WO2024059600A1 - Procédés de déshydrogénation d'hydrocarbures utilisant des régénérateurs - Google Patents

Procédés de déshydrogénation d'hydrocarbures utilisant des régénérateurs Download PDF

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Publication number
WO2024059600A1
WO2024059600A1 PCT/US2023/074022 US2023074022W WO2024059600A1 WO 2024059600 A1 WO2024059600 A1 WO 2024059600A1 US 2023074022 W US2023074022 W US 2023074022W WO 2024059600 A1 WO2024059600 A1 WO 2024059600A1
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Prior art keywords
oxygen
mol
particulate solid
regeneration unit
carrier material
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PCT/US2023/074022
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English (en)
Inventor
Matthew T. PRETZ
Charmaine BENNETT
Kevin Blann
Jordan KEITH
Davy Nieskens
Anthony PLAUCK
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Dow Global Technologies Llc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead

Definitions

  • Embodiments described herein generally relate to chemical processing and, more specifically, to processes and systems utilized for dehydrogenation of chemical species.
  • Olefinic compounds may be utilized as base materials to produce many types of goods and materials.
  • ethylene may be utilized to manufacture polyethylene, ethylene chloride, or ethylene oxides.
  • Such products may be utilized in product packaging, construction, textiles, etc.
  • olefinic compounds such as ethylene, propylene, butene, and styrene.
  • One method for producing olefinic compounds is by dehydrogenating hydrocarbons.
  • the dehydrogenation reaction may be promoted by reducing or removing hydrogen formed during dehydrogenation by reacting the hydrogen with oxygen to form water, which pushes the equilibrium towards the olefinic compound products.
  • an oxygen-carrier material may be utilized to provide the oxygen that reacts with the hydrogen.
  • the oxygen-carrier material may be included in a particulate solid.
  • Such oxygen-carrier materials may cycle through a reactor and a regeneration unit, where the content of oxygen in the oxygen carrier material may be increased in the regeneration unit.
  • a fuel is additionally utilized in the regeneration unit to heat at least the oxygen carrier material.
  • Embodiments described herein include flow patterns where the particulate solid moves generally downwards though the regenerator and the gases, including the fuel and an oxygen-containing gas, move in a generally upwards direction. Additionally, the fuel and oxygencontaining gas enter the regeneration unit through first and second gas inlets, respectively, where the second gas inlet is beneath the first gas inlet. Such an arrangement may allow for the oxygencarrier material to be both sufficiently oxidized and heated to perform a dehydrogenation reaction. During fuel combustion, oxygen from the oxygen-carrier material may be utilized, which reduces the oxygen content of the oxygen-carrier material. Exposing the oxygen-carrier material to an oxygen-containing gas after fuel combustion may help to ensure that the oxygen-carrier material exits the regeneration unit sufficiently oxidized.
  • hydrocarbons may be dehydrogenated by a process comprising contacting a feed stream comprising one or more hydrocarbons with a particulate solid in a dehydrogenation reactor.
  • the particulate solid may comprise an oxygen-carrier material.
  • the one or more hydrocarbons may be dehydrogenated to form hydrogen and one or more products.
  • At least a portion of the hydrogen may be reacted with oxygen from the oxygen-carrier material to form water and reduce the oxygen content in the oxygen-carrier material.
  • the process may further comprise passing at least a portion of the particulate solid from the dehydrogenation reactor to a regeneration unit.
  • the particulate solid may move in a generally downward direction through the regeneration unit and gases may move in a generally upwards direction through the regeneration unit, such that the particulate solid and gases move in a countercurrent flow pattern through the regeneration unit.
  • the regeneration unit may comprise a first gas inlet and a second gas inlet, the second gas inlet may be beneath the first gas inlet.
  • a fuel may enter into the regeneration unit through the first gas inlet.
  • An oxygen-containing gas may enter into the regeneration unit through the second gas inlet.
  • at least a portion of the fuel may be reacted with oxygen from one or both of the oxygen-containing gas or the oxygen-carrier material of the particulate solid.
  • the process may further comprise passing at least a portion of the particulate solid from the regeneration unit to the dehydrogenation reactor.
  • FIG. 1 schematically depicts a reactor system, according to one or more embodiments of the present disclosure.
  • FIG. 2 schematically depicts another reactor system according to additional embodiments of the present disclosure.
  • FIG. 1 and FIG. 2 When describing the simplified schematic illustration of FIG. 1 and FIG. 2, the numerous valves, temperature sensors, electronic controllers, and the like, which may be used and are well known to a person of ordinary skill in the art, are not included. Further, accompanying components that are often included in such reactor systems, such as air supplies, heat exchangers, surge tanks, and the like are also not included. However, it should be understood that these components are within the scope of the present disclosure.
  • the reactor system 100 may include a dehydrogenation reactor 110 and a regeneration unit 150.
  • a feed stream 102 may be passed into the dehydrogenation reactor 110.
  • a particulate solid 180 may be passed into the dehydrogenation reactor 110 via stream 152.
  • the particulate solid 180 may be contacted with the feed stream 102 in the dehydrogenation reactor 110.
  • the particulate solid 180 may comprise an oxygen-carrier material.
  • the feed stream 102 may comprise one or more hydrocarbons which may be dehydrogenated in the dehydrogenation reactor 110 to form one or more products and hydrogen. Oxygen from the oxygen-carrier material may react with the hydrogen to form water.
  • the one or more products may exit the dehydrogenation reactor 110 via a product stream 114.
  • the particulate solid 180 may exit the dehydrogenation reactor 110 and may be passed to the regeneration unit 150 via stream 112.
  • the regeneration unit 150 may comprise a gas/solids separator 190, a first gas inlet 160 and a second gas inlet 170.
  • the first gas inlet 160 may be above the second gas inlet 170.
  • a fuel 162 may enter into the regeneration unit 150 through the first gas inlet 160 and an oxygen-containing gas 172 may enter into the regeneration unit 150 through the second gas inlet 170.
  • the particulate solid 180 may travel in a generally downwards direction through the regeneration unit 150 first through the separator 190, then past the first gas inlet 160, and then past the second gas inlet 170.
  • the gases within the regeneration unit 150 such as the fuel 162 and the oxygen-containing gas 172 may travel in a generally upwards direction through the regeneration unit 150, such that the particulate solid 180 and the gases move in a countercurrent flow pattern through the regeneration unit 150.
  • the particulate solid 180 may then exit from the regeneration unit 150 and be passed back to the dehydrogenation reactor 110 via stream 152.
  • reactor system 100 may be operable to perform a circulating fluidized bed (CFB) dehydrogenation process.
  • the CFB dehydrogenation process may include a dehydrogenation reactor 110 and a regeneration unit 150, both fluid bed based.
  • the feed stream 102 may be passed into the dehydrogenation reactor 110.
  • the feed stream 102 may comprise one or more hydrocarbons.
  • the one or more hydrocarbons may comprise an alkyl moiety.
  • a hydrocarbon comprises an “alkyl moiety” if the molecule has at least one carbon-carbon single bond capable of being dehydrogenated to form a carbon-carbon double bond.
  • the one or more hydrocarbons may comprise one or more of ethane, propane, butane, or ethylbenzene.
  • the one or more hydrocarbons may comprise at least 50 wt.
  • the one or more hydrocarbons may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of ethane.
  • the one or more hydrocarbons may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of propane.
  • the one or more hydrocarbons may comprise at least 50 wt. %, at least 60 wt.
  • the one or more hydrocarbons may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of butane.
  • the one or more hydrocarbons may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of ethylbenzene.
  • the one or more hydrocarbons may comprise at least 50 wt. %, at least 60 wt.
  • the dehydrogenation reactor 110 may operate with a “back-mixed” fashion where the feed stream 102 enters the reactor, as to closely approximate isothermal conditions. As such, the fluid velocity at this region may be low enough and the particulate solid 180 flux may be great enough such that a dense bed may form at or around where the feed stream 102 is injected.
  • the superficial velocity of the reactor may be from 3-80 ft/s, such as from 3-40 ft/s, or 10-30 ft/s.
  • the particulate solid 180 flux in the reactor may be from 1-300 lb/ft 2 -s, such as from 40-200 lb/ft 2 -s, or from 60-160 lb/ft 2 -s.
  • the reactor may include multiple diameters, and may include one or more frustums to increase or decrease particulate solid 180 and/or gaseous reactant velocity.
  • the reactor may operate with a gas residence time of from 0.1-10 seconds, such as from 0.5-6 seconds.
  • a particulate solid 180 may be utilized in the general operation of the reactor system 100.
  • the term “particulate solid” may refer to one or more solid particles suitable for fluidization.
  • the particulate solid 180 may comprise an oxygencarrier material and a dehydrogenation catalyst material.
  • the particulate solid 180 may consist essentially of the oxygen-carrier material.
  • “consists essentially of’ refers to materials with less than 1 wt. % of the non-recited materials (i.e., consisting essentially of A means A is at least 99 wt.% of the composition).
  • the particulate solid 180 may not comprise a dehydrogenation catalyst material.
  • the oxygen-carrier material and the dehydrogenation catalyst material may be separate particles of the particulate solid 180. In some embodiments, the oxygen-carrier material and the dehydrogenation catalyst may be contained in the same particles of the particulate solid 180.
  • the dehydrogenation of the one or more hydrocarbons may be at least partially by catalytic dehydrogenation.
  • Catalytic dehydrogenation is the dehydrogenation of a hydrocarbon that is promoted by the use of a dehydrogenation catalyst.
  • the dehydrogenation of the one or more hydrocarbons may be by non-catalytic thermal dehydrogenation.
  • Non-catalytic thermal dehydrogenation refers to the dehydrogenation of a hydrocarbon that occurs without the use of a dehydrogenation catalyst and instead may occur because of high temperature, pressure or combinations thereof.
  • the particulate solid 180 may comprise a “dual-purpose material” that may act as both a dehydrogenation catalyst as well as an oxygen-carrier material. It should be understood that, in at least the embodiments described herein where an oxygen-carrier material and a dehydrogenation catalyst are utilized in the same reaction vessel (such as those of FIG. 1 ), such a dual-purpose material may be utilized either in replacement or in combination with the oxygen-carrier material of the particulate solid 180 or the dehydrogenation catalyst of the particulate solid 180.
  • an “oxygen-carrier material” may generally refer to an oxygenrich oxygen-carrier material or an oxygen-deficient oxygen-carrier material.
  • the “dual-purpose material” may generally refer to an oxygen-rich dual-purpose material or an oxygen-deficient dual-purpose material.
  • an oxygen-deficient state may be present after some oxygen is utilized for combustion and may be oxygen-rich prior to the combustion, following regeneration of the oxygen-deficient state material.
  • the reactions may take place in one or more fluidized bed reactors, such as circulating fluidized bed reactors.
  • the reactors may be, for example, risers or downers.
  • the dehydrogenation catalyst and the oxygen-carrier material may be separate particles of the particulate solid 180.
  • One contemplated advantage of such a system is that by adding, removing, or substituting one or both of the dehydrogenation catalyst and oxygen-carrier material, the functionality of the system can be altered, even when the system is on-line.
  • the reaction heat load could be adjusted by adding or removing one or both of the dehydrogenation catalyst and the oxygen-carrier material.
  • This may be advantageous, in some embodiments, as compared with a dual-purpose material, since the dual-purpose particle's heat balance must be determined prior to reaction and cannot be easily adjusted by varying the amount of dehydrogenation catalyst versus oxygen-carrier material. Control of the ratio of dehydrogenation catalyst versus oxygen-carrier material may further be advantageous since reaction selectivity may be better tuned.
  • the amount of hydrogen in the system may be used to control the degree of combustion, or component balances may be used to optimize downstream separation processes.
  • the dehydrogenation reactor 110 may include from 1 wt. % to 100 wt. %, such as from 5 wt. % to 95 wt. %, or from 75 wt. % to 25 wt. %, oxygen-carrier material based on the total weight of the particulate solid 180 in the dehydrogenation reactor 110.
  • the dehydrogenation reactor 110 may include from 50 wt. % to 75 wt. % oxygen- carrier material based on the total weight of the particulate solid 180 in the dehydrogenation reactor 110.
  • relatively large amounts of oxygen-carrier material may be present (e.g., at least 80 wt.
  • the dehydrogenation reactor 110 may include from 0 wt. % to 99 wt. %, such as from 5 wt. % to 95 wt. %, or from 25 wt. % to 75 wt. %, dehydrogenation catalyst based on the total weight of the particulate solid 180 in the dehydrogenation reactor 110. In other embodiments, the dehydrogenation reactor 110 may include from 25 wt. % to 50 wt.
  • the dehydrogenation reactor 110 may include up to 95 wt. %, 99 wt. %, or even 100 wt. % of dual-purpose material of the total weight of the particulate solid 180 in the dehydrogenation reactor 110.
  • the particulate solid 180 material may encompass all solids in the system aside from coke.
  • the oxygencarrier material may include one or more metal oxides.
  • the one or more metal oxides may be a redox-active metal oxide or a mixture of redox-active metal oxides.
  • the redox-active metal oxide includes binary, ternary, or other mixed metal oxides capable of undergoing reduction in the presence of a reducing agent (for example, hydrogen) and oxidation in the presence of oxidizing agent (for example, oxygen or air).
  • the redoxactive metal oxide may be a metal MO X , where M may be one or more metals of IUPAC group 6, 7, 8, 9, 10, 11, or 12 and “x” is the number of associated oxygen atoms in the structure.
  • M may be one or more metals of IUPAC group 6, 7, 8, 9, 10, 11, or 12 and “x” is the number of associated oxygen atoms in the structure.
  • the redox-active metal oxide may be MnzCh, FezCh, CO3O4, CuO, (LaSrjCoCh, (LaSrjMnCh, MgeMnOs, MgMnCh, MnCh, FegCM, MmCM, CuzO, NiO, N12O3, CrO, CnCh, CrCh, ZnO ; or any combination of other IUPAC group 6-12 metal oxide.
  • the redox-active metal oxide may be cerium oxide.
  • the redox-active metal oxide may be CeO2, Ce2O3, or any other mixed metal oxide containing cerium.
  • the oxygen carrier material may include lanthanum oxide, La2O3, in combination with other reducible metal oxides.
  • the redox-active metal oxide may be chosen from M112O3, Fe2O3, CO3O4, CuO, (LaSr)CoO3,(LaSr)MnO3, MgeMnOs, MgMnOs, Mn02, Fe3O4, Mn3O4, and CU2O.
  • the oxygen-carrier material may be a solid. In specific embodiments, the oxygen-carrier material may be a crushed solid or powder.
  • the oxygen- carrier material may be formulate using a redox-active metal oxide and a binder and/or support material to produce a fluidizable material with the require physical properties, for example, particle size distribution, density, and attrition resistance.
  • the binder and/or support material may include alumina, silica, titania, magnesia, zirconia, or combinations thereof.
  • the oxygen-carrier material may include a hydrogenselective oxygen-carrier material that may include a promoter or a combination of various promoters.
  • the addition of a promoter(s) may lead to the formation of a core-shell morphology.
  • the promoter(s) may include alkali or alkaline-earth metal oxides from IUPAC group 1 and 2 and/or compounds comprising alkali-transition metal oxides or alkaline-earth transition metal oxides.
  • alkali elements may include one or more of sodium, lithium, potassium, and cesium.
  • alkaline-earth elements may include one or more of calcium, magnesium, strontium, and barium.
  • transition metals may include one or more of tungsten and molybdenum.
  • the one or more alkali or alkaline- earth transition metal oxides may be NazWCM, K2MOO4, NazMoCM, K2WO4, Li2WC>4, CsWC>4, Li2MoO4, CaWC>4, CaMoCM, MgWCM, MgMoCM, SrWC>4, SrMoCM, BaWCM and BaMoC .
  • the promoter may include one or more of alkali or alkaline-earth metal salts selected from Group 1 and 2 metal cations and a counterion.
  • alkali elements may include one or more of sodium, lithium, potassium, and cesium.
  • alkaline-earth elements may include one or more of calcium, magnesium, strontium, and barium.
  • the counterion may include carbonates, sulphates, sulphites, sulfides, phosphates, phosphites and borates.
  • the alkali or alkaline-earth metal salts may be Na 2 CO 3 , Na 2 SO 4 , Na 3 PO 4 , Li 2 CO 3 , Li 2 SO 4 , Li 3 PO 4 , K 2 CO 3 , K2SO4, K 3 PO 4 , Cs 2 CO 3 , Cs 2 SO 4 , Cs 3 PO 4 , CaCO 3 , CaSO 4 , Ca 3 (PO 4 ) 2 , SrCO 3 , SrSO 4 , Sr 3 (PO 4 ) 2 , MgCO 3 , MgSO 4 , Mg 3 (PO 4 ) 2 , BaCO 3 , BaSCM, Ba 3 (PC>4)2, Na2HPO4, KHSO4, Na2SO 3 , K2B4O7, Na 3 BO 3 , or combinations thereof.
  • oxygen-carrier materials such as those disclosed in U.S. App. No. 62/725,504, entitled “METHODS OF PRODUCING HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS,” filed on, Aug. 31, 2018, and U.S. App. No. 62/725,508, entitled “HYDROGEN-SELECTIVE OXYGEN CARRIER MATERIALS AND METHODS OF USE,” filed on, Aug. 31, 2018, are contemplated as suitable for the presently disclosed processes, and the teachings of these references are incorporated by reference herein.
  • the oxygen-carrier material may include those of U.S. Pat. No. 5,430,209, U.S. Pat. No. 7,122,495, and/or WO 2018/232133, each of which are incorporated by reference in their entireties.
  • the oxygen-rich oxygen-carrier material may be reducible by releasing oxygen that may be selective for combusting hydrogen.
  • the oxygen-carrier material may be selective for the combustion of hydrogen over hydrocarbons.
  • the oxygen-rich oxygen-carrier material comprises from about 1 wt. % to about 20 wt. % releasable oxygen based on total weight of the oxygen-rich oxygen-carrier material.
  • the oxygenrich oxygen-carrier material comprises from about 1 wt. % to about 10 wt. %, from about 1 wt. % to about 5 wt. %, from about 5 wt. % to about 20 wt. %, or from about 5 wt.
  • releasable oxygen may refer to the oxygen that can be released through redox by the oxygen-carrier material.
  • Other oxygen may be present in the oxygen-carrier material that is not releasable through redox. It should be understood that in some embodiments, the oxygen may be released from a surface of the oxygen-carrier material simultaneously with the combustion of hydrogen at the surface of the oxygen-carrier material.
  • the releasable oxygen of the oxygen-rich oxygen-carrier materials may be selective for combusting hydrogen over hydrocarbons. In some embodiments, at least about 60% of the releasable oxygen of the oxygen-carrier material is selective for hydrogen combustion. In other embodiments, at least about 55% of the releasable oxygen of the oxygen- carrier material is selective for hydrogen combustion.
  • contacting the hydrogen with the oxygen-rich oxygen-carrier material removes from about 1 wt. % to 50 wt. % of the releasable oxygen from the oxygen- rich oxygen- carrier material. In other embodiments, contacting the hydrogen with the oxygen-rich oxygencarrier material removes from about 10 wt. % to about 50 wt. %, from about 10 wt. % to about 25 wt. %, or from about 25 wt. % to about 50 wt. % of the releasable oxygen from the oxygen- rich oxy gen-carrier material.
  • the oxygen-rich oxygen-carrier material when the hydrogen is contacted by the oxygen-rich oxygencarrier material, the oxygen- rich oxygen-carrier material combusts greater than about 50% of the hydrogen. In other embodiments, when the hydrogen is contacted by the oxygen-rich oxygencarrier material, the oxygen-rich oxygen-carrier material combusts about 50% to about 90%, or about 75% to about 90% of the hydrogen that is produced.
  • the contacting of the oxygen-rich oxygen-carrier material with the hydrogen may combust the hydrogen and form an oxygen-diminished oxygen-carrier material.
  • At least a portion of the oxygen-rich oxygen-carrier material may be reduced to a lower oxidation state.
  • the oxygen-diminished oxygencarrier material may be discharged from the dehydrogenation reactor 110 at a lower oxidation state.
  • the particulate solid 180 may comprise a dehydrogenation catalyst.
  • the dehydrogenation catalyst may include gallium, chromium, and/or platinum.
  • a gallium and/or platinum dehydrogenation catalyst comprises gallium, platinum, or both.
  • the dehydrogenation catalyst may be carried by an alumina or alumina silica support, and may optionally comprise potassium.
  • the dehydrogenation catalysts may include catalysts disclosed in U.S. Pat. No. 8,669,406, which is incorporated herein by reference in its entirety, such as those including Ga, Cr, and/or Fe based catalysts.
  • Pt based catalysts may be utilized.
  • those catalysts disclosed in EP 0948475B1 and/or WO 2010/133565, which are each incorporated herein by reference in its entirety, may be utilized.
  • Additional catalyst embodiments contemplated as suitable for use in the systems and methods described herein include those of U.S. Pat. No. 8,669,406, which is incorporated herein by reference in its entirety.
  • Such catalysts may contain relatively low amounts of Cr, such as less than 6%, or approximately 1.5%.
  • other suitable dehydrogenation catalysts may be utilized to perform the dehydrogenation reaction.
  • the dehydrogenation catalyst may exhibit suitable stability when in the presence of steam. As is described herein, the combustion of hydrogen may form steam, which may be in direct contact with the dehydrogenation catalyst. It is contemplated that not all dehydrogenation catalysts are equally effective in steam environments. In one or more embodiments, dehydrogenation catalysts are utilized which maintain a substantial amount of their reactivity and/or selectivity for the dehydrogenation of light alkanes.
  • one or more of the dehydrogenation catalysts utilized in the presently disclosed systems and methods may not deteriorate in alkane conversion and/or selectivity for dehydrogenation more than 25%, more than 20%, more than 15%, more than 10%, more than 5%, or may even have improved alkane conversion and/or selectivity for dehydrogenation when in the presence of steam in amounts consistent with the operation of the presently disclosed systems.
  • the dehydrogenation catalyst may function with such conversion and/or selectivity when exposed to at least 10 mol. % water (such as from 10 mol. % to 50 mol. % water) for a period of up to, e.g., 120 seconds (the time which the catalyst may be exposed to such conditions, according to some embodiments of the presently disclosed system).
  • Suitable examples of dehydrogenation catalysts may be prepared such that it meets the Geldart A definition.
  • the dehydrogenation catalyst comprises gallium and platinum supported on alumina in the delta or theta phase, or in a mixture of delta plus theta phases, or theta plus alpha phases, or delta plus theta plus alpha phases, modified with silica, and having a surface area preferably less than about 100 square meters per gram (m 2 /g), as determined by the BET method.
  • the dehydrogenation catalyst comprises: from 0.1 to 34 wt. %, preferably 0.2 to 3.8 wt.
  • gallium oxide GazCh
  • platinum from 1 to 300 parts per million (ppm), preferably 50 to 300 ppm, by weight platinum
  • ppm parts per million
  • platinum from 0 to 5 wt. %, preferably 0.01 to 1 wt. %, of an alkaline and/or earth-alkaline such as potassium
  • from 0.08 to 3 wt. % silica the balance to 100 wt. % being alumina.
  • heat may be gained or lost through the dehydrogenation reaction, the re-oxidation of the oxygen-diminished oxygen carrier material, and the reduction of the oxygen-rich oxygen carrier material may create or use heat (i.e., be exothermic or endothermic).
  • the contacting of the hydrocarbon feed with the dehydrogenation catalyst may be endothermic and results in a dehydrogenation heat loss.
  • the contacting of the hydrogen with the oxygen-rich oxygen carrier material may be exothermic and results in a combustion heat gain.
  • the re-oxidizing of the oxygen-diminished oxygen carrier material may be exothermic and results in an oxygenation heat gain.
  • embodiments of the disclosed process may allow for higher alkane conversion while reducing or eliminating needs for fuel gas, as required for conventional cracking because the heat gained throughout the process by the re-oxidizing of the oxygen carrier material, the combustion of hydrogen, or both may produce the amount of heat required for the alkanes or alkyl aromatics to olefins reaction.
  • the “dehydrogenation heat loss” refers to the amount of heat lost by the dehydrogenation of the feed alkanes
  • the “combustion heat gain” refers to the amount of heat created by the combustion of the hydrogen
  • the “oxygenation heat gain” refers to the amount of heat created by the oxidation of the oxygen-diminished oxygen carrier material.
  • the combustion heat gain may contribute heat to the system that account for at least a portion of the dehydrogenation heat loss.
  • supplemental fuel 162 may be combusted to heat one or more of the dehydrogenation catalyst or the oxygen carrier material.
  • the supplemental fuel 162 may make up for any shortcoming in heat created by the combustion of the hydrogen or the oxygenation of the oxygen carrier material. However, it should be understood that in the embodiments disclosed, the amount of necessary supplemental fuel 162 may be substantially less than would be necessary in a system that did not incorporate an oxygen carrier material.
  • the heat produced by the oxygen carrier regeneration and combustion reaction may completely cover the heat needed for the endothermic dehydrogenation reaction and other heat demands such as heating the feed gases (air, hydrocarbon, etc.) or balancing heat losses, or at least reduce any supplemental fuel 162 needs of the system.
  • dehydrogenation reactions that incorporate hydrogen combustion, those skilled in the art are referred to, for example, US Patent Publication 2021/0292259 Al, the teachings of which are incorporated herein by reference in their entirety.
  • the feed stream 102 may enter a riser within the dehydrogenation reactor 110, and the product stream 114 may exit the reactor system 100 via stream 114.
  • the reactor system 100 may be operated by feeding a chemical feed (e.g., in a feed stream 102 such as feed stream 102) into the dehydrogenation reactor 110.
  • a particulate solid 180 may be fed into the dehydrogenation reactor 110 via stream 152.
  • the particulate solid 180 may include an oxygenrich oxygen-carrier material.
  • the particulate solid 180 may also include a dehydrogenation catalyst.
  • the feed stream 102 may contact the particulate solid 180 in the dehydrogenation reactor 110.
  • Each of the feed stream 102 and the particulate solid 180 may flow upwardly into and through the dehydrogenation reactor 110 to produce one or more products, an oxygen-diminished oxygencarrier material, and hydrogen.
  • the one or more hydrocarbons in the feed stream 102 may be dehydrogenated to form one or more products and hydrogen.
  • the hydrogen may be contacted with the oxygen-rich oxygen-carrier material in the dehydrogenation reactor 110.
  • the oxygen-rich oxygencarrier material may be reducible.
  • the contacting of the oxygen-rich oxygen-carrier material with the hydrogen may combust the hydrogen and reduce the oxygen-carrier material to form an oxygen-diminished oxygen-carrier material and water.
  • one or more products may exit the dehydrogenation reactor 110 via product stream 114.
  • Stream 114 may be further processed such as by one or more subsequent separation steps or further reacted. It is contemplated that stream 114 may be utilized as a feed for another reactor system 100 or sold as a chemical product.
  • the one or more products in stream 114 may be mixed with water produced from reacting the hydrogen produced during the dehydrogenation of the one or more hydrocarbons and oxygen from the oxy gen-carrier material.
  • the water may be removed from stream 114 and the one or more products utilizing a condenser.
  • stream 114 may comprise one or more products.
  • the one or more products may comprise one or more olefinic compounds.
  • olefinic compounds refers to hydrocarbons having one or more carbon-carbon double bonds apart from the formal double bonds in aromatic compounds.
  • ethylene and styrene are olefinic compounds, but ethylbenzene would not be an olefinic compound as the only double bonds present in ethylbenzene are formal double bonds present as part of the aromatic structure.
  • the one or more olefinic compounds may comprise one or more of ethylene, propylene, butylene, or styrene.
  • the product stream 114 may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of ethylene.
  • stream 114 may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt.
  • stream 114 may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of butylene.
  • stream 114 may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt.
  • stream 114 may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of the sum of one or more of ethylene, propylene, butylene, and styrene.
  • the one or more products and the particulate solid 180 may be passed to a separation device in a separation section within the dehydrogenation reactor 110.
  • the particulate solid 180 may be separated from the one or more products in a separation device, such as a stripper (not depicted in FIG. 1) within the dehydrogenation reactor 110.
  • the one or more products may then be transported out of the separation section of the dehydrogenation reactor 110.
  • the separated vapors may be removed from the dehydrogenation reactor 110 via a pipe at a gas outlet port of the separation section within the dehydrogenation reactor 110.
  • the separation device may be a cyclonic separation system.
  • the cyclonic separation system may include two or more stages of cyclonic separation.
  • the dehydrogenation reactor 110 may operate with a residence time of the vapor in the fluidized bed reactor of less than 10 seconds (such less than 9 seconds, less than 8 seconds, less than 7 seconds, less than 6 seconds, less than 5 seconds, less than 4 seconds, or even less than 3 seconds. [0045] In one or more embodiments, the dehydrogenation reactor 110 may operate at a temperature of greater than or equal to 550 °C and less than or equal to 800 °C. In some embodiments, the temperature in the dehydrogenation reactor 110 may be from 550 °C or 600 °C to 770 °C. In other embodiments, the temperature in the dehydrogenation reactor 110 may be from 700 °C to 750 °C.
  • the primary feed component(s) may be propane, ethylbenzene, and/or butane, and the dehydrogenation reactor 110 may operate at a temperature of greater than 600 °C. In additional embodiments, the primary feed component may be ethane, and the dehydrogenation reactor 110 may operate at a temperature of at least 625 °C.
  • the dehydrogenation reactor 110 may operate at a pressure of at least atmospheric pressure (about 14.7 psia). In some embodiments, the dehydrogenation reactor 110 may operate at a pressure of about 500 psia. In other embodiments, the dehydrogenation reactor 110 may operate at a pressure from about 4 psia to about 160 psia, from about 20 psia to about 100 psia, or from about 30 psia to about 80 psia. In some embodiments, the regeneration unit 150 may operate with a pressure of within 30 psi of the dehydrogenation reactor 110.
  • the residence time of the particulate in the dehydrogenation reactor 110 may typically vary from 0.5 seconds (sec) to 240 sec. In other embodiments, the residence time of the particulate solid 180 may be from about 0.5 sec to about 200 sec, from about 0.5 sec to about 100 sec, from about 0.5 sec to about 50 sec, or about 0.5 sec to about 20 sec.
  • the ratio of the particulate solid 180 to the feed stream 102 in the dehydrogenation reactor 110 may range from 5 to 150 on a weight to weight (w/w) basis. In some embodiments, the ratio may range from 10 to 40, such as from 12 to 36, or from 12 to 24.
  • the flux of the particulate solid 180 may be from 1 pound per square foot-second (lb/ft 2 -s) (about 4.89 kg/m 2 -s) to 300 lb/ft 2 -s (to about 97.7 kg/m 2 -s), such as from 1-20 lb/ft 2 -s, in the upstream reactor section, and from 1 lb/ft 2 -s (about 48.9 kg/m 2 -s) to 300 lb/ft 2 -s (about 489 kg/m 2 -s), such as from 10-100 lb/ft 2 -s, in the downstream reactor section.
  • the particulate solid 180 may be capable of fluidization.
  • the particulate solid 180 may exhibit properties known in the industry as “Geldart A” or “Geldart B” properties. Particles may be classified as “Group A” or “Group B” according to D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), 34- 37; and D. Geldart, “Types of Gas Fluidization,” Powder Technol. 7 (1973) 285-292, which are incorporated herein by reference in their entireties.
  • Group A is understood by those skilled in the art as representing an aeratable powder, having a bubble-free range of fluidization; a high bed expansion; a slow and linear deaeration rate; bubble properties that may include a predominance of splitting/recoalescing bubbles, with a maximum bubble size and large wake; high levels of solids mixing and gas backmixing, assuming equal U-Umf (U is the velocity of the carrier gas, and Umf is the minimum fluidization velocity, typically though not necessarily measured in meters per second, m/s, i.e., there is excess gas velocity); axisymmetric slug properties; and no spouting, except in very shallow beds.
  • the properties listed tend to improve as the mean particle size decreases, assuming equal cfp; or as the ⁇ 45 micrometers (pm) proportion is increased; or as pressure, temperature, viscosity, and density of the gas increase.
  • the particles may exhibit a small mean particle size and/or low particle density ( ⁇ 1.4 grams per cubic centimeter, g/cm 3 ), fluidize easily, with smooth fluidization at low gas velocities, and may exhibit controlled bubbling with small bubbles at higher gas velocities.
  • Group B is understood by those skilled in the art as representing a “sand-like” powder that starts bubbling at Umf; that exhibits moderate bed expansion; a fast deaeration; no limits on bubble size; moderate levels of solids mixing and gas backmixing, assuming equal U-Umf; both axisymmetric and asymmetric slugs; and spouting in only shallow beds. These properties tend to improve as mean particle size decreases, but particle size distribution and, with some uncertainty, pressure, temperature, viscosity, or density of gas seem to do little to improve them.
  • the particulate solid 180, and the gas products may be separated within the dehydrogenation reactor 110 by high efficiency cyclones in a stripping section of the reactor system 100 (not pictured in FIG. 1).
  • the stripping section may be within the reactor 110 or may be a separate vessel.
  • the particulate solid 180 may be passed to the regeneration unit 150 via stream 112.
  • the dehydrogenation catalyst, the oxygen-carrier material, or both may be stripped in the stripping section with a displacement gas such as nitrogen, steam, methane, natural gas or other suitable gas before being sent to a regeneration unit 150.
  • a portion of the particulate solid 180 may be passed from the stripping section via stream 116 to stream 152 to be used again in the reactor 110 without first passing through the regeneration unit 150.
  • the oxygen-content of the oxygen-carrier material may be better controlled as the oxygencarrier material may be given more time to react off its oxygen so that the oxygen-carrier material may supply more oxygen to the reactor. It is also believed that recycling the particulate solid 180 may allow for improved temperature control of the reactor 110 because recycling the particulate solid 180 may improve control of the temperature of the materials entering the reactor 110 improving the temperature profile of the reactor 110.
  • the dehydrogenation catalyst of the particulate solid 180 may be slightly deactivated after contacting the feed stream 102. In other embodiments, the dehydrogenation catalyst of the particulate solid 180 may still be suitable for reaction in the dehydrogenation reactor 110.
  • “deactivated” may refer to a catalyst that is contaminated with a substance such as coke, is cooler in temperature than needed to promote reaction of the feed, or may refer to an oxygen-carrier material that is deficient of oxygen.
  • a contaminate, such as coke may be deposited on the particulate solid 180 that is passed from the dehydrogenation reactor 110 to the regeneration unit 150.
  • the particulate solid 180 may enter the regeneration unit 150 via stream 112.
  • the particulate solid 180 may then enter the gas/solids separator 190 within the regeneration unit 150. Exiting the separator 190, the particulate solid 180 may pass through a fuel zone 164 and past the first gas inlet 160, through which the fuel 162 may enter into the regeneration unit 150.
  • the particulate solid 180 may then pass through an air zone 174 and past the second gas inlet 170 through which an oxygen-containing gas 172 may enter into the regeneration unit 150.
  • the particulate solid 180 may then exit the regeneration unit 150 via stream 152 and be passed back to the dehydrogenation reactor 110.
  • Regeneration may remove contaminates, such as coke, raise the temperature of the particulate solid 180, increase the oxygen-content of the oxygen-carrier material of the particulate solid 180, or combinations thereof.
  • the coke on the particulate solid 180 may be removed by combustion in an oxygen-containing environment in the regeneration unit 150.
  • the particulate solid 180 may be heated by a fuel 162 to a target temperature. The particulate solid 180 may then circulate back to the dehydrogenation reactor 110, carrying the necessary heat for the dehydrogenation reaction.
  • the oxygen-carrier may be oxidized or reduced as it is utilized in a dehydrogenation process. Different oxidation states of the oxygen-carrier may behave differently within the dehydrogenation process. For example, an oxygen-carrier with a lower oxidation state may not as effectively combust hydrogen within the dehydrogenation reaction as an oxygen-carrier with a comparatively higher oxidation state. Conversely, an oxygen-carrier with a comparatively higher oxidation state may be more likely to oxidize hydrocarbons during the dehydrogenation reaction when compared to an oxygen-carrier with a comparatively lower oxidation state potentially harming the production of olefins from the process. Passing the oxygen-carrier to and through the regeneration unit 150 may help control the oxidation state of the oxygen-carrier material.
  • the oxygen-diminished oxygen carrier material of the particulate solid 180 may be re-oxidized to an oxidation state higher than the oxidation state of the oxygendiminished oxygen carrier material by combustion in an oxygen-containing environment in the regeneration unit 150.
  • the oxy gen-containing environment may be air.
  • the oxygen-diminished oxygen carrier material may be restored to its original oxidation state.
  • the oxygen-diminished oxygen carrier material may have an oxidation state of +2, +3, or +4.
  • the oxygen-rich oxygen carrier material may then circulate back to the dehydrogenation reactor 110, carrying the necessary heat for the dehydrogenation reaction.
  • nitrogen or steam may also be used to convey the oxygen-rich oxygen carrier material to the dehydrogenation reactor 110.
  • the resulting gas stream 154 from the regeneration unit 150 may consist of air depleted of or containing a lower concentration of O2.
  • a supplemental fuel 162 may be combusted in the regeneration unit 150 to produce heat and increase the temperature of the particulate solid 180.
  • the heat produced by the oxidizing of the oxygen-diminished oxygen carrier material and the combusting of the supplemental fuel 162 may be sufficient to maintain the temperature of the dehydrogenation reactor 110 at a desired temperature.
  • the desired temperature may depend upon the minimum temperature needed for operation of the dehydrogenation reactor 110, since the particulate solid 180 may enter the dehydrogenation reactor 110 and impart its temperature to the dehydrogenation reactor 110.
  • the regeneration unit 150 may operate at a temperature of 650 °C, or even 700 °C, to 900 °C, such as 725 °C to 875 °C, or 750 °C to 850 °C.
  • the regeneration unit 150 may have a temperature of at least 50 °C greater than that of the dehydrogenation reactor 110.
  • Such a temperature range may be utilized so that the temperature of the dehydrogenation reactor 110 may be maintained with a limited amount of dehydrogenation catalyst and/or oxygen carrier material. Additionally, such temperatures may be needed to activate the dehydrogenation catalyst if one is utilized.
  • the residence time of the particulate solid 180 in the regeneration unit 150 may typically vary from 0.5 seconds (sec) to 360 sec. In other embodiments, the residence time of the particulate solid 180 may be from about 0.5 sec to about 200 sec, from about 0.5 sec to about 100 sec, from about 0.5 sec to about 50 sec, or about 0.5 sec to about 20 sec.
  • the particulate solid 180 may be passed from the dehydrogenation reactor 110 to the regeneration unit 150 via stream 112.
  • the particulate solid 180 may be passed through a gas/solids separator 190.
  • the separator 190 may be a riser termination system which may include a cyclonic separation system.
  • the riser termination system includes a cyclonic separation system some of the particulate solid 180 may be passed out of the riser termination system without first passing through the cyclonic separation system.
  • the cyclonic separation system may include two or more stages of cyclonic separation.
  • the first separation device into which the fluidized stream enters is referred to a primary cyclonic separation device.
  • the fluidized effluent from the primary cyclonic separation device may enter into a secondary cyclonic separation device for further separation.
  • Primary cyclonic separation devices may include, for example, primary cyclones, and systems commercially available under the names VSS (commercially available from UOP), LD2 (commercially available from Stone and Webster), and RS2 (commercially available from Stone and Webster).
  • VSS commercially available from UOP
  • LD2 commercially available from Stone and Webster
  • RS2 commercially available from Stone and Webster
  • one or more set of additional cyclones are employed for further separation of the particulate solid from the product gas.
  • additional cyclones e.g. secondary cyclones and tertiary cyclones
  • the particulate solid 180 may be separated from exhaust gases such as flue gas.
  • the gases separated from the particulate solid 180 may combine with gases from the regeneration unit 150 and exit the regeneration unit 150 via an exhaust stream 154.
  • the particulate solid 180 may move in a generally downward direction through the regeneration unit 150.
  • generally downward direction means that the average velocity of the particulate solid 180 is in the downward direction, where the downward direction is with the pull of gravity.
  • the velocity of individual particles of the particulate solid 180 may have a distribution and may not be equal to the average, but taken as a whole the velocity of the particulate solid 180 will average out to be generally downward.
  • gases within the regeneration unit 150 may move in a generally upwards direction through the regeneration unit 150.
  • the term “generally upward direction” means that the average velocity of gases within the regeneration unit 150 is in the upward direction, where the upward direction is against the pull of gravity. As it is an average, the velocity of the gas molecules within the regeneration unit 150 may have a distribution and may not be equal to the average, but taken as a whole the velocity of the gases will average out to be generally upward. According to embodiments, the particulate solid 180 and the gases may move in a countercurrent flow pattern through the regeneration unit 150.
  • the regeneration unit 150 may comprise a first gas inlet 160 and a second gas inlet 170 beneath the first gas inlet 160.
  • gas inlet refers to any component operable to inject a gas into the regeneration unit 150.
  • a gas inlet may be a blower or distributor.
  • other suitable gas suppliers are contemplated herein, as would be known by those skilled in the art.
  • a fuel 162 may enter the regeneration unit 150 via the first gas inlet 160.
  • an oxygencontaining gas 172 may enter the regeneration unit 150 via the second gas inlet 170.
  • the fuel 162 may comprise hydrogen, methane, ethane, propane, natural gas, or combinations thereof. According to embodiments, the fuel 162 may enter the regeneration unit 150 in a generally upwards direction. In some embodiments, the fuel 162 may enter the regeneration unit in an initially downwards direction before following the flow of other gases within the regeneration unit 150 generally upwards. In embodiments, at least a portion of the fuel 162 in the area above the first gas inlet 160 may react with oxygen from one or both of the oxygencontaining gas 172 or the oxygen-carrier material of the particulate solid 180 to produce heat and increase the temperature of the particulate solid 180.
  • the area above the first gas inlet 160 may be a fuel zone 164 as the directional flow of the fuel 162 into the regeneration unit 150 may cause the concentration of fuel 162 in the area above the first gas inlet 160 to be higher than the concentration of fuel 162 in the area below the first gas inlet 160.
  • the concentration of fuel 162 in the fuel zone 164 may be less than 20 mol.%. In some embodiments, the concentration of fuel 162 in the fuel zone 164 may be from about 0.1 mol.% to about 15 mol.%, from about 0.1 mol.% to about 10 mol.%, from about 0.1 mol.% to about 5 mol.%, from about 0.1 mol.% to about 1 mol.%, from about 0.1 mol.% to about 0.5 mol.%, from about 0.5 mol.% to about 20 mol.%, from about 0.5 mol.% to about 15 mol.%, from about 0.5 mol.% to about 10 mol.%, from about 0.5 mol.% to about 5 mol.%, from about 0.5 mol.% to about 1 mol.%, from about 1 mol.% to about 20 mol.%, from about 1 mol.% to about 15 mol.%, from about 1 mol.% to about 10 mol.%.%, from about 1 mol
  • At least a portion of the fuel 162 in the fuel zone 164 may react with oxygen from the oxygen-rich oxygen-carrier material of the particulate solid 180 and the oxygen-content of at least a portion of the oxygen-rich oxygen-carrier material of the particulate solid 180 may be reduced to form the oxygen-diminished oxy gen-carrier material.
  • at least a portion of the fuel 162 in the fuel zone 164 may react with oxygen from the oxygen-containing gas 172 and oxygen from the oxygen-containing gas 172 may oxidize the oxygen-diminished oxygen-carrier material of the particulate solid 180 to form the oxygenrich oxygen-carrier material.
  • the oxygen-containing gas 172 may enter the regeneration unit 150 via the second gas inlet 170.
  • the oxygencontaining gas 172 may be air, enriched air, air mixed with steam, or flue gas. Enriched air is air with added oxygen gas.
  • the oxy gen-containing gas 172 may include at least 28 mol.% oxygen.
  • the oxygen-containing gas 172 may include from about 2 mol.% to about 28 mol.% oxygen, from about 2 mol.% to about 25 mol.% ,from about 2 mol.% to about 20 mol.%, from about 2 mol.% to about 15 mol.%, from about 2 mol.% to about 10 mol.%, from about 2 mol.% to about 5 mol.%, from about 5 mol.% to about 28 mol.%, from about 5 mol.% to about 25 mol.%, from about 5 mol.% to about 20 mol.%, from about 5 mol.% to about 15 mol.%, from about 5 mol.% to about 10 mol.%, from about 10 mol.% to about 28 mol.%, from about 10 mol.% to about 25 mol.%, from about 10 mol.% to about 20 mol.%, from about 10 mol.% to about 15 mol.%, from about 15 mol.% to about 28 mol.%, from about 10
  • the oxygen-containing gas 172 may enter the regeneration unit 150 in a generally upwards direction. In some embodiments, the oxygen-containing gas 172 may enter the regeneration unit 150 in an initially downwards direction before following the flow of other gases within the regeneration unit 150 generally upwards. In some embodiments, the area above the second gas inlet 170 and below the first gas inlet 160 may be an air zone 174 as the directional flow of the oxygen-containing gas 172 into the regeneration unit 150 may cause the concentration of oxygen in the area between the first and second gas inlets to be higher than other areas of the regeneration unit 150. In one or more embodiments, the concentration of oxygen in the air zone 174 may be greater than 25 mol.%.
  • the concentration of oxygen in the air zone 174 may be from about 4 mol.% to about 28 mol.% oxygen, from about 4 mol.% to about 21 mol.%, from about 4 mol.% to about 10 mol.%, from about 10 mol.% to about 28 mol.%, from about 10 mol.% to about 21 mol.%, or from about 21 mol.% to about 28 mol.% oxygen.
  • the name air is utilized here to simply show that oxygen is present since air is often the oxygen-containing gas utilized at least cost.
  • At least a portion of the oxygen-diminished oxygen-carrier material of the particulate solid 180 may react with oxygen from the oxygen-containing gas 172 in the air zone 174 and the oxygen content of at least a portion of the oxygen-carrier material of the particulate solid 180 may increase to form the oxygen-rich oxygen-carrier material of the particulate solid 180.
  • at least a portion of the particulate solid 180 may be passed from the regeneration unit 150 back to the dehydrogenation reactor 110 via stream 152.
  • the oxygen-carrier material may be oxidized by the oxygen-containing gas 172, replacing at least a portion of the oxygen that may have been released during fuel 162 combustion. This may cause an oxygen-carrier material exiting the regeneration unit 150 to be at a higher oxidation state when compared to an oxygen-carrier material that was not exposed to an oxygen-containing gas 172 after being exposed to a fuel 162.
  • the oxygen-carrier material may be reduced by the fuel 162 and may not be re-oxidized sufficiently before being passed back to the dehydrogenation reactor 110. Because different materials used for the oxygen-carrier material may have higher or lower oxidation state requirements for their ideal performance in the dehydrogenation reaction this scenario may negatively impact the selectivity and activity of the oxygen-carrier material in the dehydrogenation reaction, possibly reducing the overall performance of the reactor system 100.
  • the particulate solid 180 may be first passed from the dehydrogenation reactor 110 to a pre-oxidation unit 210 via stream 112 before being passed to the regeneration unit 150.
  • An oxygen-containing gas 212 may enter the pre-oxidation unit 210 and the particulate solid 180 may be exposed to the oxygen-containing gas 172.
  • the oxy gen-containing gas 212 and the particulate solid 180 may flow generally co-currently in an upward direction through the pre-oxidation unit 210 and may exit the pre-oxidation unit 210 via stream 222 and may be passed to the regeneration unit 150.
  • the particulate solid 180 may flow generally in a downward direction through the regeneration unit 150 first through the fuel zone 164, then through the air zone 174, and finally past a third gas inlet 140 beneath the second gas inlet 170 through which stripping gas 142 may enter the regeneration unit 150.
  • the particulate solid 180 may then exit the regeneration unit 150 via stream 152 and be passed back to the dehydrogenation reactor 110.
  • the pre-oxidation unit 210 and the third gas inlet 140 are optional additions to the reactor system 200. It is contemplated that the reactor system 200 may only comprise the pre-oxidation unit 210, but not the third gas inlet 140, or only the third gas inlet 140, but not the pre-oxidation unit 210.
  • the particulate solid 180 may be passed from the dehydrogenation reactor 110 to a pre-oxidation unit 210 before being passed to the regeneration unit 150.
  • an oxygen-containing gas 212 may enter the pre-oxidation unit 210 via an oxidation gas inlet (not shown in FIG. 2).
  • the oxygen-containing gas 212 may be air, enriched air, air mixed with steam, or flue gas. Enriched air is air with added oxygen gas.
  • the oxygen-containing gas 212 may include less than 28 mol.% oxygen.
  • the oxy gen-containing gas 212 may include from about 2 mol.% to about 28 mol.% oxygen, from about 2 mol.% to about 25 mol.%, from about 2 mol.% to about 20 mol.%, from about 2 mol.% to about 15 mol.%, from about 2 mol.% to about 10 mol.%, from about 2 mol.% to about 5 mol.%, from about 5 mol.% to about 28 mol.%, from about 5 mol.% to about 25 mol.%, from about 5 mol.% to about 20 mol.%, from about 5 mol.% to about 15 mol.%, from about 5 mol.% to about 10 mol.%, from about 10 mol.% to about 28 mol.%, from about 10 mol.% to about 25 mol.%, from about 10 mol.% to about 20 mol.%, from about 10 mol.% to about 15 mol.%, from about 15 mol.% to about 28 mol.%, from
  • the oxygen-carrier material of the particulate solid 180 may be exposed to the oxygen-containing gas 212 in the pre-oxidation unit 210. In some embodiments, the content of oxygen in at least a portion of the oxygen-carrier material of the particulate solid 180 may be increased in the pre-oxidation unit 210. In some embodiments, the oxygen-containing gas 212 and the particulate solid 180 may flow generally co-currently in an upward direction through the pre-oxidation unit 210. As used herein, “generally co-currently” means that the average velocities of the particulate solid 180 and the oxygen-containing gas 212 are in the same direction.
  • the velocity of individual particles of the particulate solid 180 or the individual gas molecules of the oxygen-containing gas 212 may have a distribution and may not be equal to the average, but taken as a whole the velocity of both components will average out to be generally in the same direction.
  • coke that may form on the particulate solid 180 in the dehydrogenation reactor 110 may be combusted in the pre-oxidation unit 210 heating at least a portion of the particulate solid 180.
  • the particulate solid 180 may be passed from the pre- oxidation unit 210 to the regeneration unit 150 via a stream 222.
  • the particulate solid 180 may be mixed with gases, such as the oxygen-containing gas 212 from the pre-oxidation unit 210, combustion gases from the combustion of coke in the pre-oxidation unit 210, carry-over gases from the dehydrogenation reactor 110, or combinations thereof as it is passed to the regeneration unit 150.
  • the particulate solid 180 may be passed from the regeneration unit 150 to the pre-oxidation unit 210.
  • the particulate solid 180 may be passed back to the pre-oxidation unit 210 to achieve a desired oxidation level of the oxy gen-carrier material of the particulate solid 180.
  • the particulate solid 180 may be passed from the fuel zone 164 out of the regeneration unit 150 to the pre-oxidation unit 210 to be passed through the pre-oxidation unit 210 and the regeneration unit 150 again.
  • the particulate solid 180 may be passed from the air zone 174 out of the regeneration unit 150 to the pre-oxidation unit 210 to be passed through the pre-oxidation unit 210 and the regeneration unit 150 again.
  • the particulate solid 180 may be passed from the regeneration unit 150 to the pre-oxidation unit 210 from both the air zone 174 and the fuel zone 164.
  • the regeneration unit 150 may include a third gas inlet 140.
  • a stripping gas 142 may enter the regeneration unit 150 through the third gas inlet 140.
  • the third gas inlet 140 may be beneath the second gas inlet 170.
  • the stripping gas 142 may exit the third gas inlet 140 in a generally upwards direction.
  • the stripping gas 142 may enter the regeneration unit 150 in an initially downwards direction before following the flow of other gases within the regeneration unit 150 generally upwards.
  • the area above the third gas inlet 140 and below the second gas inlet 170 may be a strip zone 144, as the directional flow of the stripping gas 142 into the regeneration unit 150 may cause the concentration of stripping gas 142 to be higher in the area above the third gas inlet 140 and below the second gas inlet 170.
  • the stripping gas 142 may comprise air, nitrogen, steam, or combinations thereof.
  • the stripping gas 142 may comprise a reductant.
  • the reductant may comprise hydrogen, methane, or combinations thereof.
  • the particulate solid 180 may be exposed to the reductant in the stripping gas 142 in the strip zone 144 and the oxygen content in at least a portion of the oxygen-carrier material of the particulate solid 180 may be reduced.
  • the concentration of reductant in the stripping gas 142 may be greater than 10 mol.%. In some embodiments the concentration of reductant in the stripping gas 142 may even be greater than 90 mol.%.
  • the concentration of reductant in the stripping gas 142 may be from about 1 mol.% to about 100 mol.%, such as from about 1 mol.% to about 90 mol.%, from about 1 mol.% to about 80 mol.%, from about 1 mol.% to about 70 mol.%, from about 1 mol.% to about 60 mol.%, from about 1 mol.% to about 50 mol.%, from about 1 mol.% to about 40 mol.%, from about 1 mol.% to about 30 mol.%, from about 1 mol.% to about 20 mol.%, from about 1 mol.% to about 10 mol.%, from about 10 mol.% to about 100 mol.%, from about 10 mol.% to about 90 mol.%, from about 10 mol.% to about 80 mol.%, from about 10 mol.% to about 70 mol.%, from about 10 mol.% to about 60 mol.%, from about 10 mol.% to about 50
  • At least a portion of the particulate solid 180 may be withdrawn from the regeneration unit 150 and passed through at least a portion of the regeneration unit 150 a second time before being passed to the dehydrogenation reactor 110. Accordingly, in some embodiments, at least a portion of the particulate solid 180 may be withdrawn from the air zone 174 and passed to the fuel zone 164. In other embodiments, at least a portion of the particulate solid 180 may be withdrawn from the strip zone 144 and passed to the fuel zone 164, the air zone 174, or both.
  • hydrocarbons may be dehydrogenated by a method comprising contacting a feed stream comprising one or more hydrocarbons with a particulate solid in a dehydrogenation reactor.
  • the particulate solid comprises an oxygen-carrier material.
  • the one or more hydrocarbons are dehydrogenated to form hydrogen and one or more products.
  • At least a portion of the hydrogen is reacted with oxygen from the oxygen-carrier material to form water and reduce the oxygen content in the oxygencarrier material.
  • the method further comprises passing at least a portion of the particulate solid from the dehydrogenation reactor to a regeneration unit.
  • the particulate solid moves in a generally downward direction through the regeneration unit and gases move in a generally upwards direction through the regeneration unit, such that the particulate solid and gases move in a countercurrent flow pattern through the regeneration unit.
  • the regeneration unit comprises a first gas inlet and a second gas inlet. The second gas inlet is beneath the first gas inlet.
  • a fuel enters into the regeneration unit through the first gas inlet.
  • An oxy gen-containing gas enters into the regeneration unit through the second gas inlet.
  • At least a portion of the fuel is reacted with oxygen from one or both of the oxygencontaining gas or the oxygen-carrier material of the particulate solid.
  • the method may further comprise passing at least a portion of the particulate solid from the regeneration unit to the dehydrogenation reactor.
  • a second aspect of the present disclosure may include the first aspect, where in an area of the regeneration unit above the second gas inlet and beneath the first gas inlet, the oxygen content in at least a portion of the oxygen-carrier material of the particulate solid increases.
  • a third aspect of the present disclosure may include the first aspect, where in the area of the regeneration unit above the first gas inlet, at least a portion of the fuel is reacted with oxygen from the oxygen-carrier material of the particulate solid and the oxygen content of at least a portion of the oxygen-carrier material is reduced.
  • a fourth aspect of the present disclosure may include the first aspect, where in the area of the regeneration unit above the first gas inlet at least a portion of the fuel is reacted with oxygen from the oxygen-containing gas and the oxygen content of at least a portion of the oxygen-carrier material is increased.
  • a fifth aspect of the present disclosure may include the first aspect, where at least a portion of the particulate solid is passed back to the dehydrogenation reactor without being passed to the regeneration unit.
  • a sixth aspect of the present disclosure may include any of the previous aspects, where the one or more hydrocarbons comprise an alkyl moiety and the one or more products comprise one or more olefinic compounds.
  • a seventh aspect of the present disclosure may include any of the previous aspects, where the fuel comprises hydrogen.
  • An eighth aspect of the present disclosure may include any of the previous aspects, where coke is deposited on the particulate solid that passes from the dehydrogenation reactor to the regeneration unit, and at least a portion of the coke is reacted in the regeneration unit.
  • a ninth aspect of the present disclosure may include any of the previous aspects, where passing the particulate solid from the dehydrogenation reactor to the regeneration unit comprises passing the particulate solid through a pre-oxidation unit, where the particulate solid is exposed to an oxy gen-containing gas in the pre-oxidation unit such that the content of oxygen in at least a portion of the oxygen-carrier material of the solid particulate is increased in the pre-oxidation unit.
  • a tenth aspect of the present disclosure may include the ninth aspect, where the particulate solid and the oxygen-containing gas flow generally co-currently in an upward direction through the pre-oxidation unit.
  • An eleventh aspect of the present disclosure may include any of the previous aspects, where the regeneration unit includes a third gas inlet beneath the second gas inlet, and a stripping gas enters into the regeneration unit through the third gas inlet, and where the stripping gas comprises from 0 mol.% to 100 mol.% of a reductant.
  • a twelfth aspect of the present disclosure may include any of the previous aspects, where a portion of the particulate solid is withdrawn from the regeneration unit and passed through at least a portion of the regeneration unit a second time before it is passed to the dehydrogenation reactor.
  • a thirteenth aspect of the present disclosure may include any of the previous aspects, where the solid particulate consists essentially of the oxygen-carrier material and the dehydrogenation of the one or more hydrocarbons is by non-catalytic thermal dehydrogenation.
  • a fourteenth aspect of the present disclosure may include the first aspect, where the particulate solid may further comprise a dehydrogenation catalyst material and where the dehydrogenation of the one or more hydrocarbons is at least partially by catalytic dehydrogenation
  • a fifteenth aspect of the present disclosure may include the fourteenth aspect, where the dehydrogenation catalyst material and the oxygen-carrier material are separate particles of the particulate solid or the dehydrogenation catalyst material and the oxygen-carrier material are contained in the same particles of the particulate solid.
  • compositions are described as “comprising” one or more elements, embodiments of that composition “consisting of’ or “consisting essentially of’ those one or more elements is contemplated herein.
  • chemicals or chemical streams are described as “passing” from one system unit or portion of a system unit to another.
  • passing may include direct passing or indirect passing.
  • direct passing has no intermediate destination between unit A and unit B (i.e., directly through a pipe or other transport passage)
  • indirect passing may include one or more intermediate destinations between unit A and unit B.
  • a stream passing from unit A to unit B may passed through, without limitation, a heat exchanger, treatment device, etc.
  • compositional ranges of a chemical constituent in a stream or in a reactor should be appreciated as containing, in some embodiments, a mixture of isomers of that constituent.
  • a compositional range specifying butene may include a mixture of various isomers of butene.
  • the examples supply compositional ranges for various streams, and that the total amount of isomers of a particular chemical composition can constitute a range.
  • any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. Where multiple ranges for a quantitative value are provided, these ranges may be combined to form a broader range, which is contemplated in the embodiments described herein.

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Abstract

Selon un ou plusieurs modes de réalisation, la présente invention concerne un procédé de déshydrogénation d'hydrocarbures qui peut comprendre la mise en contact d'un flux d'alimentation comprenant un ou plusieurs hydrocarbures avec un solide particulaire, qui peut comprendre un matériau transporteur d'oxygène, pour former de l'hydrogène et un ou plusieurs produits. Au moins une partie de l'hydrogène peut être mise à réagir avec de l'oxygène provenant du matériau transporteur d'oxygène. Une unité de régénération peut comprendre une première entrée de gaz et une seconde entrée de gaz qui peut être sous la première entrée. Un combustible peut entrer dans l'unité de régénération à travers la première entrée de gaz et un gaz contenant de l'oxygène peut entrer à travers la seconde entrée de gaz. Dans une zone de l'unité de régénération au-dessus de la première entrée de gaz, au moins une partie du combustible peut être mise à réagir avec de l'oxygène provenant du gaz contenant de l'oxygène et/ou du matériau transporteur d'oxygène.
PCT/US2023/074022 2022-09-14 2023-09-13 Procédés de déshydrogénation d'hydrocarbures utilisant des régénérateurs WO2024059600A1 (fr)

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