidic Dispal (T25N4-80) from Sasol in 55 ml of DI water for 30 minutes, followed by mixing BiO powder from Sigma Aldrich with the dispersed Dispal for 30 minutes. Excess water was evaporated by heating to obtain a paste. The paste was dried at 120°C overnight and then calcined at 800°C for 5 hours. The target BiO to AlO ratio in the mixture was 50 / 50 (wt / wt). This SOC was designated SOC E.

[0063] Example 6

[0064] A SOC was prepared as in Example 5, with the only difference being that the ratio of Bi2O3 to Al2O3 in the mixture was targeted to be 45 / 55 (wt / wt). This SOC was designated SOC F.

[0065] Example 7

[0066] A SOC was prepared as in Example 5, with the only difference being that the ratio of Bi2O3 to Al2O3 in the mixture was targeted to be 35 / 65 (wt / wt). This SOC was designated SOC G.

[0067] Example 8

[0068] The SOC was prepared by dispersing an alumina binder in the form of acidic Dispal (T25N4-80) from Sasol in 55 ml of DI water for 30 minutes, followed by mixing Bi2O3 powder from Sigma Aldrich with the dispersed Dispal for 30 minutes. Excess water was evaporated by heating to obtain a paste. The paste was dried at 120°C overnight. An aqueous solution consisting of 1 wt% CaO and 1 wt% MgO alkaline earth metal (AEM) oxides (in the form of nitrates) was dispersed on the dried SOC using the incipient wetness technique, followed by calcination at 800°C for 5 hours. The Bi2O3 to Al2O3 ratio in the mixture was targeted to be 80 / 20 (wt / wt). This SOC was designated SOC H.

[0069] Example 9

[0070] A SOC was prepared as in Example 8, with the only difference being that the ratio of Bi2O3 to Al2O3 in the mixture was targeted to be 70 / 30 (wt / wt). This SOC was designated SOC I.

[0071] Example 10

[0072] A SOC was prepared as in Example 8, with the only difference being that the ratio of Bi2O3 to Al2O3 in the mixture was targeted to be 60 / 40 (wt / wt). This SOC was designated SOC J.

[0073] Example 11

[0074] A SOC was prepared as in Example 8, with the only difference being that the ratio of Bi2O3 to Al2O3 in the mixture was targeted to be 50 / 50 (wt / wt). This SOC was designated SOC K.

[0075] Example 12

[0076] A SOC was prepared as in Example 8, with the only difference being that the ratio of Bi2O3 to Al2O3 in the mixture was targeted to be 40 / 60 (wt / wt). This SOC was designated SOC L.

[0077] Example 13

[0078] A SOC was prepared as in Example 8, with the only difference being that the ratio of Bi2O3 to Al2O3 in the mixture was targeted to be 30 / 70 (wt / wt). This SOC was designated SOC M.

[0079] Example 14

[0080] A SOC was prepared as in Example 8, with the only difference being that the ratio of Bi2O3 to Al2O3 in the mixture was targeted to be 20 / 80 (wt / wt). This SOC was designated SOC N.

[0081] Example 15

[0082] A SOC was prepared as in Example 13, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 2 wt% CaO and 2 wt% MgO. This SOC was designated SOC O.

[0083] Example 16

[0084] A SOC was prepared as in Example 13, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 3 wt% CaO and 3 wt% MgO. This SOC was designated SOC P.

[0085] Example 17

[0086] A SOC was prepared as in Example 13, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 4 wt% CaO and 4 wt% MgO. This SOC was designated SOC Q.

[0087] Example 18

[0088] A SOC was prepared as in Example 13, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 5 wt% CaO and 5 wt% MgO. This SOC was designated SOC R.

[0089] Example 19

[0090] A SOC was prepared as in Example 13, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 7.5 wt% CaO and 7.5 wt% MgO. This SOC was designated SOC S.

[0091] Example 20

[0092] A SOC was prepared as in Example 13, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 10 wt% CaO and 10 wt% MgO. This SOC was designated SOC T.

[0093] Example 21

[0094] A SOC was prepared as in Example 13, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 0 wt% CaO and 4 wt% MgO. This SOC was designated SOC U.

[0095] Example 22

[0096] SOC was prepared by adding AEM to commercial bismuth aluminate hydrate from Sigma Aldrich. An aqueous solution consisting of 3 wt% CaO and 3 wt% MgO alkaline earth metal (AEM) oxide (in the form of nitrate) was dispersed on the commercial bismuth aluminate by the incipient wetness technique, followed by drying at 120°C overnight and calcining at 550°C for 4 hours. This SOC was designated SOC V.

[0097] Example 23

[0098] A SOC was prepared as in Example 22, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 7.5 wt% CaO and 7.5 wt% MgO. This SOC was designated SOC W.

[0099] Example 24

[0100] A SOC was prepared as in Example 22, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 10 wt% CaO and 10 wt% MgO. This SOC was designated SOC X.

[0101] Example 25

[0102] A SOC was prepared as in Example 22, with the only difference that the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisted of 15 wt% CaO and 15 wt% MgO. This SOC was designated SOC Y

[0103] Example 26

[0104] The SOC was prepared by dispersing an alumina binder in the form of acidic Dispal (T25N4-80) from Sasol in 25 ml of DI water for 30 minutes. 50 wt% BiO and 50 wt% YO powders from Sigma Aldrich and Alfa Aesar were then mixed with the dispersed Dispal for 30 minutes. Excess water was evaporated by heating to obtain a paste. The paste was dried at 120°C overnight and calcined at 800°C for 5 hours. The target ratio of the total amount of BiO and YO to AlO in the mixture was 80 / 20 (wt / wt). This SOC was designated SOC Z.

[0105] Example 27

[0106] A SOC was prepared as in Example 26, with the only difference being that the ratio of the total amount of Bi2O3 and Y2O3 to Al2O3 in the mixture was targeted to be 70 / 30 (wt / wt). This SOC was designated SOC AA.

[0107] Example 28

[0108] SOC was prepared by precipitation. An aqueous solution of 3M nitric acid was prepared by mixing 54ml of 70% nitric acid in 146ml of DI water and then dissolving yttrium nitrate, zirconyl nitrate, and bismuth nitrate salts at room temperature. A water-insoluble precipitate of bismuth, zirconium oxide, and yttrium hydroxide was obtained by dropwise addition of 2M NH4OH until the solution reached a pH of 8 and filtering. The precipitate was dried at 120°C overnight and calcined at 800°C for 5 hours. The target ratio of Bi2O3 to Y2O3 in the mixture was 25 / 75 (wt / wt). This SOC was designated SOC AB.

[0109] Example 29

[0110] A SOC was prepared as in Example 28, with the only difference being that the ratio of Bi2O3 to Y2O3 in the mixture was targeted to be 50 / 50 (wt / wt). This SOC was designated SOC AC.

[0111] Example 30

[0112] A SOC was prepared as in Example 28, with the only difference being that the ratio of Bi2O3 to Y2O3 in the mixture was targeted to be 75 / 25 (wt / wt). This SOC was designated SOC AD.

[0113] SOC test

[0114] The SOC of Examples 28-30 was tested as follows: SOC was loaded into a packed bed reactor such that d T / d p >10 and L / d p >50. The SOC was activated by flowing air at 550°C for 4 hours. The experiments were conducted in a fixed bed reactor at a temperature of 550°C and a GHSV of 5000 / hr, which are typical conditions for the dehydrogenation process.

[0115] PDH+SOC combination test

[0116] The SOC of Example 29 was combined with an ExOlt dehydrogenation catalyst (4:1 wt / wt ratio) to run the reaction in conjunction with selective hydrogen oxidation under commercial reactor conditions. Exelus used its patented ExOlt dehydrogenation catalyst (U.S. Patent No. 11,478,778). The results are shown in Figure 5. The test showed high propane conversion (>45%) as well as high propylene selectivity (>85%) and low COx formation (SP <0.1). TCD measurements showed that for approximately 45% propane conversion, 100% of the hydrogen evolved in the dehydrogenation reaction was consumed. This demonstrates that the SOC is effective under PDH reaction conditions without excessive combustion of hydrocarbons.

[0117] Although there have been many studies in the literature (1)(2) Selective hydrogen combustion has been combined with the PDH reaction, but no study has demonstrated combined reaction temperatures above 500°C and / or high propane conversions with high propylene selectivity. Our experiments also show that SOC is selective for hydrogen combustion not only in the presence of propane, but also in the presence of significant amounts of propylene. To our knowledge, this is the first successful application of a chemical-looping-based catalyst system to achieve high conversions (>45%) with high propylene selectivity (>90 mol%).

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Claims

1. A mixed metal oxide selective oxygen carrier (SOC) suitable for selectively oxidizing hydrogen in the presence of hydrocarbons and steam at elevated temperatures, having the general formula (AC)(ST)(DP), wherein a) The active carrier (AC) represents bismuth oxide, b) the active support stabilizer (ST) represents an oxide of a rare earth metal selected from the group consisting of cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), terbium (Tb), ytterbium (Yb) and yttrium (Y) or a mixture thereof, and c) the dopant (DP) represents an oxide of a Group 4 metal titanium (Ti), zirconium (Zr), hafnium (Hf), or a mixture thereof; and Characterized by OC, oxygen carrying capacity> 20 kg O2 / ton of support, selectivity parameter ≤ 0.1 and stability parameter ≤ 0.0025, using the following test: SOC is loaded in a fixed bed reactor so that 50> dT / dP> 10 (ratio of tube diameter to SOC particle diameter), 200> L / dP> 50 (ratio of SOC bed length to SOC particle diameter) and 2> dP> 0.5 mm, at a temperature of 550 ° C, a pressure of 0.05 atm and a temperature of 0.5 hr -1 The reactor was exposed to a feed stream of a 1:1 molar mixture of propylene and hydrogen at a feed rate of 100 wt hourly space velocity (WHSV) for 20 cycles of 9 minutes of reaction followed by 9 minutes of air regeneration with a 5 minute nitrogen purge between reaction and air regeneration.

2. The SOC composition of claim 1, wherein the AC (active carrier) species comprises 1 wt% to 75 wt% of the total weight of the SOC, wherein the weight includes the transition metal and the associated oxygen required to balance the oxidation state of the transition metal.

3. The SOC composition of claim 1, wherein the active carrier (AC) species accounts for 1 wt% to 50 wt% of the total weight of the SOC.

4. The SOC composition of claim 1, wherein the active carrier (AC) species accounts for 1 wt% to 40 wt% of the total weight of the SOC. The SOC composition according to claim 1 , wherein the DP (dopant) accounts for 1 wt % to 15 wt % of the total weight of the SOC. The SOC composition according to claim 1 , wherein the DP (dopant) accounts for 1 wt % to 10 wt % of the total weight of the SOC. The SOC composition according to claim 1 , wherein the DP (dopant) accounts for 1 wt % to 5 wt % of the total weight of the SOC. The SOC composition according to claim 1 , wherein ST (SOC stabilizer) accounts for 1 wt % to 50 wt % of the total weight of the SOC. 9 . The SOC composition according to claim 1 , wherein ST (SOC stabilizer) accounts for 1 wt % to 35 wt % of the total weight of the SOC.

10. The SOC composition according to claim 1, wherein ST (SOC stabilizer) accounts for 1 wt% to 15 wt% of the total weight of the SOC.

11. The SOC composition according to any one of claims 1 to 9, wherein the SOC composition has less than 2 wt% of copper (Cu) or manganese (Mn) or magnesium (Mg).

12. The SOC composition according to any one of claims 1 to 9, wherein the BET surface area is >30 m 2 / g.

13. A method for preparing the SOC according to claim 1, wherein the SOC is synthesized using an inorganic salt, comprising the following steps: a) dissolving appropriate salts of AC, ST and DP or a mixture thereof in water; b) co-precipitating the salt using a precipitant such as ammonium hydroxide; c) drying and calcining the resulting precipitate to produce the SOC; d) adding a carrier support CS to the SOC to form particles.

14. A method for preparing the SOC as claimed in claim 1, wherein the SOC is synthesized using a sol-gel procedure, comprising the following steps: a) dissolving an organic alkoxide, an acetate of AC, ST and DP or a mixture thereof in an organic solvent; b) hydrolyzing the organic alkoxide or acetate solution, preferably in the presence of an acid or base catalyst, to produce a gel; c) drying and calcining the resulting gel to produce the SOC; d) adding a carrier support CS to the SOC to form particles.

15. The method according to any one of claims 13 to 14, wherein the SOC and support are calcined in an oxygen-containing atmosphere, preferably air, at 500-1100°C, preferably 550-800°C and most preferably 550-650°C for 2-6 hr.

16. A method for preparing the SOC according to claim 1, wherein the SOC is synthesized using an inorganic salt, comprising the following steps: a) dissolving appropriate salts of AC, ST and DP or a mixture thereof in water; b) impregnating a carrier support CS with the salt solution; c) drying and calcining the resulting precipitate in an oxygen-containing atmosphere, preferably air, preferably at 550-800° C. and most preferably at 550-650° C. for 2-6 hrs to produce SOC particles.

17. The SOC composition according to any one of claims 1 to 9, wherein the mixed metal oxide SOC has a particle size of 30-3000 micrometers (μm).

18. A method of dehydrogenating a paraffin wax, the method comprising contacting the paraffin wax with the SOC of any one of claims 1 to 9 and a suitable dehydrogenation catalyst in a reaction chamber under conditions sufficient to dehydrogenate the paraffin wax and produce olefins.

19. A method for continuously dehydrogenating paraffin wax having 2 to 8 carbon atoms, the method comprising: At a reaction temperature of 500-800°C, 0.1-60hr -1 contacting the paraffin wax with the SOC composition according to any one of claims 1 to 9 and a suitable dehydrogenation catalyst for a reaction period ranging from 0.05 seconds to 10 minutes at a space velocity of 0.01-0.2 MPa and a SOC to dehydrogenation catalyst ratio of 0.1 to 10 wt / wt; The SOC and the dehydrogenation catalyst are regenerated with an oxygen-containing gas, wherein the regeneration is performed at a reaction temperature of 500-800° C., a pressure of 0.01-0.2 MPa, and a regeneration period ranging from 0.05 seconds to 10 minutes.

20. The method of claim 19, wherein the contacting is performed in a fluidized bed reactor or a fixed bed swing reactor.

21. A method for cracking hydrocarbons, the method comprising: The hydrocarbon having 4 to 40 carbon atoms is contacted with the SOC of any one of claims 1 to 9 and a suitable cracking catalyst in a reaction chamber under conditions sufficient to crack the hydrocarbon into smaller molecules.

22. A method for cracking hydrocarbons, the method comprising: The hydrocarbon having 4 to 40 carbon atoms is contacted with the SOC according to any one of claims 1 to 9 and a suitable cracking catalyst in a reaction chamber under conditions sufficient to crack the hydrocarbon into smaller molecules, and the hydrocarbon is contacted with the SOC composition according to any one of claims 1 to 9 and a suitable cracking catalyst at a reaction temperature of 500 to 800° C. for 0.1 to 60 hours. -1 contacting for a reaction period ranging from 0.05 seconds to 10 minutes at a space velocity of 0.01-0.2 MPa, a steam concentration of 0-30 wt % and a SOC to cracking catalyst ratio of 0.1 to 10 wt / wt; The SOC and the cracking catalyst are regenerated with an oxygen-containing gas, wherein the regeneration is performed at a reaction temperature of 500-800° C., a pressure of 0.01-0.2 MPa, and a regeneration period ranging from 0.05 seconds to 10 minutes.

23. The method of claim 22, wherein the contacting is performed in a fluidized bed reactor or a fixed bed swing reactor.

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