US20050257566A1 - Method and unit for the production of hydrogen from a hydrogen-rich feed gas - Google Patents

Method and unit for the production of hydrogen from a hydrogen-rich feed gas Download PDF

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US20050257566A1
US20050257566A1 US10/504,810 US50481005A US2005257566A1 US 20050257566 A1 US20050257566 A1 US 20050257566A1 US 50481005 A US50481005 A US 50481005A US 2005257566 A1 US2005257566 A1 US 2005257566A1
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adsorber
hydrogen
adsorption
recycled
pressure
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Guillaume De Sousa
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA a Directoire et Conseil de Surveillance pour lEtude et lExploitation des Procedes Georges Claude
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Assigned to L'AIR LIQUIDE, SOCIETE ANONYME A DIRECTOIRE ET CONSEIL DE SURVEILLANCE POUR L'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE reassignment L'AIR LIQUIDE, SOCIETE ANONYME A DIRECTOIRE ET CONSEIL DE SURVEILLANCE POUR L'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DE SOUZA, GUILLAUME
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    • 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
    • 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
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
    • B01D2257/108—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40001—Methods relating to additional, e.g. intermediate, treatment of process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40013—Pressurization
    • B01D2259/40015—Pressurization with two sub-steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40028—Depressurization
    • B01D2259/40033—Depressurization with more than three sub-steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40035—Equalization
    • B01D2259/40039—Equalization with three sub-steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40043—Purging
    • B01D2259/4005—Nature of purge gas
    • B01D2259/40052—Recycled product or process gas
    • B01D2259/40054—Recycled product or process gas treated before its reuse
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/406—Further details for adsorption processes and devices using more than four beds
    • B01D2259/4062—Further details for adsorption processes and devices using more than four beds using six beds
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention concerns a method for producing hydrogen from a hydrogen-rich feed mixture.
  • an adsorption treatment unit of the PSA (Pressure Swing Adsorption) type employs a method in which at least one adsorber is used which follows a cycle where there are, successively, an adsorption phase substantially at a high cycle pressure and a regeneration phase comprising at least one depressurization step to a low cycle pressure and a repressurization step to the high cycle pressure.
  • a conventional PSA unit has the ability to produce a flow of substantially pure hydrogen (with a hydrogen content above 95%) at a high pressure, but exhibits the defect of being limited to a hydrogen yield of around 90%, even in the case of a feed mixture that is very rich in hydrogen (for example with a hydrogen content between 90 and 98%).
  • the hydrogen yield reached by a PSA unit is generally of the order of 90%. In order to exceed such a yield it is necessary to bring the hydrogen content in waste gases discharged from the PSA unit to below 20%, which at the present time only seems achievable by the use of selective adsorbents that are better suited to the feed gas to be treated and that are therefore costly.
  • an improved hydrogen recovery method is known from document EP-A-1 023 934 that consists of recycling, within a PSA unit, a variable part of the waste gases coming from the PSA unit, into the feed gas. More precisely, in this document, the regeneration phase commences with a first cocurrent depressurization substep by completely balancing the pressure with an adsorber during repressurization, followed by a second cocurrent depressurization substep during which the gas coming from the adsorber in the second cocurrent depressurization substep is used as a gas for eluting the adsorbent material of another adsorber. The flow leaving this last adsorber during elution is then compressed to the high cycle pressure in order to be mixed with the gas feeding the PSA unit.
  • Such an arrangement for the operating cycle of a PSA unit ensures recycling of part of the waste gases that are hydrogen-rich to a varying degree. However, such recycling can prove to be detrimental to the productivity of the PSA unit.
  • the object of the present invention is to provide a method of the type described above, that improves the recovery of hydrogen from a given feed gas, while keeping constant, or even improving, the productivity of the PSA unit implementing this method and/or while reducing the overall investment in this unit.
  • the invention concerns a method for producing hydrogen from a main hydrogen-rich feed mixture in which N adsorbers are used, with N being greater than or equal to one, each following with a time lag a cycle where there are, successively, an adsorption phase substantially at a high cycle pressure and a regeneration phase, this regeneration phase comprising a depressurization step to a low cycle pressure including a cocurrent depressurization substep, an elution step at the low cycle pressure, and a repressurization step to the high cycle pressure, wherein all of the flow or flows leaving the adsorber or adsorbers during cocurrent depressurization are sent to the adsorber or adsorbers during the elution step, and wherein at least part of the flow or flows leaving the adsorber or adsorbers in the regeneration phase is or are recycled, by compressing said recycled part to the high cycle pressure and by feeding the adsorber or adsorbers in the adsorption phase with said recycled part.
  • the invention also concerns a method for the production of hydrogen from a main hydrogen-rich feed mixture, wherein N adsorbers are used, with N being greater than or equal to one, each following with a time lag a cycle where there are, successively, an adsorption phase substantially at a high cycle pressure and a regeneration phase, this regeneration phase comprising a depressurization substep to a low cycle pressure including a cocurrent depressurization substep, an elution step at the low cycle pressure, and a repressurization step to the high cycle pressure wherein, during the depressurization step, a partial balancing of the pressures is carried out between at least one adsorber at the start of cocurrent depressurization and at least one adsorber in the repressurization step, until the pressure of said adsorber at the start of cocurrent depressurization is brought to a partial balancing pressure, strictly below the high cycle pressure, and the flow or flows leaving the adsorber or adsorbers in cocurrent depressurization of which the
  • the invention also concerns a unit for producing hydrogen from a main hydrogen-rich mixture, which comprises N adsorbers, with N being greater than or equal to one, each following with a time lag a cycle where there are, successively, an adsorption phase substantially at a high cycle pressure and a regeneration phase, this regeneration phase comprising a depressurization step to a low cycle pressure, including a countercurrent depressurization substep, an elution step at the low cycle pressure, and a repressurization step to the high cycle pressure, said unit being associated with a fuel gas network, this unit including a line for recycling at least one of the flows leaving the adsorber or adsorbers in the regeneration phase, provided with a recycling compressor, and a branch adapted so as to convey part of the fuel gas from the fuel gas network to said recycling line.
  • FIG. 1 is a schematic view of a PSA unit
  • FIG. 2 is a diagram of an operating cycle of the unit of FIG. 1 according to one aspect of the invention.
  • FIG. 3 is a table of data corresponding to the performance of units for producing hydrogen according to the prior art and according to the invention.
  • FIG. 4 is an operational diagram similar to that of FIG. 2 , of a variant of the method according to the invention.
  • FIG. 5 is a diagram illustrating the influence of a parameter of the cycle of FIG. 4 on the energy consumption and productivity of a PSA unit for performing the cycle of FIG. 4 ;
  • FIG. 6 is a schematic view of an installation for producing hydrogen, including a unit for performing a cycle according to the invention
  • FIG. 7 is a schematic view of an installation for the combined production of hydrogen and carbon monoxide, including a unit for performing a cycle according to the invention
  • FIG. 8 is a schematic view of a hydrocarbon hydrodesulfuration installation, including a unit for the production of hydrogen for performing a cycle according to the invention
  • FIG. 9 is a similar view to FIG. 1 , of a variant of the unit according to the invention.
  • FIG. 10 is a diagram of the operating cycle of the unit of FIG. 9 with conveyance of a secondary low pressure feed.
  • a unit 1 for producing hydrogen from a hydrogen-rich gas, for example installed in an oil refinery.
  • this feed gas contains 75% by volume of hydrogen and impurities, namely 11% methane, 7% ethane, 4% propane, 2.9% butane and 0.1% hydrogen sulfide (H 2 S).
  • H 2 S hydrogen sulfide
  • Such a feed gas comes from a catalytic reforming unit and is available at a pressure of around 26 bar.
  • types of this gas will be expanded on later on, in particular with regard to FIGS. 6 to 8 .
  • Unit 1 is adapted so as to produce, from the feed gas led through a line 2 , a flow of high-purity hydrogen (with a hydrogen content above 99% by volume) via an output line 3 , while discharging therefrom a flow of waste gas through a discharge line 4 designed to be connected to an evacuation network at around 6 bar, at present installed in oil refineries.
  • Unit 1 includes an adsorption purification apparatus 5 , provided with a recycling line 6 .
  • This recycling line is provided, from upstream to downstream, with a mixing tank 7 and a compression apparatus 8 , for example a compressor.
  • the unit 1 includes an optional compressor 9 , drawn in dotted lines, on the waste line 4 .
  • This compressor 9 is typically dedicated to bringing the flow through the line 4 to the pressure of around 6 bar in the evacuation network, if this is at an insufficient pressure.
  • One of the features of the invention is to dispense with this compressor 9 , with compressor 8 in preference, as will be explained below.
  • the purification apparatus 5 comprises six adsorbers R 1 to R 6 , each containing an adsorbent material adapted so as to fix impurities by adsorption (hydrocarbons and hydrogen sulfide) contained in the feed mixture.
  • adsorbent materials such as activated carbons, silica gels and/or molecular sieves.
  • the purification apparatus 5 is of the PSA type. It comprises to this end lines, valves and control means, not shown, adapted so as to cause each adsorber R 1 to R 6 to follow a cycle of period T, which consists of six phase times of substantially the same duration, and of which a first example is shown in FIG. 2 .
  • a cycle of period T which consists of six phase times of substantially the same duration, and of which a first example is shown in FIG. 2 .
  • the operation of the adsorber R 5 is deduced from this by a time lag T/6, that of the adsorber R 4 by a time lag of 2T/6 and so on until that of the adsorber R 1 obtained by a time lag of 5T/6.
  • the stream enters the adsorber through the entry end of this adsorber; if the arrow, pointing upward, is situated above the line indicating the pressure, the stream leaves the adsorber through the outlet end of the adsorber, the inlet and outlet ends being respectively those of the gas to be treated and the gas withdrawn as an output; when an arrow is in the direction of decreasing ordinates (toward the bottom of the diagram), the stream is said to be countercurrent in the adsorber.
  • the stream leaves the adsorber through the inlet end of this adsorber; if the arrow pointing downward is situated above the line indicating the pressure, the stream enters the adsorber through the outlet end of this adsorber, the inlet and outlet ends being still those of the gas to be treated and the gas withdrawn as an output.
  • the inlet end of the adsorbers is their lower end.
  • This elution step comprises:
  • the line 6 receives a gas richer in hydrogen than the gas conveyed to the waste line 4 , which amounts to only recycling the flows, coming in countercurrent from the adsorbers in the regeneration phase that are richest in hydrogen, the impurities having been mainly desorbed at the end of countercurrent depressurization and at the start of elution.
  • the duration of the intervals [t2;t3] and [t4;5T/6] can be modified according to the desired gas volume entering the recycling line 6 .
  • t3 can be chosen equal to t2, which amounts to only having available the flow leaving the adsorber in the elution substep toward recycling in order to feed line 6 .
  • t4 can be chosen equal to 4T/6 which makes it possible to recycle to line 6 all the flows coming from the adsorbers in the elution step.
  • the gas from line 6 has been homogenized in the mixing tank 7 and compressed from the low pressure PB to the high pressure PH of the cycle by the compressor 8 , it forms the gas feeding the adsorber in the second treatment step (from T/6 to 2T/6 as described above).
  • the adsorber also receives the flow coming from the adsorber at the start of the cocurrent depressurization substep, until the pressure of the adsorber reaches the total balancing pressure PE which has a value for example of around (PH+PB)/2.
  • the secondary feed gas conveyed through the line 6 is more depleted in hydrogen than the main feed gas conveyed through the line 2 , and these two feed gases are asymmetrical in terms of the hydrogen content, when successively feeding each adsorber in the adsorption phase.
  • This asymmetry makes it possible to achieve higher productivity than that of a PSA apparatus with a single feed flow.
  • this gain is even greater as there is an increase in the recycled flow, coming from adsorbers of the apparatus 5 , on account of the fact that this asymmetry is increased by lowering the hydrogen content of the second feed gas.
  • FIG. 3 Column I of the table of FIG. 3 corresponds to a standard PSA unit, not shown, with six adsorbers that follow a known cycle without recycling (this PSA unit does not therefore include a recycling compressor like the compressor 8 for unit 1 of FIG. 1 ), which is awkward to put into operation by reason of its complexity although recognized for its good performance.
  • This is the case, for example, for a cycle commonly called “613 cycle”, with an adsorber in the adsorption phase and three total pressure balancing operations between adsorbers during cocurrent depressurization and adsorbers during repressurization.
  • a compressor is necessary placed at the outlet from the waste line, such as the compressor 9 for unit 1 .
  • Column II corresponds to unit 1 of FIG. 1 which follows PSA cycles for which the recycling compressor 8 returns a recycling gas at a high pressure PH that is mixed with the main feed of line 2 before being conveyed to the adsorber.
  • These cycles called 613R and 612R (“R” for recycling) correspond to a cycle on six adsorbers with an adsorber during the adsorption phase and with respectively three and two total pressure balancing operations between adsorbers during cocurrent depressurization and adsorbers during repressurization.
  • FIG. 4 A variant of the operating cycle of the PSA unit 5 of FIG. 1 is shown in FIG. 4 .
  • P partial has a value (PH+PB)/2, that is to say the value PE of the cycle of FIG. 2 .
  • P partial PH
  • the cycle of FIG. 4 makes it possible to have a greater eluting power available than in the cycle of FIG. 2 . Indeed, for a ratio r strictly less than 1, the volume of the flows coming from the adsorbers during cocurrent depressurization and used for eluting the adsorber in the elution step is greater than that of flows of the same nature of the cycle of FIG. 2 . Accordingly, the elution step is reinforced, which promotes regeneration of the adsorber and therefore the productivity of the PSA. Moreover, this gain in productivity compensates to a large extent for the increase in the quantity of hydrogen recycled through line 6 , there being no deterioration in energy consumption.
  • column III of the table of FIG. 3 gives the performance of the PSA unit 5 of FIG. 1 which follows:
  • FIG. 5 shows the influence of the ratio r on the energy consumption and productivity of the PSA unit 5 , with a constant yield and constant hydrogen purity of the output flow. It will be noted that the nearer the ratio r approaches 0, the greater the increase in productivity of the PSA unit, without any significant increase in energy consumption (less than 5%). This is confirmed both by the examples of column II and column III of FIG. 3 .
  • FIGS. 6 to 8 show several examples of installations incorporating a hydrogen production unit similar to the unit of FIG. 1 . These different applications will be described below as non-limiting examples of fields for implementing the method according to the invention.
  • FIG. 6 shows an installation 10 for producing hydrogen from a feed gas consisting of natural gas GN.
  • the installation includes a line 12 for treating natural gas, the outlet from which being connected to a PSA unit 14 for producing hydrogen.
  • This unit 14 is similar to unit 1 of FIG. 1 : firstly it includes the same elements denoted by the same references, except that its adsorption purification apparatus has ten absorbers and not six and, secondly, it operates substantially in the same way, except that it follows a cycle with ten phase periods, which will be detailed subsequently.
  • the treatment line 12 has, from upstream to downstream:
  • unit 24 can be replaced by a unit with selective membranes which promotes the permeation of carbon dioxide with respect to hydrogen.
  • the adsorption phase of the operating cycle of the PSA unit 14 extends over three phase periods and includes successively a first step for treating the synthesis gas leaving the line 12 , a second step for treating the recycling gas leaving the recycling line 6 of the unit 14 , and a third optional step for treating part of the prereformed natural gas withdrawn at the outlet from the prereforming unit 18 .
  • the hydrogen content of these three successive feed gases is decreasing, whereas the carbon dioxide content of these three gases is on the other hand increasing. A dissymetry effect will thus be found here, in terms of hydrogen content, for the feed gases of the PSA unit, with the previously mentioned advantages on hydrogen production.
  • the regeneration phase of the cycle of PSA unit 14 extends over seven phase periods and comprises successively:
  • the extent of its calorific value is arranged so as not to exceed the requirements of the burners.
  • the cycle of the unit 14 makes it possible to optimize the distribution of flows leaving the unit 14 in the regeneration phase: part of these flows, which forms the waste gas depleted in hydrogen is put to use to the best extent in the burners 26 , and the remaining part, that is richest in hydrogen, is recycled to feed the PSA unit of which the performance (hydrogen yield, productivity, etc.) is increased, as previously explained.
  • FIG. 7 shows an installation 40 for the combined production of hydrogen and carbon monoxide from a feed gas consisting of natural gas GN.
  • the installation includes a line 42 for treating natural gas, downstream from which are connected simultaneously a cryogenic unit 44 for producing carbon monoxide (CO) and a PSA unit 46 for producing hydrogen of which the cycle does not include pressure balancing.
  • This unit 46 is identical to the unit 14 of the installation 10 and will not be detailed above.
  • the treatment line 42 includes, from upstream to downstream:
  • a first outlet 58 from the drying unit 56 is connected to the cryogenic unit 44 , which includes a return line 60 to the drying unit.
  • a second outlet 62 from the drying unit 56 is connected to the PSA unit 46 so as to form, with part of the flow from the return line 60 , the first feed mixture used by this unit.
  • the second feed mixture is withdrawn from the recycling line 6 of the unit 46 .
  • the third optional feed mixture is formed in the same way as for installation 10 of FIG. 6 , namely by part of the natural prereformed gas, withdrawn at the outlet from the prereforming unit 50 .
  • the installation 40 ensures a good hydrogen yield (for the same reasons as those set out with respect to FIG. 6 ) and, at the same time, a good carbon monoxide yield, accompanied by production of waste gas at the outlet from the PSA unit 46 rich in methane, that can be employed as a fuel gas for the burners for the reforming unit 52 .
  • the waste gas can be partly recycled to the feed flow of the reforming unit 52 while profiting from the compressor for recycling carbon dioxide.
  • FIG. 8 shows an installation 80 for reforming heavy hydrocarbons HCX, for example crude oil, the installation 80 forming part of an oil refinery.
  • the object of this installation is to hydrogenate and desulfurize a crude oil feed so as to produce a ready-to-use petroleum fuel, for example diesel fuel.
  • the hydrogen production method proposed with respect to FIGS. 1, 2 and 4 is here directly applicable to the treatment of these heavy hydrocarbon feeds, that are more or less rich in hydrogen, the hydrogen yield of the method according to the invention being able to exceed the limitations in yield of standard PSA units.
  • the installation 80 includes to this end:
  • the operating cycle of the PSA unit 96 is very close to that of the unit 14 of FIG. 6 .
  • the adsorption phase includes successively a first step for treating a first feed gas leaving the line 94 , a second step for treating a second feed gas formed of a compressed top-up gas, for example coming from a catalytic reforming unit, not shown, and a third step for treating a third feed gas leaving the recycling line 6 .
  • the regeneration phase without pressure balancing, is substantially identical to that of the cycle of the unit 14 of FIG. 6 , the discharge flow from the line 4 (formed of hydrogen sulfide, hydrocarbons and traces of hydrogen) being for example conveyed to a fuel gas network, that can be profitably used within the refinery.
  • this “closed loop cycle on the reactor 82 ” operates with a flow rate of 40,000 Nm 3 /h of a flow of 95% pure hydrogen by volume in the main feed line 94 of the PSA unit, and with a flow rate of 8,000 Nm 3 /h of top-up gas with a hydrogen content equal to around 75% by volume, for a recycling gas in 6 with a hydrogen content equal to around 45% by volume.
  • FIG. 9 shows a unit 120 for producing hydrogen, a variant of the unit 1 of FIG. 1 . Elements common to these two units carry the same references and will not be detailed again.
  • the unit 120 is associated with a high pressure source of synthesis gas and with a fuel gas network 124 , provided at the downstream end of burners 126 .
  • the high pressure source is for example a catalytic reformer and the network 124 is the so-called fuel gas network that collects, typically at a pressure of around 6 bar, waste gases discharged from reforming and chemical treatment units currently installed in the refinery, and from which the burners 126 produce heat, profitably utilized in the refinery.
  • the flow of synthesis gas leaving the catalytic reforming unit 122 is at a pressure of 26 bar, has a hydrogen content of 75% by volume and possesses a flow rate of the order of 1,100 Nm 3 /h.
  • the fuel gas network 124 at around 6 bar has a hydrogen content of between 30 and 60% for a flow rate of around 4,000 Nm 3 /h.
  • An example of the composition of the flow of network 124 is: 50.3% hydrogen, 14.5% methane, 25.2% ethane, 7.8% butane, 2.1% propane and 0.1% hydrogen sulfide.
  • the unit 120 is fed with a charge from the source 122 through a line 128 delivering, in our example, a flow of around 1,100 Nm 3 /h. It is also connected to the medium pressure network 124 : firstly, part of the fuel gas is conveyed, via a branch 130 , to the recycling line 6 , the upstream part of the line 6 (namely the part collecting the recycled flows coming from the adsorbers in the regeneration phase) being referenced 6 A; and secondly, the outlet from the waste line 4 is connected by a discharge line 132 to the fuel gas network, downstream of the branch 130 .
  • the operating cycle of the PSA unit 120 is shown in FIG. 12 , with the same notational conventions as for the cycle of FIG. 4 , its low pressure PB having a value of around 6 bar. It is identical to the cycle of FIG. 4 , except for the connection of the branch 130 to the recycling line 6 .
  • the point of connection of the branch 130 to the line 6 is, as shown in FIG. 12 , situated upstream of the mixing tank 7 .
  • a high-pressure source of fuel gas can be directly mixed with the delivery from the compressor 8 .
  • the yield of this unit 120 is explained by the profitable use of hydrogen by the fuel network 124 , the calculated yield in the table being the ratio between the quantity of hydrogen produced in 3 and the quantity of hydrogen introduced in 2 .
  • the overall hydrogen yield (quantity of hydrogen added/quantity of hydrogen withdrawn as an output) has a value of 89%.
  • the material balance in % by volume) of the installation of FIG.
  • one or more buffer tanks can be provided so as to permit temporary storage and deferred use of the flow leaving the adsorber or adsorbers.

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  • Separation Of Gases By Adsorption (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
US10/504,810 2002-02-15 2003-02-07 Method and unit for the production of hydrogen from a hydrogen-rich feed gas Abandoned US20050257566A1 (en)

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FR0201914A FR2836060B1 (fr) 2002-02-15 2002-02-15 Procede et unite de production d'hydrogene a partir d'un gaz de charge riche en hydrogene
FR02/01914 2002-02-15
PCT/FR2003/000400 WO2003070358A1 (fr) 2002-02-15 2003-02-07 Procédé et unité de production d'hydrogène a partir d'un gaz de charge riche en hydrogène

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AT (1) ATE463297T1 (ja)
AU (1) AU2003226868A1 (ja)
BR (1) BR0307713A (ja)
CA (1) CA2476001A1 (ja)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060044624A1 (en) * 2004-08-26 2006-03-02 Xerox Corporation Networked scanning
WO2011067326A1 (en) 2009-12-03 2011-06-09 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for the production of hydrogen combined with carbon dioxide capture
US9358495B2 (en) 2011-05-16 2016-06-07 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method of purification by means of adsorption with regeneration using a gas containing an undesired component in the purified gas

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2892322A1 (fr) * 2005-10-24 2007-04-27 Air Liquide Procede psa h2 avec elution additionnelle
FR2909570A1 (fr) * 2006-12-08 2008-06-13 Air Liquide Procede de production d'hydrogene a partir d'un gaz riche en hydrogene
CN105268282A (zh) * 2015-09-18 2016-01-27 北京环宇京辉京城气体科技有限公司 一种低温变压吸附制备超纯氢的方法
FR3046550B1 (fr) * 2016-01-13 2020-02-21 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Psa h2 avec modification du flux gazeux d'alimentation
WO2020239384A1 (en) * 2019-05-31 2020-12-03 Haldor Topsøe A/S Hydrogen purification
US11773873B2 (en) * 2021-03-15 2023-10-03 Air Products And Chemicals, Inc. Process and apparatus for compressing hydrogen gas in a centrifugal compressor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4077780A (en) * 1976-10-20 1978-03-07 Union Carbide Corporation Recovery of hydrogen and nitrogen from ammonia plant purge gas
US4840647A (en) * 1985-07-08 1989-06-20 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for treating a gaseous mixture by adsorption
US5254154A (en) * 1991-10-17 1993-10-19 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for the purification of a gas by adsorption
US6315818B1 (en) * 1999-01-29 2001-11-13 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for the purification of a gas by adsorption
US20050139069A1 (en) * 2002-02-15 2005-06-30 Denis Cieutat Method for treatment of a gaseous mixture comprising hydrogen and hydrogen sulphide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02281096A (ja) * 1989-04-24 1990-11-16 Seibu Gas Kk 富メタン混合ガスの炭酸ガス及び水分を除去する装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4077780A (en) * 1976-10-20 1978-03-07 Union Carbide Corporation Recovery of hydrogen and nitrogen from ammonia plant purge gas
US4840647A (en) * 1985-07-08 1989-06-20 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for treating a gaseous mixture by adsorption
US5254154A (en) * 1991-10-17 1993-10-19 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for the purification of a gas by adsorption
US6315818B1 (en) * 1999-01-29 2001-11-13 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for the purification of a gas by adsorption
US20050139069A1 (en) * 2002-02-15 2005-06-30 Denis Cieutat Method for treatment of a gaseous mixture comprising hydrogen and hydrogen sulphide

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060044624A1 (en) * 2004-08-26 2006-03-02 Xerox Corporation Networked scanning
WO2011067326A1 (en) 2009-12-03 2011-06-09 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for the production of hydrogen combined with carbon dioxide capture
FR2953505A1 (fr) * 2009-12-03 2011-06-10 Air Liquide Procede pour une production d'hydrogene combinee a une capture de dioxyde de carbone
US20120241678A1 (en) * 2009-12-03 2012-09-27 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for the production of hydrogen combined with carbon dioxide capture
US8852456B2 (en) * 2009-12-03 2014-10-07 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for the production of hydrogen combined with carbon dioxide capture
US9358495B2 (en) 2011-05-16 2016-06-07 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method of purification by means of adsorption with regeneration using a gas containing an undesired component in the purified gas

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CA2476001A1 (fr) 2003-08-28
JP2005517622A (ja) 2005-06-16
MXPA04007823A (es) 2004-10-15
EP2095862A1 (fr) 2009-09-02
FR2836060B1 (fr) 2004-11-19
ATE463297T1 (de) 2010-04-15
EP1480732B1 (fr) 2010-04-07
CN1633323A (zh) 2005-06-29
BR0307713A (pt) 2005-01-25
DE60332008D1 (de) 2010-05-20
AU2003226868A1 (en) 2003-09-09
CN1315564C (zh) 2007-05-16
FR2836060A1 (fr) 2003-08-22
WO2003070358A1 (fr) 2003-08-28
EP1480732A1 (fr) 2004-12-01
CN101024491A (zh) 2007-08-29
JP4316386B2 (ja) 2009-08-19

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