Classifications

• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
• • 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
  • B01J23/90—Regeneration or reactivation
• • 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
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/02—Heat treatment
• • 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
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
  • B01J38/12—Treating with free oxygen-containing gas
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/005—Separating solid material from the gas/liquid stream
  • B01J8/006—Separating solid material from the gas/liquid stream by filtration
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/0278—Feeding reactive fluids
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/1836—Heating and cooling the reactor
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/02—Alkenes
  • C07C11/06—Propene
• • 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
  • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
  • C07C5/321—Catalytic processes
  • C07C5/322—Catalytic processes with metal oxides or metal sulfides
• • 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
  • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
  • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
  • C07C5/333—Catalytic processes
  • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
  • C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2247/00—Details relating to the separation of dispersed particles from gases, air or vapours by liquid as separating agent
  • B01D2247/04—Regenerating the washing fluid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
  • B01D47/14—Packed scrubbers
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00743—Feeding or discharging of solids
  • B01J2208/00761—Discharging
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00743—Feeding or discharging of solids
  • B01J2208/00769—Details of feeding or discharging
  • B01J2208/00787—Bringing the solid in the form of a slurry before feeding it to the reactor
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00796—Details of the reactor or of the particulate material
  • B01J2208/00946—Features relating to the reactants or products
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00796—Details of the reactor or of the particulate material
  • B01J2208/00991—Disengagement zone in fluidised-bed reactors
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/70—Catalyst aspects
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/584—Recycling of catalysts

Definitions

• the present invention relates to a process for removing catalyst from an effluent, and more particularly relates to a process for removing catalyst from a Propane Dehydrogenation (PDH) reactor effluent stream using a wash fluid and filtration.
• PDH Propane Dehydrogenation
• a potential deficiency in processes for alkane or paraffin dehydrogenation employing a riser or fluidized-bed type reactor is the amount of catalyst particles including fines in the effluent streams leaving the dehydrogenation reactor.
• a water quench tower is used to cool the reactor effluent and condense the water therein, particularly if dilution steam is used to lower the partial pressure of the alkane or paraffin.
• the catalyst and fines contained in the reactor effluent stream cannot easily be separated from quench water, leading to excessive fouling in the equipment and consequential high maintenance costs.
• Some catalyst is entrained from the reactor and needs to be removed before entering downstream separation steps.
• the reactor effluent contains steam (water) from either dilution steam or stripping / fluidizing steam added in the reactor.
• steam water
• stripping / fluidizing steam added in the reactor.
• separation of catalyst from water is problematic since the mixture becomes mud-like, which is difficult to filter or transport. Even if the catalyst is filtered, the resulting water-catalyst slurry is not suitable to be returned to the reactor for catalyst recovery.
• FIG. 1 is a non-limiting, schematic illustration of a process for using a fuel oil wash to remove catalyst from a fluidized-bed propane dehydrogenation reactor effluent described herein;
• FIG. 2 is schematic illustration of another non-limiting embodiment a process for using a fuel oil wash to remove catalyst from a fluidized-bed propane dehydrogenation reactor effluent employing a flash zone described herein.
• a method for recovering catalyst from a fluidized-bed propane dehydrogenation reactor effluent gas includes (a) cooling fluidized-bed propane dehydrogenation reactor effluent gas, (b) contacting the effluent gas with fuel oil in a wash section to wash out catalyst to obtain a cooled effluent gas essentially free of catalyst, (c) withdrawing an oil-catalyst slurry from the wash section and circulating the oil- catalyst slurry through a filter thereby removing catalyst from the fuel oil giving filtered wash oil, (d) returning filtered wash oil to the wash section as recirculated wash oil; and (e) backwashing the filter thereby recovering catalyst.
• the method further includes contacting the effluent gas with fuel oil in a direct contact inline device prior to entering a flash zone, followed by removing a net amount of fuel oil and a majority of the catalyst as a concentrated bottom oil-catalyst slurry.
• a system for recovering catalyst from a fluidized-bed propane dehydrogenation reactor effluent gas where the system includes a quench tower having an inlet for receiving the effluent gas, vapor-liquid contacting elements disposed above the inlet for cooling the effluent gas and washing out the catalyst, a gas outlet above the contacting elements for discharging cooled effluent gas essentially free of catalyst, and a liquid holdup zone below the inlet for collecting the fuel oil from the contacting elements, at least one filter operable in filtration and backwashing modes, and a filtration loop for circulating fuel oil from the liquid holdup zone through a filter and returning filtrate to the liquid holdup zone.
• the system further includes a direct contact inline device that receives and mixes the fluidized- bed propane dehydrogenation reactor effluent and the fuel oil prior to injecting them into a flash zone.
• metal oxide catalysts with a paraffin having 2-8 carbon atoms in a dehydrogenation reaction for a period ranging from about 0.05 seconds to about 10 minutes in a reactor, in a non-limiting embodiment, may lead to better selectivity for certain olefins, such as propylene and butylene. It has also been discovered that metal oxide catalyst particles and fines, generated because of attrition in a riser or fluidized-bed type reactor, are contained within the reactor effluent stream.
• catalyst particles and fines may be recovered by contacting the effluent stream of the reactor with a wash fluid, in one non-limiting embodiment external fuel oil, to form a cooled catalyst effluent stream and a substantially catalyst-free product stream and then filtering the cooled catalyst effluent stream with one or more filters to capture the catalyst fines for potential reuse.
• a wash fluid in one non-limiting embodiment external fuel oil
• filtering the cooled catalyst effluent stream with one or more filters to capture the catalyst fines for potential reuse.
• essentially free of catalyst is defined as having no problematic amounts of catalyst particles or fines, or catalyst is removed up to the practical limits.
• the paraffin to be contacted with the metal oxide catalyst(s) may include, but not necessarily be limited to, propane, ethane, n- butane, isobutane, and combinations thereof.
• the paraffin may be introduced to the reactor with or without an inert diluent or steam.
• the metal oxide catalysts useful in dehydrogenating the paraffin to produce a light olefin product gas may be made up of one or more of the following oxides: zinc, titanium, copper, iron, manganese, aluminum, silicon, zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, or niobium.
• the metal oxide catalyst(s) used are substantially free of platinum and chromium.
• the dehydrogenation of the paraffin using metal oxide catalysts of the kinds described above and recovery of catalyst fines in the reactor effluent stream may be accomplished, in one non-limiting embodiment, by a process in which a paraffin feedstock comprising paraffins having 2-8 carbons is contacted with one or more metal oxide catalysts in a riser or fluidized bed reactor under dehydrogenation conditions. This process may be performed at a reaction temperature of about 500-800 °C, a space velocity of about 0.1 -1 h 1 , and a pressure of about 0.01-0.2 MPa. In one non-restrictive version, the reaction period may range from about 0.05 seconds to about 10 minutes.
• the dehydrogenation reaction between the paraffin and the metal oxide catalyst(s) may also be carried out in a fixed-bed swing or riser or fluidized- bed reactor from which a reactor effluent stream is formed.
• effluent from a fluidized bed propane dehydrogenation reactor 1 contains small amounts of entrained catalyst, which may be understood to be catalyst particles and/or fines, such as metal oxide catalysts and/or fines previously discussed.
• the gas 1 After cooling the effluent 1 against reactor feed 1, the gas 1 is contacted with a circulating oil in a quench tower A or other vessel, in a non-limiting embodiment, an external fuel oil 2 to wash out any entrained catalyst, and carry it back to the reactor regenerator to recover the catalyst and provide fuel for regeneration.
• the washing step occurs in an oil wash section B of quench tower A, which oil wash section B utilizes a contact device such as trays or packing to ensure good contact between the wash oil 2 and the process effluent gas 1 , for effective removal of the catalyst. Wash oil 2 from an external sources is added to the top of this wash section B.
• An oil-catalyst slurry 3 is withdrawn from the bottom of the wash section B and at least part of the flow is circulated through a filtration system or filter C that removes catalyst from the oil-catalyst slurry 3.
• Filtered wash oil 4 is cooled (heat is used for process heating) in filtered oil heat exchanger D and returned to the top of the wash section B.
• recovered catalyst 5 along with the net amount of wash oil that was added to the system is routed to the reactor system regenerator, where the wash oil provides the net heat required for catalyst regeneration.
• Cooled effluent gas 6 is recirculated to the quench water (QW) section.
• the oil wash section B could be a separate column or in one nonlimiting embodiment be integrated as a lower section of a water quench tower A, as shown in FIG. 1.
• catalyst filtration device C One option for the catalyst filtration device C would be to use a multibed system with fixed filtration medium such as a sintered metal-type filter. After the filtration bed is loaded with catalyst, the circulating oil flow 3 would be switched to a second filter, while the first would be regenerated to clean the filter and recover the catalyst.
• An alternative filtration device(s) C would be to use a continuous filtration system where oil flows through a drum-type filter, and catalyst is continuously removed from the inside surface of the filter and the concentrated catalyst-oil slurry is continuously removed and routed to the reactor regenerator.
• the effluent gas 1 is contacted with fuel oil 4 in a direct contact inline device E (such as a quench fitting) before entering a flash zone F in a vessel A.
• a direct contact inline device E such as a quench fitting
• a net amount of oil 2 and the majority of entrained catalyst is removed as a concentrated bottom catalyst-oil slurry 5 which can be directed to the reactor regeneration system (not shown) for catalyst recovery and to provide the net fuel requirements.
• the gas from the flash zone F (which is nearly free of catalyst) next enters a wash section B that utilizes a contact device such as trays or packing to ensure good contact between the wash oil and the process gas, for effective removal of the remaining catalyst, as previously described.
• the oil 3 from the wash section B is pumped around and cooled (heat is used for process heating) in the oil heat exchanger D and returned to the top of the wash section B.
• a portion of this oil 4 is used in the direct contact inline device E as described above.
• the flash zone and oil wash section together could be accommodated in a separate column or be integrated as a lower section of a water quench tower as schematically illustrated in FIG. 2.
• paraffins, metal oxide catalysts, dehydrogenation reaction conditions and equipment, fuel oils, fluidized-bed propane dehydrogenation reactor effluents, catalyst fine recovery conditions and equipment falling within the claimed or disclosed parameters, but not specifically identified or tried in a particular example, are expected to be within the scope of this invention.
• the present invention may be practiced in the absence of an element not disclosed.
• the present invention may suitably comprise, consist or consist essentially of the elements disclosed.
• a method for recovering catalyst from a fluidized-bed propane dehydrogenation reactor effluent gas where the method consists essentially of or consists of (a) cooling fluidized-bed propane dehydrogenation reactor effluent gas, (b) contacting the effluent gas with fuel oil in a wash section to wash out catalyst to obtain a cooled effluent gas essentially free of catalyst, (c) withdrawing an oil-catalyst slurry from the wash section and circulating the oil-catalyst slurry through a filter thereby removing catalyst from the fuel oil giving filtered wash oil, (d) returning filtered wash oil to the wash section as recirculated wash oil; and (e) backwashing the filter thereby recovering catalyst.
• the method further consists essentially of or consists of contacting the effluent gas with fuel oil occurs in a direct contact inline device prior to entering a flash zone, followed by removing a net amount of fuel oil and a majority of the catalyst as a concentrated bottom oil-catalyst slurry.
• a system for recovering catalyst from a fluidized-bed propane dehydrogenation reactor effluent gas where the system consists essentially of or consists of a quench tower having an inlet for receiving the effluent gas, vapor-liquid contacting elements disposed above the inlet for cooling the effluent gas and washing out the catalyst, a gas outlet above the contacting elements for discharging cooled effluent gas essentially free of catalyst, and a liquid holdup zone below the inlet for collecting the fuel oil from the contacting elements, at least one filter operable in filtration and backwashing modes, and a filtration loop for circulating fuel oil from the liquid holdup zone through a filter and returning filtrate to the liquid holdup zone.
• the system further consists essentially of or consists of a direct contact inline device that receives and mixes the fluidized-bed propane dehydrogenation reactor effluent and the fuel oil prior to injecting them into a flash zone.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Combustion & Propulsion (AREA)
• Physics & Mathematics (AREA)
• Water Supply & Treatment (AREA)
• Thermal Sciences (AREA)
• Analytical Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Filtration Of Liquid (AREA)
• Catalysts (AREA)
• Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

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• 2019
  • 2019-09-13 US US16/570,029 patent/US11117108B2/en active Active
• 2020
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