Classifications

• • 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
• • 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
  • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/02—Alkenes
  • C07C11/04—Ethene
• • 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
  • 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
  • C10G11/04—Oxides
• • 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
  • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
• • 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
  • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
  • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
  • C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
• • 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
  • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
  • C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
  • C10G70/048—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by liquid-liquid extraction
• • 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
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/20—C2-C4 olefins
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/22—Higher olefins

Definitions

• the present invention relates to a process for dehydrogenation of paraffins by reacting a paraffin stream with metal oxide catalyst(s) to produce light olefins, such as propylene, and a process for the recovery of metal oxide catalyst fines from the reactor effluent stream using a wash fluid and filtration.
• a potential deficiency in processes for alkane or paraffin dehydrogenation employing a riser or fluidized-bed type reactor is the amount of catalyst 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 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.
• FIGURE 1 is a schematic illustration of a process for catalytic paraffin dehydrogenation and catalyst recovery of the kind described herein.
• a process for dehydrogenating paraffins by contacting a metal oxide catalyst with a paraffin having 2-8 carbon atoms in a riser, fluidized bed, or fixed-bed swing reactor for a reaction period ranging from about 0.05 seconds to about 10 minutes.
• the metal oxide catalyst is selected from group consisting of oxides of zinc, titanium, copper, iron, manganese, aluminum, silicon, zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, niobium, and combinations thereof, wherein the metal oxide catalyst is substantially free of platinum and chromium.
• a process for recovering catalyst fines from the reactor effluent stream of a catalytic paraffin dehydrogenation reaction in a riser or fluid ized-bed type reactor comprising: contacting a metal oxide catalyst with a paraffin having 2-8 carbon atoms; generating a reactor effluent stream comprising metal oxide catalyst fines after contacting the metal oxide catalyst with the paraffin; and contacting the reactor effluent stream with a wash fluid to transfer the metal oxide catalyst fines from the reactor effluent stream into the wash fluid and form a cooled catalyst effluent stream and a substantially catalyst- free product stream.
• metal oxide catalyst fines generated because of attrition in a riser or fluidized-bed type reactor, are contained within the reactor effluent stream.
• catalyst fines may be recovered by contacting the effluent stream of the reactor with a wash fluid, typically oil or water, to form a cooled catalyst effluent stream and a substantially catalyst-free product stream and then filtering the cooled catalyst effluent stream with a set of filters to capture the catalyst fines for potential reuse.
• a wash fluid typically oil or water
• the paraffin to be contacted with the metal oxide catalyst(s) may be 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 cata!yst(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 the process depicted in the FIGURE 1 in which a paraffin feedstock 10 comprising paraffins having 2-8 carbons is contacted with one or more metai oxide catalysts in a riser or fluidized bed reactor under dehydrogenation conditions.
• This process may be performed at a reaction temperature of 500-800 °C, a space velocity of 0.1 -1 IT 1 , and a pressure of 0.01-0.2 MPa.
• the reaction period may range from about 0.05 seconds to about 10 minutes.
• the dehydrogenation reaction between the paraffin and the metal oxide cataFyst(s) may also be carried out in a fixed-bed swing or riser or fluidized-bed reactor from which a reactor outlet stream 20 is formed.
• the reactor outlet stream 20, in one non- restrictive embodiment, is then sent to a cyclone or disengager to separate catalyst from the reactor outlet stream and form an overhead reactor effluent stream 30.
• the reactor effluent stream 30 contains light olefins, such as, without limitation, propylene and/or ethylene.
• the bulk of the catalyst is retained within the reactor or recovered in the cyclone/disengager and then sent as a separated catalyst stream 40 to a regenerator, which uses combustion air 50 to produce a flue gas stream 60 and a regenerated catalyst stream 70 that is returned to the reactor.
• some catalyst fines may be contained in the reactor effluent stream 30.
• These metal oxide catalyst fines may be recovered in a process in which the reactor effluent stream 30 is contacted in a quench tower with a wash fluid 90, typically oil or water, to transfer the metal oxide catalyst fines from the reactor outlet stream into the wash fluid and form a cooled catalyst effluent stream 100 and a substantially catalyst-free product stream 80.
• the reactor effluent stream 30 is contacted with the wash fluid in a quench tower that contains vapor-liquid contacting elements, such as, without limitation, packing or trays.
• the quench tower in another embodiment, may also have a recirculation loop for continuously recirculating a wash fluid to the contacting elements.
• the cooled catalyst effluent stream 100 may subsequently be converted into a slurry and then directed to one or more filters to separate the metal oxide catalyst fines.
• the slurry is continuously passed through a first filter in a filtration mode to separate the metal oxide catalyst fines therefrom while a second filter in parallel with the first filter is in backflushing mode to remove the separated metal oxide catalyst fines therefrom.
• the filtration of the slurry may comprise periodically alternating the first and the second filters between filtration and backflushing mode.
• the separated metal oxide catalyst fines may be collected and accumulated in a catalyst accumulator. The catalyst fines may then be prepared for reuse in the dehydrogenation reaction.
• 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.
• the process may comprise, consist of, or consist essentially of: contacting a metal oxide catalyst with a paraffin having 2-8 carbon atoms in a reactor for a reaction period ranging from about 0.05 seconds to about 10 minutes.
• the recovery of the catalyst fines from a reactor effluent stream may comprise, consist of, or consist essentially of: contacting a metal oxide catalyst with a paraffin having 2-8 carbon atoms, generating a reactor effluent stream comprising metal oxide catalyst fines after contacting the metal oxide catalyst with the paraffin, and contacting the reactor effluent stream with a wash fluid to transfer the metal oxide catalyst fines from the reactor effluent stream into the wash fluid and form a cooled catalyst effluent stream and a substantially catalyst-free product stream.
• the word“substantially” shall mean“being largely but not wholly that which is specified.”
• the term“about” in reference to a given parameter is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the given parameter).

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• Water Supply & Treatment (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2020
  • 2020-03-19 SG SG11202110419TA patent/SG11202110419TA/en unknown
  • 2020-03-19 JP JP2021556846A patent/JP2022526905A/ja active Pending
  • 2020-03-19 EP EP20773264.5A patent/EP3941893A4/en not_active Withdrawn
  • 2020-03-19 CN CN202080028734.4A patent/CN113710633A/zh active Pending
  • 2020-03-19 KR KR1020217033232A patent/KR20210142677A/ko not_active Ceased
  • 2020-03-19 WO PCT/US2020/023627 patent/WO2020191192A1/en not_active Ceased
  • 2020-03-19 US US16/823,733 patent/US20200299212A1/en not_active Abandoned

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