WO2017074790A1 - Process for maximizing hydrogen recovery - Google Patents

Process for maximizing hydrogen recovery Download PDF

Info

Publication number
WO2017074790A1
WO2017074790A1 PCT/US2016/057934 US2016057934W WO2017074790A1 WO 2017074790 A1 WO2017074790 A1 WO 2017074790A1 US 2016057934 W US2016057934 W US 2016057934W WO 2017074790 A1 WO2017074790 A1 WO 2017074790A1
Authority
WO
WIPO (PCT)
Prior art keywords
stream
hydrogen
permeate
mole
membrane
Prior art date
Application number
PCT/US2016/057934
Other languages
French (fr)
Inventor
Eleftherios Adamopoulos
Original Assignee
Uop Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Uop Llc filed Critical Uop Llc
Priority to EP16860538.4A priority Critical patent/EP3368193A4/en
Publication of WO2017074790A1 publication Critical patent/WO2017074790A1/en
Priority to US15/796,709 priority patent/US10710879B2/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B01D71/643—Polyether-imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/146—At least two purification steps in series
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • This invention generally relates to a process for maximizing hydrogen recovery.
  • a hydrogen recovery system can be used for processes producing hydrogen. Generally, a net production of hydrogen occurs during catalytic reforming or through processes that convert saturated hydrocarbons to olefins or to aromatics and recovery of the hydrogen for use in chemical processing or fuel is typically desired.
  • Another industrial process in which hydrogen is produced is a feed stream from a coke oven.
  • a coke oven is a device used to produce coke from coal. In this process, large quantities of synthesis gas are produced and it is desirable to recover as much of the hydrogen as possible from this process and from other processes that involve the heating and/or gasification of hydrocarbons.
  • Purified methane serves as the building block for a variety of chemicals produced in a petrochemical complex. It is advantageous to develop processes that not only recover hydrogen but also allow for recovery and use of valuable hydrocarbons including methane and ethane. Therefore, there is a desire to provide other separation and/or hydrogen recovery systems to overcome these deficiencies.
  • an effluent from a reaction zone comprising a mixture of hydrocarbons and hydrogen is sent to an adsorption zone.
  • a hydrogen product stream is produced and a tail gas from the adsorption zone is compressed and sent as a feed stream across a feed side of a membrane having a feed side and a permeate side, and being selective for hydrogen over one or more of C1-C6 hydrocarbons.
  • the process further comprises withdrawing from the permeate side a permeate stream enriched in hydrogen compared with a residue stream withdrawn from the feed side that has a low concentration of hydrogen. The permeate stream is then recycled to be combined with the effluent that is sent to the adsorption zone.
  • the residue stream may be sent to be used for fuel or it may be returned to a product recovery part of the process such as being sent to a de-ethanizer column to recover propane (feed) and propylene (product). Depending upon the process being employed, other products may be recovered. This process allows for an increase in the overall recovery of both the hydrogen and the hydrocarbon.
  • One exemplary embodiment can be a process for catalytic reforming.
  • the process can include catalytically reforming a hydrocarbon feed in a reaction zone, obtaining an effluent stream having hydrogen and hydrocarbons from the reaction zone, obtaining from at least a portion of the effluent stream a waste hydrocarbon stream from an adsorption zone, passing at least a portion of the waste hydrocarbon stream as a feed stream across a feed side of a membrane having the feed side and a permeate side, and being selective for hydrogen over one or more C1-C6 hydrocarbons, and withdrawing from the permeate side a permeate stream enriched in hydrogen compared with a residue stream withdrawn from the feed side.
  • the residue stream is then be returned to the adsorption zone for further processing.
  • Another exemplary embodiment may be a process for dehydrogenation of light paraffins, such as in UOP's Oleflex process.
  • the process may involve reacting a hydrocarbon feed in a reaction zone, obtaining an effluent stream having hydrogen and hydrocarbons from the reaction zone, obtaining from at least a portion of the effluent stream a waste hydrocarbon stream from an adsorption zone, passing at least a portion of the waste hydrocarbon stream as a feed stream across a feed side of a membrane having the feed side and a permeate side, and being selective for hydrogen over nitrogen, carbon monoxide, and one or more C1-C6 hydrocarbons, and withdrawing from the permeate side a permeate stream enriched in hydrogen and having at least 85%, by mole, hydrogen which then is returned to the adsorption zone.
  • a non-permeate or residue stream may be recycled to a de-ethanizer to recover propane and propylene to improve the product yield of the process.
  • the term "stream” can include various hydrocarbon molecules, such as straight-chain, branched, or cyclic alkanes, alkenes, alkadienes, and alkynes, and optionally other substances, such as gases, e.g., hydrogen, or impurities, such as heavy metals, carbon oxides, and sulfur and nitrogen compounds.
  • the stream can also include aromatic and non-aromatic hydrocarbons.
  • the hydrocarbon molecules may be abbreviated CI, C2, C3...Cn where "n” represents the number of carbon atoms in the one or more hydrocarbon molecules.
  • a superscript "+” or “-” may be used with an abbreviated one or more hydrocarbons notation, e.g., C3 + or C3 " , which is inclusive of the abbreviated one or more hydrocarbons.
  • C3 + means one or more hydrocarbon molecules of three carbon atoms and/or more.
  • a "stream” may also be or include substances, e.g., fluids or substances behaving as fluids, other than hydrocarbons, such as air, hydrogen, or catalyst.
  • the term "zone” can refer to an area including one or more equipment items and/or one or more sub-zones.
  • Equipment items can include one or more reactors or reactor vessels, heaters, exchangers, pipes, pumps, compressors, and controllers. Additionally, an equipment item, such as a reactor, dryer, or vessel, can further include one or more zones or sub-zones.
  • the term “rich” can mean an amount of at least generally 50%, and preferably 70%, by mole, of a compound or class of compounds in a stream.
  • the term “substantially” can mean an amount of at least generally 80%), preferably 90%, and optimally 99%, by mole, of a compound or class of compounds in a stream.
  • adsorbent and “adsorber” include, respectively, an absorbent and an absorber, and relates, but is not limited to, adsorption, and/or absorption.
  • liquid hourly space velocity can be defined as volumes of fresh charge stock per hour per volume of catalyst particles in the reaction zone and be abbreviated "LHSV”.
  • the term “hour” may be abbreviated “hr”
  • the term “kilogram” may be abbreviated “kg”
  • the term “kilopascal” may be abbreviated “KPa”
  • the terms “degrees Celsius” may be abbreviated “° C”. All pressures are absolute.
  • process flow lines in the figures can be referred to interchangeably as, e.g., lines, pipes, feeds, effluents, products, portions, remainders, discharges, or streams.
  • FIGURE is a schematic depiction of an exemplary hydrogen recovery process flow scheme.
  • a feed 10 comprising a mixture of hydrocarbon and hydrogen 10 can be from a reforming process, a paraffin dehydrogenation process or a synthesis gas producing process. Feed 10 may then proceed to a mix point 20 and continue as PSA feed 30 to a PSA unit 40 to produce a hydrogen product stream 50 that may comprise over 99%) hydrogen and a tail gas 60 that still has an appreciable content of hydrogen such as 35%) hydrogen. Tail gas 60 is compressed in compressor 70 to produce compressed tail gas stream 80.
  • PSA unit 40 is a pressure swing adsorption (which may be abbreviated "PSA") zone which produces hydrogen product stream 50 with a purity of 90.0 - 99.9999%, by mole, hydrogen, or preferably of 95.0 - 99.99%, by volume, hydrogen.
  • the hydrogen product stream 50 may recover 80 - 95%, by mole, or even 85 - 90%), by mole, of the hydrogen feed stream 30.
  • tail gas stream 60 that is produced by the PSA unit 40 during a desorption or purge step at a desorption pressure ranging from 30 - 550 KPa.
  • the PSA zone 40 can include a plurality of adsorption beds containing an adsorbent selective for the separation of hydrogen from the hydrocarbons. Often, each adsorption bed within the adsorption zone undergoes, on a cyclic basis, high pressure adsorption, optional cocurrent depressurization to intermediate pressure levels with the release of product from void spaces, countercurrent depressurization to lower desorption pressure with the release of desorbed gas from the feed end of the adsorption bed, with or without purge of the bed, and repressurization to higher adsorption pressure.
  • This process may also include an addition to this basic cycle sequence, such as a cocurrent displacement step, or co-purge step in the adsorption zone following the adsorption step in which the less readily adsorbable component, or hydrogen, is essentially completely removed therefrom by displacement with an external displacement gas introduced at the feed end of the adsorption bed.
  • the adsorption zone may then be counter currently depressurized to a desorption pressure that is at or above atmospheric pressure with the more adsorbable component being discharged from the feed end thereof.
  • the displacement gas used for each bed may be obtained by using at least a portion of the debutanizer overhead vapor stream, although other suitable displacement gas, such as an external stream including one or more C1-C4 hydrocarbons, may also be employed.
  • the high pressure adsorption includes introducing the feedstream or hydrogen-rich gas stream to the feed end of the adsorption bed at a high adsorption pressure.
  • the hydrogen passes through the bed and is discharged from the product end thereof.
  • An adsorption front or fronts are established in the bed with the fronts likewise moving through the bed from the feed end toward the product end thereof.
  • the PSA zone 40 can include pressures of 300 - 6,890 KPa.
  • the PSA zone 40 can be carried out using any adsorbent material selective for the separation of hydrogen from hydrocarbons in the adsorbent beds.
  • Suitable adsorbents can include one or more crystalline molecular sieves, activated carbons, activated clays, silica gels, activated aluminas, and combinations thereof.
  • the adsorbents are one or more of an activated carbon, an alumina, an activated alumina, and a silica gel.
  • An exemplary PSA zone is disclosed in, e.g., US 5,332,492.
  • the PSA zone 40 can provide the hydrogen product stream 50 that can be provided to a reaction zone that requires hydrogen, and the tail gas stream 60.
  • the membrane unit 90 forms a feed side 120 and a permeate side 130.
  • the membrane unit 90 may be a hollow fiber membrane, a spiral wound membrane or other suitable type of membrane.
  • the hollow fiber membrane can be made of at least one of a polyimide, cellulose acetate, cellulose triacetate, and polysulfone.
  • the polyimide may be formed by reacting a dianhydride and a diamine or a dianhydride and a diisocyanate.
  • Such membranes are disclosed in, e.g., US 4,863,492.
  • a residue or non-permeate stream 100 can be withdrawn from the feed side 120 of the membrane 90.
  • the residue stream 100 may include nitrogen; one or more carbon oxides, typically carbon monoxide although carbon dioxide may be present instead or additionally; and one or more C1-C6 hydrocarbons.
  • the residue stream 100 is enriched in nitrogen, the one or more carbon oxides, typically carbon monoxide, and the one more C1-C6 hydrocarbons compared with the tail gas stream 60.
  • the residue stream 100 can be provided to a fuel header, provided as a feed to another process such as a steam-methane reforming unit, or optionally recontacted in a vessel to recover liquefied petroleum gases prior to being sent to the fuel header.
  • the compressed tail gas stream 80 contacts the membrane 90 with the smaller hydrogen molecules passing through the membrane 90 and other molecules, such as C1-C6 hydrocarbons, nitrogen, carbon dioxide, and carbon monoxide, are blocked.
  • the membrane 90 can block nitrogen and carbon oxides, such as carbon monoxide.
  • the membrane 90 can be operated in such a way that the permeate stream 110 can include no more than 8 mol%, or 20 ppm, by mole, of nitrogen and no more than 0.3 mol%, or 40 ppm, by mole, of carbon monoxide.
  • the amount of hydrogen by mole percent in the permeate stream 110 is substantially the same as the feed stream 10 and typically the amount of hydrogen composed in the permeate stream 110 is within ⁇ 15%, ⁇ 5%, ⁇ 2%, or ⁇ 1%, by mole, of the feed stream 10.
  • the permeate stream 110 can include at least 60%, or even at least 95% or 97%, by mole, hydrogen.
  • the permeate stream 110 may recover at least 90%, by mole, of the hydrogen in the compressed tail gas stream 80. Meanwhile, the membrane 90 rejects at least 70%, by mole, carbon monoxide; 76%), by mole, nitrogen; 79%, by mole, methane; 91%, by mole, ethane; and almost 100%), by mole, of the one or more C3+ hydrocarbons in the vapor stream 30.
  • the non-permeate or residue stream 100 may be sent to a product recovery zone 140.
  • the process and system of the invention can achieve an overall hydrogen recovery of at least 98%, by mole, of the hydrogen present in the feed stream 10.
  • the PSA tail gas pressure is 5 psig.
  • the fuel header pressure is set at 85 psig.
  • Scheme #2 PSA with 72% tail gas recycle.
  • the compressed, recycled tail gas gets mixed with the raw net gas upstream of the net gas compressor.
  • the overall hydrogen recovery is 97%.
  • Scheme #4 shows that by compressing the PSA tail gas to 467 psig instead of 204 psig cuts the number of membrane modules (housings) by more than half while the total power consumption increases by less than 4%.
  • a membrane non-permeate or residue stream may be recycled to a product recovery section, such as a de-ethanizer for recovery of propane and propylene.
  • a first embodiment of the invention is a process for recovery of hydrogen, comprising A) obtaining a stream comprising hydrogen, hydrocarbons, carbon monoxide, carbon dioxide, oxygen and nitrogen from a reaction zone; B) sending the stream through an adsorption zone to produce a hydrogen stream and a tail gas stream; C) passing at least a portion of the tail gas stream across a feed side of a membrane having the feed side and a permeate side, and being selective for hydrogen over one or more C1-C6 hydrocarbons, carbon monoxide, carbon dioxide, oxygen and nitrogen; D) withdrawing from the permeate side a permeate stream enriched in hydrogen compared with a residue stream withdrawn from the feed side; and E) recycling the permeate stream into the stream from the reaction zone.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the residue stream is sent to a product recovery section of an upstream process for additional recovery of feed and product.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate stream comprises no more than 8 percent, by mole, of nitrogen and no more than 0.3 percent, by mole, of carbon monoxide.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate stream comprises no more than 100 ppm, by mole, of nitrogen and no more than 100 ppm, by mole, of carbon monoxide.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate stream comprises no more than 20 ppm, by mole, of nitrogen and no more than 40 ppm, by mole, of carbon monoxide.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein an amount of hydrogen by mole percent in the permeate stream is substantially the same as a gas stream obtained from the effluent stream and upstream of the waste hydrocarbon stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the amount of hydrogen composition in the permeate stream is within 15%, by mole, of the gas stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the amount of hydrogen composition in the permeate stream is within 2%, by mole, of the gas stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the amount of hydrogen composition in the permeate stream is within 1%, by mole, of the gas stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the membrane comprises a hollow fiber membrane.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the membrane comprises a spiral wound membrane.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate comprises from 60 to 97%, by mole, hydrogen.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate comprises at least 98%, by mole, hydrogen.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the hollow fiber membrane comprises at least one polymer selected from the group consisting of polyimide, cellulose acetate, cellulose triacetate, and polysulfone.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The process can be used in any hydrocarbon process in which it is desirable to recover hydrogen. The process can include catalytically reforming a hydrocarbon feed, a paraffin dehydrogenation to produce light olefins or a synthesis gas generating process. There is an effluent stream having hydrogen and hydrocarbons that is first sent to an adsorption zone to produce a pure hydrogen stream and a tail gas stream. The tail gas stream is then sent across a feed side of a membrane having the feed side and a permeate side. The membrane that is selected is selective for hydrogen over one or more C1-C6 hydrocarbons and light ends including CO, CO2, N2 and O2, and withdrawing from the permeate side a permeate stream enriched in hydrogen compared with a residue stream withdrawn from the feed side. The permeate stream is then recycled to be sent through the adsorption zone.

Description

PROCESS FOR MAXIMIZING HYDROGEN RECOVERY
STATEMENT OF PRIORITY
[OOOl] This application claims priority to U.S. Application No. 62/246,269 which was filed October 26, 2015, the contents of which are hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention generally relates to a process for maximizing hydrogen recovery.
DESCRIPTION OF THE RELATED ART
[0003] Various types of catalytic hydrocarbon conversion reaction systems utilized in petroleum and petrochemical industries can convert hydrocarbons to different products. The reactions employed in such systems can be either exothermic or endothermic. Usually, the reactions result in either the net production of hydrogen or the net consumption of hydrogen.
A hydrogen recovery system can be used for processes producing hydrogen. Generally, a net production of hydrogen occurs during catalytic reforming or through processes that convert saturated hydrocarbons to olefins or to aromatics and recovery of the hydrogen for use in chemical processing or fuel is typically desired. Another industrial process in which hydrogen is produced is a feed stream from a coke oven. A coke oven is a device used to produce coke from coal. In this process, large quantities of synthesis gas are produced and it is desirable to recover as much of the hydrogen as possible from this process and from other processes that involve the heating and/or gasification of hydrocarbons.
[0004] However, current hydrogen recovery systems suffer from several shortcomings.
Many fail to remove sufficient amounts of heavier compounds, such as nitrogen, carbon oxides, including carbon monoxide, methane, ethane, and ethene, resulting in greater energy consumption by a compressor. Also, insufficient systems for separating hydrogen gas from contaminants can allow catalytic poisoning if the hydrogen gas is recycled to a reforming zone or used in other hydroprocessing catalytic processes. Additionally, if the recovered hydrogen has a sufficiently different composition and is combined with another hydrogen gas, such a combination may result in process upsets, such as impeding compressor efficiency. In addition, in some processes it is advantageous to the economics of the process to maximize the recovery of hydrogen to levels of 98% or better. In one possible process scheme maximizing hydrogen recovery results in build-up of methane (and ethane to a lesser degree) in a tail gas recycle loop that limits the amount of PSA tail gas that can be recycled, and that in turn limits hydrogen recovery. There is a need to remove this methane
"bottleneck" and push the overall hydrogen recovery to 98% or better. In addition, in some embodiments of the invention the need for purified methane is achieved. Purified methane serves as the building block for a variety of chemicals produced in a petrochemical complex. It is advantageous to develop processes that not only recover hydrogen but also allow for recovery and use of valuable hydrocarbons including methane and ethane. Therefore, there is a desire to provide other separation and/or hydrogen recovery systems to overcome these deficiencies.
SUMMARY OF THE INVENTION
[0005] In the practice of the invention, an effluent from a reaction zone comprising a mixture of hydrocarbons and hydrogen is sent to an adsorption zone. A hydrogen product stream is produced and a tail gas from the adsorption zone is compressed and sent as a feed stream across a feed side of a membrane having a feed side and a permeate side, and being selective for hydrogen over one or more of C1-C6 hydrocarbons. The process further comprises withdrawing from the permeate side a permeate stream enriched in hydrogen compared with a residue stream withdrawn from the feed side that has a low concentration of hydrogen. The permeate stream is then recycled to be combined with the effluent that is sent to the adsorption zone. The residue stream may be sent to be used for fuel or it may be returned to a product recovery part of the process such as being sent to a de-ethanizer column to recover propane (feed) and propylene (product). Depending upon the process being employed, other products may be recovered. This process allows for an increase in the overall recovery of both the hydrogen and the hydrocarbon.
[0006] One exemplary embodiment can be a process for catalytic reforming. The process can include catalytically reforming a hydrocarbon feed in a reaction zone, obtaining an effluent stream having hydrogen and hydrocarbons from the reaction zone, obtaining from at least a portion of the effluent stream a waste hydrocarbon stream from an adsorption zone, passing at least a portion of the waste hydrocarbon stream as a feed stream across a feed side of a membrane having the feed side and a permeate side, and being selective for hydrogen over one or more C1-C6 hydrocarbons, and withdrawing from the permeate side a permeate stream enriched in hydrogen compared with a residue stream withdrawn from the feed side. The residue stream is then be returned to the adsorption zone for further processing.
[0007] Another exemplary embodiment may be a process for dehydrogenation of light paraffins, such as in UOP's Oleflex process. The process may involve reacting a hydrocarbon feed in a reaction zone, obtaining an effluent stream having hydrogen and hydrocarbons from the reaction zone, obtaining from at least a portion of the effluent stream a waste hydrocarbon stream from an adsorption zone, passing at least a portion of the waste hydrocarbon stream as a feed stream across a feed side of a membrane having the feed side and a permeate side, and being selective for hydrogen over nitrogen, carbon monoxide, and one or more C1-C6 hydrocarbons, and withdrawing from the permeate side a permeate stream enriched in hydrogen and having at least 85%, by mole, hydrogen which then is returned to the adsorption zone. A non-permeate or residue stream may be recycled to a de-ethanizer to recover propane and propylene to improve the product yield of the process.
DEFINITIONS
[0008] As used herein, the term "stream" can include various hydrocarbon molecules, such as straight-chain, branched, or cyclic alkanes, alkenes, alkadienes, and alkynes, and optionally other substances, such as gases, e.g., hydrogen, or impurities, such as heavy metals, carbon oxides, and sulfur and nitrogen compounds. The stream can also include aromatic and non-aromatic hydrocarbons. Moreover, the hydrocarbon molecules may be abbreviated CI, C2, C3...Cn where "n" represents the number of carbon atoms in the one or more hydrocarbon molecules. Furthermore, a superscript "+" or "-" may be used with an abbreviated one or more hydrocarbons notation, e.g., C3+ or C3", which is inclusive of the abbreviated one or more hydrocarbons. As an example, the abbreviation "C3+" means one or more hydrocarbon molecules of three carbon atoms and/or more. A "stream" may also be or include substances, e.g., fluids or substances behaving as fluids, other than hydrocarbons, such as air, hydrogen, or catalyst.
[0009] As used herein, the term "zone" can refer to an area including one or more equipment items and/or one or more sub-zones. Equipment items can include one or more reactors or reactor vessels, heaters, exchangers, pipes, pumps, compressors, and controllers. Additionally, an equipment item, such as a reactor, dryer, or vessel, can further include one or more zones or sub-zones. [0010] As used herein, the term "rich" can mean an amount of at least generally 50%, and preferably 70%, by mole, of a compound or class of compounds in a stream.
[0011] As used herein, the term "substantially" can mean an amount of at least generally 80%), preferably 90%, and optimally 99%, by mole, of a compound or class of compounds in a stream.
[0012] As used herein, the terms "adsorbent" and "adsorber" include, respectively, an absorbent and an absorber, and relates, but is not limited to, adsorption, and/or absorption.
[0013] As used herein, the term "liquid hourly space velocity" can be defined as volumes of fresh charge stock per hour per volume of catalyst particles in the reaction zone and be abbreviated "LHSV".
[0014] As used herein, the term "hour" may be abbreviated "hr", the term "kilogram" may be abbreviated "kg", the term "kilopascal" may be abbreviated "KPa", and the terms "degrees Celsius" may be abbreviated "° C". All pressures are absolute.
[0015] As depicted, process flow lines in the figures can be referred to interchangeably as, e.g., lines, pipes, feeds, effluents, products, portions, remainders, discharges, or streams.
BRIEF DESCRIPTION OF THE DRAWING
[0016] The FIGURE is a schematic depiction of an exemplary hydrogen recovery process flow scheme.
DETAILED DESCRIPTION
[0017] Referring to the FIGURE, a feed 10 comprising a mixture of hydrocarbon and hydrogen 10 can be from a reforming process, a paraffin dehydrogenation process or a synthesis gas producing process. Feed 10 may then proceed to a mix point 20 and continue as PSA feed 30 to a PSA unit 40 to produce a hydrogen product stream 50 that may comprise over 99%) hydrogen and a tail gas 60 that still has an appreciable content of hydrogen such as 35%) hydrogen. Tail gas 60 is compressed in compressor 70 to produce compressed tail gas stream 80. Then tail gas stream 80 is sent through membrane unit 90 which produces a non- permeate stream 100 that contains a small amount of hydrogen that can be further processed to recover hydrocarbons or used as fuel and permeate 110 from membrane unit 90 is recycled to mix point 20. [0018] PSA unit (also referred to as PSA zone, herein) 40 is a pressure swing adsorption (which may be abbreviated "PSA") zone which produces hydrogen product stream 50 with a purity of 90.0 - 99.9999%, by mole, hydrogen, or preferably of 95.0 - 99.99%, by volume, hydrogen. The hydrogen product stream 50 may recover 80 - 95%, by mole, or even 85 - 90%), by mole, of the hydrogen feed stream 30. Additionally, tail gas stream 60 that is produced by the PSA unit 40 during a desorption or purge step at a desorption pressure ranging from 30 - 550 KPa.
[0019] The PSA zone 40 can include a plurality of adsorption beds containing an adsorbent selective for the separation of hydrogen from the hydrocarbons. Often, each adsorption bed within the adsorption zone undergoes, on a cyclic basis, high pressure adsorption, optional cocurrent depressurization to intermediate pressure levels with the release of product from void spaces, countercurrent depressurization to lower desorption pressure with the release of desorbed gas from the feed end of the adsorption bed, with or without purge of the bed, and repressurization to higher adsorption pressure. This process may also include an addition to this basic cycle sequence, such as a cocurrent displacement step, or co-purge step in the adsorption zone following the adsorption step in which the less readily adsorbable component, or hydrogen, is essentially completely removed therefrom by displacement with an external displacement gas introduced at the feed end of the adsorption bed. The adsorption zone may then be counter currently depressurized to a desorption pressure that is at or above atmospheric pressure with the more adsorbable component being discharged from the feed end thereof.
[0020] In a multibed adsorption system, the displacement gas used for each bed may be obtained by using at least a portion of the debutanizer overhead vapor stream, although other suitable displacement gas, such as an external stream including one or more C1-C4 hydrocarbons, may also be employed. Usually, the high pressure adsorption includes introducing the feedstream or hydrogen-rich gas stream to the feed end of the adsorption bed at a high adsorption pressure. The hydrogen passes through the bed and is discharged from the product end thereof. An adsorption front or fronts are established in the bed with the fronts likewise moving through the bed from the feed end toward the product end thereof. Preferably, the PSA zone 40 can include pressures of 300 - 6,890 KPa.
[0021] The PSA zone 40 can be carried out using any adsorbent material selective for the separation of hydrogen from hydrocarbons in the adsorbent beds. Suitable adsorbents can include one or more crystalline molecular sieves, activated carbons, activated clays, silica gels, activated aluminas, and combinations thereof. Preferably, the adsorbents are one or more of an activated carbon, an alumina, an activated alumina, and a silica gel. An exemplary PSA zone is disclosed in, e.g., US 5,332,492.
[0022] The PSA zone 40 can provide the hydrogen product stream 50 that can be provided to a reaction zone that requires hydrogen, and the tail gas stream 60. The membrane unit 90 forms a feed side 120 and a permeate side 130. The membrane unit 90 may be a hollow fiber membrane, a spiral wound membrane or other suitable type of membrane. The hollow fiber membrane can be made of at least one of a polyimide, cellulose acetate, cellulose triacetate, and polysulfone. Typically, the polyimide may be formed by reacting a dianhydride and a diamine or a dianhydride and a diisocyanate. Such membranes are disclosed in, e.g., US 4,863,492.
[0023] A residue or non-permeate stream 100 can be withdrawn from the feed side 120 of the membrane 90. The residue stream 100 may include nitrogen; one or more carbon oxides, typically carbon monoxide although carbon dioxide may be present instead or additionally; and one or more C1-C6 hydrocarbons. Often, the residue stream 100 is enriched in nitrogen, the one or more carbon oxides, typically carbon monoxide, and the one more C1-C6 hydrocarbons compared with the tail gas stream 60. The residue stream 100 can be provided to a fuel header, provided as a feed to another process such as a steam-methane reforming unit, or optionally recontacted in a vessel to recover liquefied petroleum gases prior to being sent to the fuel header.
[0024] Generally, the compressed tail gas stream 80 contacts the membrane 90 with the smaller hydrogen molecules passing through the membrane 90 and other molecules, such as C1-C6 hydrocarbons, nitrogen, carbon dioxide, and carbon monoxide, are blocked.
Particularly, the membrane 90 can block nitrogen and carbon oxides, such as carbon monoxide.
[0025] The membrane 90 can be operated in such a way that the permeate stream 110 can include no more than 8 mol%, or 20 ppm, by mole, of nitrogen and no more than 0.3 mol%, or 40 ppm, by mole, of carbon monoxide. Generally, the amount of hydrogen by mole percent in the permeate stream 110 is substantially the same as the feed stream 10 and typically the amount of hydrogen composed in the permeate stream 110 is within ±15%, ±5%, ±2%, or ±1%, by mole, of the feed stream 10. Additionally, the permeate stream 110 can include at least 60%, or even at least 95% or 97%, by mole, hydrogen. The permeate stream 110 may recover at least 90%, by mole, of the hydrogen in the compressed tail gas stream 80. Meanwhile, the membrane 90 rejects at least 70%, by mole, carbon monoxide; 76%), by mole, nitrogen; 79%, by mole, methane; 91%, by mole, ethane; and almost 100%), by mole, of the one or more C3+ hydrocarbons in the vapor stream 30. The non-permeate or residue stream 100 may be sent to a product recovery zone 140. The process and system of the invention can achieve an overall hydrogen recovery of at least 98%, by mole, of the hydrogen present in the feed stream 10.
EXAMPLE
[0026] The following example demonstrates the specifics and benefits of this invention:
Net gas Conditions:
30
Figure imgf000008_0001
PSA Product Specifications:
Figure imgf000009_0001
Tail Gas Specifications: The PSA tail gas pressure is 5 psig. The fuel header pressure is set at 85 psig.
Process Schemes: The following process schemes were evaluated:
Scheme #1 : Once-through PSA with the tail gas being compressed to fuel header pressure. The PSA feed pressure is set at 350 psig. The hydrogen recovery is 90%.
Scheme #2: PSA with 72% tail gas recycle. The compressed, recycled tail gas gets mixed with the raw net gas upstream of the net gas compressor. The overall hydrogen recovery is 97%.
Scheme #3 : The PSA tail gas is compressed to 204 psig (instead of 85 psig) and is fed to a membrane unit. The membrane permeate gas is recycled and mixed with the raw net gas upstream of the net gas compressor. The overall hydrogen recovery is 99%.
Scheme #4: The PSA tail gas is compressed to 467 psig (instead of 85 psig) and is fed to a membrane unit. The membrane permeate gas is recycled and mixed with the raw net gas upstream of the net gas compressor. The overall hydrogen recovery is 99%.
Results:
The table below summarizes the four process schemes described above.
Figure imgf000010_0001
[0027] With a once-through PSA operating at 350 psig (Scheme #1), the maximum hydrogen recovery is 90%. A tail gas compressor is required to boost the tail gas pressure to fuel header pressure (85 psig). The total power consumption over the netgas and tail gas compressors is 9,098 hp.
[0028] By employing the tail gas recycle concept (Scheme #2), the overall hydrogen recovery can be increased to 96%-97%, max. In doing so, the total power consumption increases to 12,473 hp (or plus 37% compared to Scheme #1).
[0029] The overall hydrogen recovery and total power consumption of Scheme #2 are dictated by the tail gas impurities that build up in the recycle loop. Compressing the PSA tail gas to at least 204 psig and passing it through a membrane unit (Scheme #3) eliminates this impurity "bottleneck" since the bulk of the impurities get rejected in the membrane's non- permeate (residue) stream. The membrane's permeate stream can be recycled in its entirety and mixed with the raw Oleflex netgas upstream of the netgas compressor. As a result, the overall hydrogen recovery can improve to 99%+ while the total power consumption increases to 11,288 hp (or plus 24% compared to Scheme #1). Looking at the netgas compressor alone, the increase in power consumption compared to Scheme #1 is 16%.
[0030] Scheme #4 shows that by compressing the PSA tail gas to 467 psig instead of 204 psig cuts the number of membrane modules (housings) by more than half while the total power consumption increases by less than 4%. In this process, a membrane non-permeate or residue stream may be recycled to a product recovery section, such as a de-ethanizer for recovery of propane and propylene.
SPECIFIC EMBODIMENTS
[0031] While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.
[0032] A first embodiment of the invention is a process for recovery of hydrogen, comprising A) obtaining a stream comprising hydrogen, hydrocarbons, carbon monoxide, carbon dioxide, oxygen and nitrogen from a reaction zone; B) sending the stream through an adsorption zone to produce a hydrogen stream and a tail gas stream; C) passing at least a portion of the tail gas stream across a feed side of a membrane having the feed side and a permeate side, and being selective for hydrogen over one or more C1-C6 hydrocarbons, carbon monoxide, carbon dioxide, oxygen and nitrogen; D) withdrawing from the permeate side a permeate stream enriched in hydrogen compared with a residue stream withdrawn from the feed side; and E) recycling the permeate stream into the stream from the reaction zone. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the residue stream is sent to a product recovery section of an upstream process for additional recovery of feed and product. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate stream comprises no more than 8 percent, by mole, of nitrogen and no more than 0.3 percent, by mole, of carbon monoxide. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate stream comprises no more than 100 ppm, by mole, of nitrogen and no more than 100 ppm, by mole, of carbon monoxide. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate stream comprises no more than 20 ppm, by mole, of nitrogen and no more than 40 ppm, by mole, of carbon monoxide. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein an amount of hydrogen by mole percent in the permeate stream is substantially the same as a gas stream obtained from the effluent stream and upstream of the waste hydrocarbon stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the amount of hydrogen composition in the permeate stream is within 15%, by mole, of the gas stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the amount of hydrogen composition in the permeate stream is within 2%, by mole, of the gas stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the amount of hydrogen composition in the permeate stream is within 1%, by mole, of the gas stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the membrane comprises a hollow fiber membrane. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the membrane comprises a spiral wound membrane. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate comprises from 60 to 97%, by mole, hydrogen. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the permeate comprises at least 98%, by mole, hydrogen. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the hollow fiber membrane comprises at least one polymer selected from the group consisting of polyimide, cellulose acetate, cellulose triacetate, and polysulfone.
[0033] Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be constmed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.
[0034] In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.
[0035] From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

Claims

1. A process for recovery of hydrogen, comprising:
A) obtaining a stream comprising hydrogen, hydrocarbons, carbon monoxide, carbon dioxide, oxygen and nitrogen from a reaction zone;
B) sending said stream through an adsorption zone to produce a hydrogen stream and a tail gas stream;
C) passing at least a portion of the tail gas stream across a feed side of a membrane having the feed side and a permeate side, and being selective for hydrogen over one or more C1-C6 hydrocarbons, carbon monoxide, carbon dioxide, oxygen and nitrogen;
D) withdrawing from the permeate side a permeate stream enriched in hydrogen compared with a residue stream withdrawn from the feed side; and
E) recycling said permeate stream into said stream from said reaction zone.
2. The process of claim 1 wherein said residue stream is sent to a product recovery section of an upstream process for additional recovery of feed and product.
3. The process according to claim 1, wherein the permeate stream comprises no more than 8 percent, by mole, of nitrogen and no more than 0.3 percent, by mole, of carbon monoxide.
4. The process according to claim 1, wherein the permeate stream comprises no more than 100 ppm, by mole, of nitrogen and no more than 100 ppm, by mole, of carbon monoxide.
5. The process according to claim 1, wherein an amount of hydrogen by mole percent in the permeate stream is substantially the same as a gas stream obtained from the effluent stream and upstream of the waste hydrocarbon stream.
6. The process according to claim 5, wherein the amount of hydrogen composition in the permeate stream is within 15%, by mole, of the gas stream.
7. The process according to claim 5, wherein the amount of hydrogen composition in the permeate stream is within 2%, by mole, of the gas stream.
8. The process according to claim 1, wherein the membrane comprises a hollow fiber membrane or a spiral wound membrane.
9. The process according to claim 1, wherein the permeate comprises at least 98%, by mole, hydrogen.
10. The process according to claim 9, wherein the hollow fiber membrane comprises at least one polymer selected from the group consisting of polyimide, cellulose acetate, cellulose triacetate, and polysulfone.
PCT/US2016/057934 2015-10-26 2016-10-20 Process for maximizing hydrogen recovery WO2017074790A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP16860538.4A EP3368193A4 (en) 2015-10-26 2016-10-20 Process for maximizing hydrogen recovery
US15/796,709 US10710879B2 (en) 2015-10-26 2017-10-27 Process for maximizing hydrogen recovery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562246269P 2015-10-26 2015-10-26
US62/246,269 2015-10-26

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/796,709 Continuation US10710879B2 (en) 2015-10-26 2017-10-27 Process for maximizing hydrogen recovery

Publications (1)

Publication Number Publication Date
WO2017074790A1 true WO2017074790A1 (en) 2017-05-04

Family

ID=58631053

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/057934 WO2017074790A1 (en) 2015-10-26 2016-10-20 Process for maximizing hydrogen recovery

Country Status (3)

Country Link
US (1) US10710879B2 (en)
EP (1) EP3368193A4 (en)
WO (1) WO2017074790A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11383200B2 (en) 2020-09-03 2022-07-12 Saudi Arabian Oil Company Membrane process for H2 recovery from sulfur recovery tail gas stream of sulfur recovery units and process for environmentally greener sales gas
EP4025324A4 (en) * 2019-09-04 2023-09-06 Uop Llc Membrane permeate recycle process for use with pressure swing adsorption processes
EP4025325A4 (en) * 2019-09-04 2023-09-06 Uop Llc Membrane permeate recycle system for use with pressure swing adsorption apparatus
WO2024107639A1 (en) * 2022-11-18 2024-05-23 Uop Llc Process for increasing hydrogen recovery by chilling hydrogen with product co2 stream

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6091681B1 (en) * 2016-03-31 2017-03-08 大阪瓦斯株式会社 Pressure fluctuation adsorption gas production equipment
DE102019007142A1 (en) * 2019-10-14 2021-04-15 Linde Gmbh Method and plant for producing a product gas stream which contains at least carbon monoxide
DE102019007265A1 (en) * 2019-10-18 2021-04-22 Linde Gmbh Process and plant for producing a carbon monoxide rich gas product
EP4168353A1 (en) * 2020-06-18 2023-04-26 Air Products and Chemicals, Inc. Ammonia cracking for green hydrogen

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4863492A (en) 1988-11-28 1989-09-05 Uop Integrated membrane/PSA process and system
US5096468A (en) * 1987-10-19 1992-03-17 W. R. Grace & Co.-Conn. Cellulose acetate butyrate gas separation membranes
US5332492A (en) 1993-06-10 1994-07-26 Uop PSA process for improving the purity of hydrogen gas and recovery of liquefiable hydrocarbons from hydrocarbonaceous effluent streams
US6592650B2 (en) * 2000-05-19 2003-07-15 Membrane Technology And Research, Inc. Gas separation using organic-vapor-resistant membranes and PSA
WO2012158680A1 (en) * 2011-05-18 2012-11-22 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for the production of hydrogen and carbon dioxide
EP2733115A1 (en) * 2012-11-14 2014-05-21 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for recovering hydrogen and carbon dioxide
US20150086472A1 (en) 2013-09-23 2015-03-26 Uop, Llc Process for catalytic reforming

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5435836A (en) * 1993-12-23 1995-07-25 Air Products And Chemicals, Inc. Hydrogen recovery by adsorbent membranes
US6592749B1 (en) * 1999-03-19 2003-07-15 Membrane Technology And Research, Inc. Hydrogen/hydrocarbon separation process, including PSA and membranes
WO2008123337A1 (en) * 2007-03-29 2008-10-16 Nippon Oil Corporation Method of hydrogen production and carbon dioxide recovery and apparatus therefor
US20100126180A1 (en) * 2007-07-25 2010-05-27 Jonathan Alec Forsyth Separation of carbon dioxide and hydrogen
US20110085966A1 (en) * 2009-10-14 2011-04-14 Air Liquide Process & Construction, Inc. High Hydrogen Recovery From Residual Fuels And Biomass

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5096468A (en) * 1987-10-19 1992-03-17 W. R. Grace & Co.-Conn. Cellulose acetate butyrate gas separation membranes
US4863492A (en) 1988-11-28 1989-09-05 Uop Integrated membrane/PSA process and system
US5332492A (en) 1993-06-10 1994-07-26 Uop PSA process for improving the purity of hydrogen gas and recovery of liquefiable hydrocarbons from hydrocarbonaceous effluent streams
US6592650B2 (en) * 2000-05-19 2003-07-15 Membrane Technology And Research, Inc. Gas separation using organic-vapor-resistant membranes and PSA
WO2012158680A1 (en) * 2011-05-18 2012-11-22 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for the production of hydrogen and carbon dioxide
EP2733115A1 (en) * 2012-11-14 2014-05-21 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for recovering hydrogen and carbon dioxide
US20150086472A1 (en) 2013-09-23 2015-03-26 Uop, Llc Process for catalytic reforming

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3368193A4

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4025324A4 (en) * 2019-09-04 2023-09-06 Uop Llc Membrane permeate recycle process for use with pressure swing adsorption processes
EP4025325A4 (en) * 2019-09-04 2023-09-06 Uop Llc Membrane permeate recycle system for use with pressure swing adsorption apparatus
US11383200B2 (en) 2020-09-03 2022-07-12 Saudi Arabian Oil Company Membrane process for H2 recovery from sulfur recovery tail gas stream of sulfur recovery units and process for environmentally greener sales gas
WO2024107639A1 (en) * 2022-11-18 2024-05-23 Uop Llc Process for increasing hydrogen recovery by chilling hydrogen with product co2 stream

Also Published As

Publication number Publication date
US10710879B2 (en) 2020-07-14
US20180111831A1 (en) 2018-04-26
EP3368193A1 (en) 2018-09-05
EP3368193A4 (en) 2019-06-26

Similar Documents

Publication Publication Date Title
US10710879B2 (en) Process for maximizing hydrogen recovery
US9517933B2 (en) Process for catalytic reforming
US6589303B1 (en) Hydrogen production by process including membrane gas separation
CA1119201A (en) Process for methanol production
CA2332704C (en) Very large-scale pressure swing adsorption processes
JP5011127B2 (en) Management of hydrogen in hydrogen-containing streams from hydrogen sources
CZ282153B6 (en) Process for preparing hydrogen-enriched gas
AU2018341260B2 (en) Methods and apparatus for production of hydrogen
Wiessner Basics and industrial applications of pressure swing adsorption (PSA), the modern way to separate gas
US9630138B2 (en) Pressure swing adsorption processes and systems for recovery of hydrogen and C2+ hydrocarbons
WO2017064255A1 (en) Process for the oxidative coupling of methane
US6667409B2 (en) Process and apparatus for integrating an alkene derivative process with an ethylene process
WO2011068642A2 (en) Use of calcium exchanged x-type zeolite for improvement of refinery off-gas pressure swing adsorption
CZ133197A3 (en) Process for preparing partial oxidation products derived from ethylene
US12036505B2 (en) Three-product pressure swing adsorption system
US20240226798A1 (en) Treatment of biogas by pressure swing adsorption
RU2779804C2 (en) Methods and devices for hydrogen production
US9365783B2 (en) Process and apparatus for producing synthesis gas
WO2024145328A1 (en) Treatment of biogas by pressure swing adsorption
US20140058153A1 (en) Carbon dioxide removal and methane conversion process using a supersonic flow reactor
MXPA06004866A (en) Method for converting hydrogenous gaseous flows arising from chemical reactor units using hydrogen

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16860538

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016860538

Country of ref document: EP