EP0358714A1 - Procede d'enrichissement d'helium - Google Patents

Procede d'enrichissement d'helium

Info

Publication number
EP0358714A1
EP0358714A1 EP88904951A EP88904951A EP0358714A1 EP 0358714 A1 EP0358714 A1 EP 0358714A1 EP 88904951 A EP88904951 A EP 88904951A EP 88904951 A EP88904951 A EP 88904951A EP 0358714 A1 EP0358714 A1 EP 0358714A1
Authority
EP
European Patent Office
Prior art keywords
pressure
helium
adsorber
relief
build
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP88904951A
Other languages
German (de)
English (en)
Inventor
Karl Knoblauch
Erwin Pilarczyk
Klaus Giessler
Hans Bukowski
Joseph S. D'amico
Herbert Reinhold
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bergwerksverband GmbH
Original Assignee
Bergwerksverband GmbH
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 Bergwerksverband GmbH filed Critical Bergwerksverband GmbH
Publication of EP0358714A1 publication Critical patent/EP0358714A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • B01D53/0476—Vacuum pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B23/00—Noble gases; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/116—Molecular sieves other than zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/308—Pore size
    • 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
    • B01D2256/18—Noble gases
    • 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
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • 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
    • B01D2259/4003—Depressurization 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
    • B01D2259/40035—Equalization
    • B01D2259/40041—Equalization 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
    • B01D2259/40058—Number of sequence steps, including sub-steps, per cycle
    • B01D2259/40071—Nine
    • 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
    • B01D2259/404—Further details for adsorption processes and devices using four beds
    • 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
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • 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
    • 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
    • Y02P20/156—Methane [CH4]

Definitions

  • the invention relates to a process for helium enrichment after a pressure-swing adsorption process from gas mixtures which contain helium, nitrogen and methane and optionally further gases and are passed through carbon molecular sieves which adsorb nitrogen and methane and optionally the further gases, the gas mixture cyclically four adsorbers connected in parallel are given, each of which successively goes through a pressure build-up phase, an adsorption phase and a pressure relief phase, and pressure build-up and pressure relief take place partly by pressure equalization with another adsorber.
  • Such a pressure swing adsorption process is known from EP 00 02 695, which is used for the purification of helium from a starting gas mixture with helium and essentially nitrogen, argon and oxygen and smaller proportions of carbon dioxide and methane, and in which using carbon molecular sieves helium with a purity of over 99.9 vol .-. ⁇ is obtained.
  • the starting gas mixture already contains 50-95 vol .-% helium.
  • helium cannot be enriched from gas mixtures with up to 10% helium because the procedure and the combination of the process steps are not suitable for this.
  • Helium is increasingly required for various applications, e.g. B.
  • helium is required which has a high purity.
  • several process stages are required for gas mixtures which have only low helium contents, in order first to enrich the gas mixture with helium and then finally to obtain helium with high purity from the gas mixture enriched with helium.
  • Helium is mainly enriched and extracted from helium-containing natural gases.
  • the main constituents of helium-containing natural gases include methane and nitrogen and up to 10% by volume of helium in addition to smaller amounts of various higher hydrocarbons and carbon dioxide.
  • the helium-containing natural gas is cooled in a refrigeration system to approx. -150 ° C, whereby mainly the hydrocarbons are condensed out.
  • the gas mixture produced in this way contains, apart from small amounts of other gases, more than 50 vol. Helium and nitrogen. »In some cases, this crude helium is further processed on-site to high-purity helium, namely by a process combination in which a pressure ⁇ interchangeable adsorption system interacts with a second refrigeration system.
  • the crude helium is also commercially available as an intermediate product and in these cases is further processed to pure helium elsewhere.
  • the invention has for its object to achieve the enrichment of helium from natural gases with low helium contents to crude helium with a higher helium content than 50 .. solely by pressure swing adsorption and without intermediate enrichment in refrigeration systems with a high yield.
  • the pressure build-up phase comprises three steps:
  • the pressure-relief phase comprises four steps:
  • the pressure equalization takes place in two stages and the first stage from the outlet of a first adsorber, which load step (from P _. to P.) to the output of a second adsorber, which carries out the second pressure build-up step (from P, to P.) and the second step from the output of the first adsorber, which carries out the second relief step (from P. on P,), to the input of a third adsorber, which carries out the first pressure build-up step (from P to P,), and
  • the 3rd relief step and the 4th relief step take place in countercurrent, a low-helium exhaust gas being produced, and the 3rd pressure build-up step is carried out with product gas.
  • Carbon molecular sieves with an average adsorption pore diameter between 0.1 and 0.4 nm, preferably 0.3 and 0.4 nm, are used as adsorbents for the process according to the invention, because they can separate nitrogen and methane from helium extremely effectively , so that, surprisingly, crude helium with a comparatively high helium content of over 50% can already be produced in a single stage, an unexpectedly high helium yield of over 90% being achieved when the proposed teaching is used. According to the proposed enrichment process, this can be achieved by using the pressure swing technique alone from starting gas mixtures with a comparatively low helium content of about 2 to 8% without the need for a refrigeration system. h_, with very low energy consumption.
  • the adsorbers are preceded by prefilters which are filled with activated carbon in order to avoid higher hydrocarbons and possibly further impurities. separate from the natural gas beforehand. In this way it is avoided that these impurities get into the carbon molecular sieves and impair their ability to adsorb and regenerate.
  • the following pressure values are assigned to the individual pressure stages:
  • the total cycle time can be between 450 and 3600 s, preferably 720 s.
  • the pressure relief phase comprises the following time intervals with a total cycle time of 720 s:
  • the pressure build-up phase comprises the following time intervals with a total cycle time of 720 s.
  • the time interval for product gas extraction is expediently 180 s with a total cycle time of 720 s.
  • the method according to the invention is particularly suitable for An ⁇ enrichment of helium from feed gases, the helium content 10 vol .- ⁇ . Or less, preferably 2 to 8 vol ?. is, the helium content in the recovered crude helium up to 95 V0I.- .0 can be.
  • the method according to the invention is preferably used in the helium enrichment from natural gases which, after a prior separation of higher hydrocarbons and trace impurities, eg. B. in known adsorption prefilters, the following composition (data in Vol .-. ⁇ ) _
  • FIG. 1 shows a single-stage system with four parallel adsorbers for the enrichment of helium up to 95 vol.
  • FIG. 2 shows a pressure-time diagram of an adsorber of the system according to FIG. 1;
  • FIG. 3 shows a pressure-time diagram with an assigned partial step sequence table for the four adsorbers of the plant according to FIG. 1;
  • FIG. 4 shows a valve circuit diagram for the four adsorbers of the system according to FIG. 1;
  • FIG. 5 shows a diagram of the dependence of the helium yield on the helium purity in a system according to FIG. 1;
  • the system according to FIG. 1 consists of four adsorbers A to D filled with a carbon molecular sieve in a parallel circuit and optionally of four prefilters F1 to F4 filled with activated carbon, in which, if necessary, higher hydrocarbons and trace impurities present in the feed gas mixture can be removed before entering adsorbers A to D.
  • Each adsorber cycles through the following eight sub-steps cyclically, with a time lag to the other three adsorbers:
  • Fig. 2 shows an example of. an adsorption pressure of 20 bar and a total cycle time of 720 s the pressure-time profile that occurs in each of the four adsorbers, staggered from the other adsorbers.
  • Five pressure values Pl to P5 are marked on the pressure axis, between which the pressure build-up and pressure relief steps take place in the present example.
  • FIG 3 shows the time-shifted pressure-time profiles in the four adsorbers A to D.
  • the procedure for adsorber A is described below by way of example. Corresponding procedures apply to the other three adsorbers B, C and D.
  • the adsorption (sub-step T1) takes place at a constant increased pressure, for example at 20 bar.
  • the adsorber A is flowed through at this pressure with the feed gas mixture, nitrogen, methane and other gas components being adsorbed by the carbon molecular sieve, so that helium which is not adsorbed flows out at the adsorber outlet in a highly enriched manner.
  • the loaded adsorber A is regenerated by several pressure relief steps (sub-steps T2 to T5).
  • first pressure equalization Da 1 (sub-step T2), the gas under adsorption pressure from adsorber A being in cocurrent from the adsorption pressure P _. is relaxed in the adsorber C, which is at a lower pressure P.
  • the gas release from adsorber A (T2) to adsorber C (T7) is in the Partial sequence table of FIG. 3 illustrated by an arrow.
  • the pressure in the adsorber A is released to a pressure P, for example to 11.7 bar, while at the same time the pressure in the adsorber C increases from the pressure P to the pressure P. (pressure build-up DA 2) .
  • adsorber A is further expanded in countercurrent from the pressure P to atmospheric pressure P (GEE, substep T4).
  • GEE countercurrent expansion
  • Adsorber A is then evacuated to the final vacuum pressure P, for example 50 mbar, using a vacuum pump 80 (Ev, substep T5).
  • a vacuum pump 80 Ev, substep T5
  • the extracted gas is extremely low in helium and is also discarded as waste gas.
  • the pressure in the sub-steps T6 to T8 is then increased successively to the adsorption pressure P_.
  • pressure equalization there is pressure equalization (sub-step T6) between adsorber A and adsorber B, which has previously gone through sub-step T2 and is at a higher intermediate pressure P. at the end of the evacuation of adsorber A.
  • a helium-enriched gas mixture flows from adsorber B into adsorber A, the gas mixture preferably being drawn off from adsorber B in cocurrent and introduced into adsorber A in cocurrent (head-to-bottom pressure equalization).
  • the pressure in the adsorber A (pressure build-up DA 1) increases from the final vacuum pressure P to an intermediate pressure P, for example 4 bar, while at the same time the pressure in the adsorber B drops from the intermediate pressure P to the intermediate pressure P 3 .
  • the pressure in adsorber A (pressure build-up DA 2) is increased further by a further pressure equalization (sub-step T7) with adsorber C.
  • Adsorber C has previously passed through the sub-step T1, adsorption, and is at adsorption pressure P_ before the pressure equalization with adsorber A.
  • the pressure equalization is carried out in such a way that the helium-enriched gas mixture is drawn off from adsorber C in cocurrent and expanded in countercurrent into adsorber A (head-to-head pressure equalization).
  • the pressure in the adsorber A rises from the intermediate pressure P to the intermediate pressure P., for example 11.7 bar, while at the same time the pressure in the adsorber C drops from the adsorption pressure P 1 to the intermediate pressure P.
  • the pressure in adsorber A is finally reduced by the higher intermediate pressure using product gas.
  • P. on the adsorption pressure P _. for example 20 bar, increased (pressure build-up DA 3, substep T8).
  • a new adsorption step then begins in adsorber A (sub-step T1).
  • the four adsorbers A to D are, as shown in FIG. 1, connected via a series of valves in such a way that one of the four adsorbers is constantly on adsorption and produces high purity helium as product gas.
  • the circuit of the valves is shown in Fig. 4.
  • the gas supply and discharge in the pressure change system shown in FIG. 1 is explained below with reference to FIGS. 4 and 1, by way of example for adsorber A.
  • prefilters F1 to F4 can be provided, which are state of the art and in which strongly adsorbing gas components, such as, for. B. higher hydrocarbons from borehole gases can be pre-separated. Its operation is as shown in the 'rule in the example, the same as that of the downstream in the series circuit main adsorbers A to D takes, so to be not addressed theretolich ⁇ in detail below.
  • adsorber A is at the adsorption pressure P_.
  • the feed gas mixture flows through a line 1 at a pressure which is slightly above the adsorption pressure to overcome the pressure loss in the system, with valves 10 and 13 open, which are upstream and downstream in the direction of flow the adsorber A are arranged through the adsorber A.
  • helium Apart from helium, all other components of the feed gas mixture, such as nitrogen and methane, are adsorbed on the carbon molecular sieve, so that at the head of the adsorber A a helium rich gas flows out via a line 4 into a product gas line 91, in which a needle valve 71 (control valve) is arranged.
  • the adsorption is divided into three time steps ZI, Z2 and Z3.
  • time step ZI a valve 50 contained in a line 5 is closed, so that the entire product gas flows via line 4 into the product gas line 91.
  • valve 50 is opened, so that part of the product gas flows through a downstream throttle valve 72 and via line 5 and an open valve 25, which is connected upstream of adsorber B, into adsorber B, which flows with the Product gas in substep T8 from the intermediate pressure P. to the adsorption pressure P ,. is pressed.
  • the duration of the three time steps ZI, Z2 and Z3 can be 55 s for time step ZI, 115 s for time step Z2 and 10 s for time step Z3.
  • adsorber A is expanded to a higher intermediate pressure P 1 in sub-step T2 (Da 1), the gas flowing out of the adsorber A when the valve 15 is open (valve 50 is closed) in a head-to-head pressure compensation a throttle valve 73 in line 5 flows into the adsorber C when the valve 35 is open, which is pressed in step T7 from an intermediate pressure P to an intermediate pressure P.
  • a time step ZI is required for this pressure compensation (Da 1), which in the example has a duration of 55 s with a total cycle time of 720 s.
  • adsorber A is increased in sub-step T3 (Da 2) via a further pressure equalization with adsorber D from the higher intermediate pressure P. a lower intermediate pressure P, further relaxed.
  • gas is released from the adsorber A via a ring line 3 (valve 60 in line 92 is closed) and a throttle valve 74 in the adsorber D, which is released in the partial step T6 of the final vacuum pressure P to the intermediate pressure P-. is pushed open.
  • the pressure equalization takes place in the example, as described, as head-to-floor pressure equalization.
  • a time step Z3 is required for pressure equalization Da 2, which in the example has a duration of 10 s with a total cycle time of 720 s.
  • Adsorber A is then further relaxed in partial step T4 (GEE) with opened valves 12 and 60 via throttle valve 75 in counterflow from the intermediate pressure P to the atmospheric pressure P.
  • the gas flowing out is fed into an exhaust pipe 92.
  • the countercurrent relaxation in the example has a duration of 55 s.
  • adsorber A is evacuated in sub-step T5 (Ev) with the valve 11 open using the vacuum pump 80 from the atmospheric pressure P "to the final vacuum pressure P-, for example to 50 mbar.
  • the low-helium gas mixture extracted in the process is fed into an exhaust line 93.
  • the evacuation in the example has a duration of 115 s.
  • the evacuated adsorber A is then pressed in partial step T6 (DA 1) in a pressure equalization with adsorber B, which is preferably carried out as head-to-bottom pressure equalization, from the initial vacuum pressure P to the intermediate pressure P.
  • a helium-enriched gas mixture is expanded from the outlet end of adsorber B with valves 24 and 12 open (valve 60 is closed) via ring line 3 and throttle valve 74 into the inlet end of adsorber A.
  • Adsorber B passes through sub-step T3. When the pressure is equalized, the pressure in the adsorber B falls from the intermediate pressure P 1 the intermediate pressure P ,. With a total cycle time of 720 s, the pressure compensation DA 1 in the example takes 10 s.
  • Adsorber A which is partially pressed onto intermediate pressure P, is then further pressed onto intermediate pressure P. in partial step T7 (DA 2) by a further pressure equalization with adsorber C.
  • This pressure equalization is preferably carried out as head-to-head pressure equalization in such a way that a gas mixture enriched with hydrogen is expanded from the outlet end of the adsorber C when the valves 35 and 15 are open via throttle valve 73 in line 5 into the outlet end of the adsorber A.
  • Adsorber C passes through sub-step T2, the pressure in adsorber C dropping from adsorption pressure P, _ to intermediate pressure P.
  • the time for pressure equalization DA 2 is 55 s in the example with a total cycle time of 720 s.
  • step T8 adsorber A is pressed with product gas from the intermediate pressure P. to the adsorption pressure P_.
  • P_ adsorption pressure
  • part of the product gas is passed into the adsorber A via the throttle valve 72 when the valves 50 and 15 are open.
  • the pressure build-up DA 3 is composed of the two time steps Z2 and Z3, which in the example have a duration of 115 or 10 s with a total cycle time of 720 s.
  • regeneration of the adsorbent is achieved by an evacuation step.
  • gas components to be removed here from the helium-containing feed gas such as nitrogen and methane, are also desorbed according to the prior art by flushing with product gas.
  • Such a rinsing desorption would, however, occur in helium enrichment from natural gases with a helium content of ax.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

Le procédé concerne l'enrichissement d'hélium à faible teneur en hélium pour obtenir de l'hélium brut présentant une teneur en hélium supérieure à 50%, par adsorption en pression alternée, avec un rendement en hélium supérieur. Le mélange gazeux contenant par exemple de l'oxygène et/ou du méthane en plus de l'hélium passe à travers des adsorbeurs remplis de tamis moléculaires au carbone qui adsorbent l'azote et/ou le méthane. Quatre adsorbeurs (A, B, C, D) reliés en parallèle sont chargés cycliquement, la phase de montée en pression se déroulant en trois étapes et la phase de détente en pression en quatre étapes. La montée et la détente en pression dans chaque adsorbeur s'effectuent en alternance par égalisation de la pression, partiellement à contre-courant. La phase finale de montée en pression s'effectue avec du gaz reconstitué. Des hydrocarbures supérieurs et d'autres impuretés peuvent être séparés dans des filtres préliminaires (F1, F2, F3, F4) remplis de charbon actif. Le procédé s'utilise de préférence pour enrichir de l'hélium à partir de gaz naturels contenant de 2 à 10% d'hélium et exige moins d'énergie que l'enrichissement par décomposition à basse température dans des installations frigorifiques.
EP88904951A 1987-05-20 1988-05-19 Procede d'enrichissement d'helium Pending EP0358714A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873716898 DE3716898A1 (de) 1987-05-20 1987-05-20 Verfahren und vorrichtung zur heliumanreicherung
DE3716898 1987-05-20

Publications (1)

Publication Number Publication Date
EP0358714A1 true EP0358714A1 (fr) 1990-03-21

Family

ID=6327950

Family Applications (2)

Application Number Title Priority Date Filing Date
EP88108030A Expired - Lifetime EP0291975B1 (fr) 1987-05-20 1988-05-19 Procédé d'enrichissement d'hélium
EP88904951A Pending EP0358714A1 (fr) 1987-05-20 1988-05-19 Procede d'enrichissement d'helium

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP88108030A Expired - Lifetime EP0291975B1 (fr) 1987-05-20 1988-05-19 Procédé d'enrichissement d'hélium

Country Status (10)

Country Link
US (1) US5089048A (fr)
EP (2) EP0291975B1 (fr)
JP (1) JPH0832549B2 (fr)
AU (1) AU604140B2 (fr)
DD (1) DD270125A5 (fr)
DE (2) DE3716898A1 (fr)
ES (1) ES2023976B3 (fr)
PL (1) PL160299B1 (fr)
RU (1) RU1816229C (fr)
WO (1) WO1988009306A1 (fr)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3716899C1 (de) * 1987-05-20 1988-08-04 Bergwerksverband Gmbh Verfahren und Vorrichtung zur Heliumgewinnung
ZA915939B (en) * 1990-08-23 1992-06-24 Boc Group Inc Process for helium purification
US5203888A (en) * 1990-11-23 1993-04-20 Uop Pressure swing adsorption process with multiple desorption steps
US5255519A (en) * 1992-08-14 1993-10-26 Millennium Technologies, Inc. Method and apparatus for increasing efficiency and productivity in a power generation cycle
US5536300A (en) * 1994-10-21 1996-07-16 Nitrotec Corporation Natural gas enrichment process
US5707425A (en) * 1994-10-21 1998-01-13 Nitrotec Corporation Helium recovery from higher helium content streams
US5632803A (en) * 1994-10-21 1997-05-27 Nitrotec Corporation Enhanced helium recovery
US5542966A (en) * 1994-10-21 1996-08-06 Nitrotec Corporation Helium recovery
US5792239A (en) * 1994-10-21 1998-08-11 Nitrotec Corporation Separation of gases by pressure swing adsorption
US5906673A (en) * 1997-05-15 1999-05-25 Nitrotec Corporation Pressure swing system with auxiliary adsorbent bed
DE19927773A1 (de) * 1999-06-17 2000-12-21 Otten Ernst Wilhelm Rückgewinnung von ·3·He
DE10007440A1 (de) * 2000-02-18 2001-08-23 Linde Ag Verfahren zum Abtrennen einer Helium-reichen Fraktion aus einem wenigstens Methan, Stickstoff und Helium enthaltenden Strom
BR0211507A (pt) * 2001-07-31 2004-09-14 Praxair Technology Inc Sistema e processo de recuperação de gás
US20040194513A1 (en) * 2003-04-04 2004-10-07 Giacobbe Frederick W Fiber coolant system including improved gas seals
US20050217479A1 (en) * 2004-04-02 2005-10-06 Membrane Technology And Research, Inc. Helium recovery from gas streams
DE102008007925A1 (de) * 2008-02-07 2009-08-13 Linde Aktiengesellschaft Verfahren zur Helium-Gewinnung
US7780764B2 (en) 2008-06-27 2010-08-24 Praxair Technology, Inc. Methods and systems for helium recovery
JP5968252B2 (ja) 2013-03-04 2016-08-10 大阪瓦斯株式会社 メタンガス濃縮方法
KR102317284B1 (ko) 2014-03-28 2021-10-25 스미토모 세이카 가부시키가이샤 목적 가스의 정제 방법 및 정제 장치
US9623370B2 (en) 2015-02-10 2017-04-18 Praxair Technology, Inc. Integrated process and apparatus for recovery of helium rich streams
US9676628B2 (en) 2015-02-10 2017-06-13 Praxair Technology, Inc. Integrated process and apparatus for recovery of helium rich streams
JP6384960B2 (ja) * 2015-03-23 2018-09-05 住友精化株式会社 ヘリウムガスの精製方法および精製システム
DE102017205598A1 (de) 2017-04-03 2018-10-04 Inficon Gmbh Verfahren zur Gewinnung von Helium aus einem Helium und Sauerstoff enthaltenden Gasgemisch
KR102366060B1 (ko) * 2017-09-27 2022-02-23 존슨 컨트롤스 테크놀러지 컴퍼니 Hvac＆r 시스템을 위한 방출 캐니스터 시스템
US10843121B2 (en) 2017-12-21 2020-11-24 Air Products And Chemicals, Inc. Separation process and apparatus for light noble gas
US10478770B2 (en) * 2017-12-21 2019-11-19 Air Products And Chemicals, Inc. Separation process and apparatus for light noble gas

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3430418A (en) * 1967-08-09 1969-03-04 Union Carbide Corp Selective adsorption process
US3564816A (en) * 1968-12-30 1971-02-23 Union Carbide Corp Selective adsorption process
US3636679A (en) * 1971-01-04 1972-01-25 Union Carbide Corp Selective adsorption gas separation process
FR2135388B1 (fr) * 1971-05-03 1973-05-11 Air Liquide
US3738087A (en) * 1971-07-01 1973-06-12 Union Carbide Corp Selective adsorption gas separation process
GB1449864A (en) * 1973-10-24 1976-09-15 Boc International Ltd Adsorption system
US4077779A (en) * 1976-10-15 1978-03-07 Air Products And Chemicals, Inc. Hydrogen purification by selective adsorption
FR2510539A1 (fr) * 1981-07-28 1983-02-04 Expertises Sa Cie Maritime Procede et installation d'epuration de l'helium contenu dans un melange de gaz
DE3132758A1 (de) * 1981-08-19 1983-03-03 Linde Ag, 6200 Wiesbaden Absorptionsverfahren
DE3214771A1 (de) * 1982-04-21 1983-10-27 Bergwerksverband Gmbh, 4300 Essen Verfahren zur gewinnung von edelgasen mit kleinen atomdurchmessern, insbesondere helium, aus sauerstoff und/oder stickstoff enthaltenden gasgemischen
JPS5992907A (ja) * 1982-11-19 1984-05-29 Seitetsu Kagaku Co Ltd 高濃度アルゴンの製造方法
JPS6096508A (ja) * 1983-10-27 1985-05-30 Zenji Hagiwara 吸着法により酸素ガスを濃縮する方法
JPS6177613A (ja) * 1984-09-25 1986-04-21 Kobe Steel Ltd ヘリウムガスの精製方法
DE3716899C1 (de) * 1987-05-20 1988-08-04 Bergwerksverband Gmbh Verfahren und Vorrichtung zur Heliumgewinnung
US4892565A (en) * 1987-12-29 1990-01-09 Air Products And Chemicals, Inc. Adsorptive separation utilizing multiple adsorption beds
US4790858A (en) * 1988-01-29 1988-12-13 Air Products And Chemicals, Inc. Fractionation of multicomponent gas mixtures by pressure swing adsorption
US4913709A (en) * 1989-02-17 1990-04-03 Ravi Kumar Adsorption process for recovering two high purity gas products from multicomponent gas mixtures
US4914218A (en) * 1989-02-17 1990-04-03 Ravi Kumar Adsorptive process for separating multicomponent gas mixtures

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8809306A1 *

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WO1988009306A1 (fr) 1988-12-01
AU604140B2 (en) 1990-12-06
DE3716898C2 (fr) 1991-01-17
PL272594A1 (en) 1989-03-06
DE3716898A1 (de) 1988-12-15
DE3863391D1 (de) 1991-08-01
JPH0832549B2 (ja) 1996-03-29
AU1930788A (en) 1988-12-21
JPH02503553A (ja) 1990-10-25
ES2023976B3 (es) 1992-02-16
EP0291975B1 (fr) 1991-06-26
EP0291975A1 (fr) 1988-11-23
PL160299B1 (en) 1993-02-26
US5089048A (en) 1992-02-18
DD270125A5 (de) 1989-07-19
RU1816229C (ru) 1993-05-15

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