USRE32590E - Methods for obtaining high-purity carbon monoxide - Google Patents

Methods for obtaining high-purity carbon monoxide Download PDF

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USRE32590E
USRE32590E US06/922,323 US92232386A USRE32590E US RE32590 E USRE32590 E US RE32590E US 92232386 A US92232386 A US 92232386A US RE32590 E USRE32590 E US RE32590E
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adsorption
column
stage
gas
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Toshikazu Sakuraya
Tetsuya Fujii
Shigeo Matsui
Shigeki Hayashi
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JFE Steel Corp
Osaka Oxygen Industries Ltd
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Osaka Oxygen Industries Ltd
Kawasaki Steel Corp
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Priority claimed from JP58110616A external-priority patent/JPS605012A/ja
Priority claimed from JP58187479A external-priority patent/JPS6078612A/ja
Priority claimed from JP58188117A external-priority patent/JPS6078615A/ja
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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
    • 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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active 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
    • B01D2253/102—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
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • 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
    • B01D2256/10—Nitrogen
    • 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
    • B01D2256/20—Carbon monoxide
    • 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
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    • B01D2257/108—Hydrogen
    • 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
    • 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
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    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40028—Depressurization
    • B01D2259/4003—Depressurization with two sub-steps
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    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40035—Equalization
    • B01D2259/40037—Equalization with two sub-steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01D2259/40064—Five
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
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    • 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
    • B01D2259/40066—Six
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • 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
    • B01D2259/40069—Eight
    • 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
    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • 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
    • Y02C20/40—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

  • the present invention relates to a method for obtaining high-purity carbon monoxide from a feed gas, such as off-gases from converters furnace or blast furnaces, containing carbon dioxide and nitrogen in addition to carbon monoxide by a modification of the pressure swing adsorption (PSA) technique.
  • a feed gas such as off-gases from converters furnace or blast furnaces
  • PSA pressure swing adsorption
  • the chemical composition of off-gases from a converter and a blast furnace are listed below.
  • High-purity CO recovered from these off-gases at low cost could be used as a raw material for synthesis of chemicals or as a gas to be blown into molten metal in refining vessels.
  • Most reactions for the synthesis of chemicals require high temperatures and pressures, and therefore, the CO used should have the lowest possible content of CO 2 that corrodes the reactor by oxidation.
  • N 2 that usually does not take part in the reaction should be removed as much as possible.
  • argon that is expensive is typically used in order to avoid the increase in the concentrations of impure gases (e.g. H 2 and N 2 ) in the molten metal.
  • the nitrogen content of the high-purity CO should be as low as possible for the purpose of preventing the increase in the N 2 content of molten iron.
  • the CO 2 concentration should desirably be low in order to prevent oxidative attack of the carbon-base refractory lining of refining vessesl.
  • the present inventors looked to adsorption techniques for recovering high-purity CO by a simpler and less expensive process.
  • the objective of the inventors was to recover high-purity CO not only from off-gases from refining furnaces but also from off-gases from petroleum refineries and chemical synthesis plants, as well as from off-gases resulting from the partial oxidation or hydroreforming of natural gas and heavy hydrocarbon oils.
  • An object of this invention is to provide a process for separating CO from a mixture comprising at least CO and CO 2 through a PSA process.
  • Another object of this invention is to provide a process for separating CO from a mixture comprising at least CO in which the Matsui et al process is improved.
  • Still another object of this invention is to provide a process for separating CO from a mixture comprising at least CO in which the adsorption step is carried out at near atmospheric pressure thereby saving energy normally needed for pressurizing adsorption columns.
  • This invention relates to a process for separating carbon monoxide from a feed gas comprising CO 2 , CO and less adsorbable component than CO, such as N 2 , H 2 , CH 4 through PSA by using at least a two adsorption columns in two stage adsorption operation, which comprises a first adsorption stage for removing CO 2 from said feed gas and a second adsorption stage for separating CO from gaseous mixture withdrawn from the first adsorption stage:
  • the first adsorption stage comprising a pressure swing adsorption repeating adsorption and desorption by using at least two adsorption columns containing an adsorbent such as activated carbon, or natural or synthetic zeolite exhibiting a selective .[.absorbtion.]. .Iadd.adsorption .Iaddend.property to carbon dioxide to remove carbon dioxide from said feed gas, and
  • the second adsorption stage comprising a process for separating carbon monoxide from the gaseous mixture, which has been withdrawn from the first adsorption stage, through PSA by using at least two adsorption columns containing an adsorbent, such as activated carbon, or natural or synthetic zeolite exhibiting a selective adsorb property to carbon monoxide which comprises:
  • step (i) a step of pressurizing an adsorption column by the gaseous mixture, which has been withdrawn from the first adsorption stage, (sometimes hereinunder be referred to as first stage product gas), in which the step (vi) was previously completed;
  • step (ii) a step of introducing the first stage product gas into the adsorption column, in which step (i) was previously completed, so as to adsorb carbon monoxide on or in the adsorbent;
  • step (iii) a step of connecting the adsorption column, in which step (ii) was previously completed, to the other adsorption column in which step (v) was previously completed, to reduce the pressure in the former adsorption column, and increase pressure in the latter adsorption column;
  • step (iv) a step of purging less adsorbable component than CO, such as nitrogen, by concurrently passing product gas through the adsorption column, in which step (iii) was previously completed;
  • step (v) a step of depressurizing the adsorption column, in which step (iv) was previously completed, to a pressure below one atmospheric pressure to recover carbon monoxide adsorbed on or in the adsorbent of the adsorption column;
  • step (vi) a step of connecting the adsorption column, in which step (v) was previously completed, to the other adsorption column, in which step (ii) was previously completed to increase pressure in the former column;
  • step (ii) is completed and before step (iii) is started, part of the gaseous mixture remaining in the columns may be removed outside all the adsorption columns.
  • the gas withdrawn in step (iv) of the other column may be introduced into the adsorption column, in which step (vi) was previously completed.
  • This invention also relates to a process for separating carbon monoxide from a feed gas comprising carbon monoxide and .[.less a.]. .Iadd.a less .Iaddend.adsorbable component than CO, such as N 2 , H 2 or CH 4 through pressure swing adsorption by using at least two adsorption columns containing an adsorbent exhibiting a selective .[.absorption.]. .Iadd.adsorption .Iaddend.property to carbon monoxide which comprises:
  • step (i) a step of pressurizing an adsorption column by the feed gas, in which the step (vi) was previously completed;
  • step (ii) a step of introducing the feed gas into the adsorption column, in which step (i) was previously completed, so as to adsorb carbon monoxide on or in the adsorbent;
  • step (iii) a step of connecting the adsorption column, in which step (ii) was previously completed, to the other adsorption column in which step (v) was previously completed, to reduce the pressure in the former adsorption column, and to increase pressure in the latter adsorption column;
  • step (iv) a step of purging less adsorbable component than CO, such as N 2 , by passing product gas through the adsorption column, in which step (iii) was previously completed;
  • step (v) a step of depressurizing the adsorption column, in which step (iv) was previously completed, to a pressure below one atmospheric pressure to recover carbon monoxide adsorbed on or in the adsorbent of the adsorption column;
  • step (vi) a step of a connecting the adsorption column, in which step (v) was previously completed, to the other adsorption column in which step (ii) was previously completed to increase pressure in the former column;
  • step (vii) a step of introducing into the adsorption column, in which step (vi) was previously completed, the gas withdrawn in step (iv) of the other column,
  • step (ii) is completed and before step (iii) is started, part of the gaseous mixture remaining in the column may be removed outside all the adsorption columns.
  • This invention also relates to a process for separating carbon monoxide from a feed gas comprising carbon monoxide oxide and a less adsorbable component than CO, such as N 2 through pressure swing adsorption by using at least two adsorption columns containing an adsorbent exhibiting a selective absorption property to carbon monoxide which comprises:
  • step (i) a step of pressurizing an adsorption column by the feed gas, in which the step (vi) was previously completed;
  • step (ii) a step of introducing the feed gas into the adsorption column, in which step (i) was previously completed, so as to adsorb carbon monoxide on or in the adsorbent;
  • step (iii) a step of removing part of the gas remaining the adsorption column, in which step (ii) was previously completed, outside all the adsorption columns;
  • step (iv) a step of connecting the adsorption column, in which step (iii) was previously completed, to the other adsorption column in which step (v) was previously completed, to reduce the pressure in the former adsorption column, and to increase pressure in the latter adsorption column;
  • step (v) a step of purging less adsorbable component than CO, such as nitrogen, by passing product gas through the adsorption column, in which step (iv) was previously completed;
  • step (vi) a step of depressurizing the adsorption column, in which step (v) was previously completed, to a pressure below one atmospheric pressure to desorb carbon monoxide adsorbed on or in the adsorbent of the adsorption column;
  • step (vii) a step of a connecting the adsorption column, in which step (vi) was previously completed, to the other adsorption column in which step (ii) was previously completed to increase pressure in the former column;
  • FIG. 1 is a graph showing relationship between adsorption pressure and adsorbed CO
  • FIG. 2 is a graph showing comparison of energy in case of using reciprocating compressor with that in case of using blower
  • FIGS. 3-5 are flowsheets showing preferable apparatuses of this invention.
  • the adsorbents employed in the practice of the first and second adsorption stages of this invention include natural or synthetic zeolites, molecular sieves, activated carbon and the like. Mordenite type zeolite and adsorbent obtained by grinding mordenite type zeolite, followed by sintering the reformed zeolite with a binding agent, are preferable.
  • carbon dioxide is removed from a mixture comprising CO, CO 2 and more poorly adsorbable component than CO, such as nitrogen through PSA.
  • the preferable first adsorption stage comprises in the following:
  • At least two adsorption columns containing an adsorbent exhibiting selective absorb property to carbon dioxide are used.
  • the process comprises:
  • step (i) a step of pressurizing the adsorption column, in which step (v) was previously completed, to a pressure of 0.2-3.0 kg/cm 2 .
  • G by introducing the first stage product gas into the column countercurrently;
  • step (ii) a step of introducing the feed gas into the adsorption column, in which step (i) was previously completed, so as to adsorb carbon dioxide on or in the adsorbent;
  • step (iii) a step of depressurizing the adsorption column, in which step (ii) was previously completed, to near atmospheric pressure countercurrently;
  • step (iv) a step of evacuating the adsorption column, in which step (iii) was previously completed by means of vacuum pump, blower or ejector, and preferably the column is evaporated to 30-300 Torr;
  • step (v) a step of purging carbon dioxide by countercurrently passing the waste gas of the second adsorption stage through the adsorption column, in which step (iv) was previously completed;
  • the first stage product gas is introduced into an adsorption column to increase pressure in the column. Since gas to be recovered according to this invention is easily adsorbable high adsorption pressure is unnecessary.
  • an adsorption pressure of as low as 3 kg./cm 2 .G is sufficient.
  • the adsorption pressure of less than 1 kg/cm 2 .G, for example 0.1 kg/cm 2 .G can also be used.
  • an .Iaddend.adsorption pressure of more than 3 kg/cm 2 .G may be used also if desired.
  • Adsorption step is continued until the concentration of the easily adsorbable component, for example CO, in the gas leaving the adsorption column becomes equal to the concentration of the same component entering the adsorption column, or until just before the time when the two concentrations become equal, or until a given amount of the feed gas flows into the column after the equilibrium has been reached. It is preferable that the adsorption is continued until the concentration of the easily adsorbable component in the gas leaving the adsorption column equal to the concentration of the same component entering the adsorption column, or until just before the time when the two concentrations become equal.
  • the concentration of the easily adsorbable component for example CO
  • step (ii) When step (ii) is completed, the concentration of the poorly adsorbable component is relatively high around the exit of the column.
  • part of the gaseous mixture remaining in the column may be removed outside all the adsorption columns in order to enhance purity of the product gas. It is preferable that the gaseous mixture remaining in the column may be removed to a pressure of three fourth- one fifth of the adsorption pressure. This step is optional.
  • the adsorption column in which step (iii) was previously completed, is connected to the other adsorption column, in which step (vi) is previously completed to withdraw the gas component from the former column and introduce it into the latter column, thereby reducing the pressure in the former adsorption column to one atmosphere or a pressure close to it.
  • the pressure in the former adsorption column may be reduced to near pressure equalization of the two columns.
  • Product gas is passed through the adsorption column, in which step (iv) was previously completed, to purge poorly adsorbable component, such as nitrogen from between the adsorbent particles. It is preferable that the pressure in this step is lower than the adsorption pressure and is higher than one atmosphere. In general, it may be unnecessary to use a pump; and the step may be carried out by connecting the adsorption column to storage tank for product gas. Preferably the product gas is concurrently passed through the column.
  • the adsorption column in which step (v) was previously completed, is evacuated to a pressure below one atmospheric pressure by means of vacuum pump, blower ejector in the like in order to recover product gas, CO. It is preferable that the column is evacuated to a pressure less than 300 Torr, more preferable to 30-100 Torr.
  • the adsorption column in which step (vi) was previously completed, is connected to the other adsorption column, in which step (ii) was previously completed, to pressurize the former column by introducing gas from the latter column to the former column. Preferably, introduction of the gas is concurrently carried out.
  • This step is continued until the pressure in the latter column is reduced to one atmosphere or a pressure close to it. At the end of this step, the pressure in the former column is less than one atmosphere.
  • the pressure in the former adsorption column may be increased to near pressure equalization of the two columns.
  • step (v) of the other adsorption column may be introduced into the adsorption column, in which step (vii) was previously completed. This step is optional.
  • adsorption is carried out at nearly atmospheric pressure.
  • the present invention generally relates to a method of separating carbon monoxide in a feed gas containing nitrogen as well as carbon monoxide, using at least two adsorption columns packed with an adsorbent selective for carbon monoxide such as activated carbon, synthetic or natural zeolite or a mixture thereof.
  • the method comprises the following steps:
  • a suction means such as a blower provided on the exit side of the column and/or a pumping means capable of pumping at a near atmospheric pressure such as a compressor provided on the entry side of the column;
  • step (1) the feed gas is introduced into the regenerated adsorption column by the driving force which is equal to the difference between pressure in the buffer tank and the pressure buildup created by recovering the gas discharged from the purging step.
  • step (2) the feed gas is kept introduced into the adsorption column by the suction means and/or the pumping means.
  • the easily adsorbed gas is desorbed under vacuum, and this results in energy saving as compared with the case where adsorption is effected at superatmospheric pressure and desorption is performed at a lower but still superatmospheric pressure.
  • the difference between the adsorption of CO at a near atmospheric pressure and that under vacuum is substantially the same as the difference between the adsorption at one atmosphere and that under vacuum.
  • What counts for the purpose of the present invention is the adsorption due to the difference between the final pressure reached in gas recovery step under vacuum and the final pressure developed in the purging step which is performed at a near atmospheric pressure or a lower pressure.
  • FIG. 2 Power requirement for pressurization by a compressor as compared with the power required for suction by a blower is shown in FIG. 2.
  • step (3) that follows the adsorption step, the product gas is introduced concurrently into the adsorption column in order to displace the easily adsorbed component between adsorbent particles.
  • Sufficient results are obtained by introducing the product gas at a pressure equal to or a little higher than the pressure used in the adsorption step; or other words, the pressure used in step (3) need not be higher than is required to substitute the strongly adsorbable gas for the feed gas or a gas more rich in the less strongly adsorbable component than said feed gas.
  • the purity of the gas recovered is determined by the amount of the gas used or the purging period.
  • the CO content of the gas leaving the purging step is higher than that of the feed gas because the former has a composition equal to that of the product gas except that is contains a small amount of the poorly adsorbable component that has been displaced from the space between the adsorbent particles. Therefore, the gas leaving the purging step may be directly recycled to the adsorption column that has completed the desorption step in vacuum.
  • step (4) the adsorption column that has been purged is evacuated with a vacuum pump, ejector, blower or any other suitable device to a subatmospheric pressure, preferably not higher than 300 Torr, more preferably between 300 and 30 Torr.
  • a vacuum pump, ejector, blower or any other suitable device to a subatmospheric pressure, preferably not higher than 300 Torr, more preferably between 300 and 30 Torr.
  • FIG. 3 is a flowsheet of the continuous adsorptive process of separating and concentrating carbon monoxide after removing carbon dioxide and nitrogen from converter off-gases. Valves are shown at 7-13 and 22-39. Adsorption columns A and B are packed with an adsorbent selective for carbon dioxide. The two columns are evacuated to 100 Torr, preferably to 60 Torr, with a vacuum pump. Then, the feed gas is introduced into column A through a valve 1, with the other valves in the system left closed.
  • column B is maintained in at underpressure, that is, in vacuum.
  • column A is pressurized, and is maintained at 0.01-3.0 kg/cm 2 .G, preferably 0.2-1.0 kg/cm 2 .G.
  • Valve 2 is opened, and CO 2 and part of CO are adsorbed on or in the adsorbent and the remainder of the feed gas.
  • valves 1 and 2 are closed.
  • valve 3 is open, and pressure of column A is decreased to near one atmospheric pressure.
  • Valve 3 is closed and valve 4 is open, so column A is evacuated by vacuum pump 40, blower or ejector to, preferably 100 Torr and more preferably, 30 Torr in order to desorb carbon dioxide.
  • Valve 5 is open (at this time, amount of gas for purge is adjusted by hand valve 14), whereby CO 2 remaining on or in the adsorbent is purged by passing through the waste gas of the second adsorption stage. Then the pressure of column A is 270 Torr. Then valves 4 and 5 are closed, and valve 6 is open, so column A is pressurized by introducing the product gas thereto. The flow between or among said columns is switched. The first stage product gas is transported to the second stage through a pump 44.
  • Adsorption columns C, D, E and F contain an adsorbent exhibiting selective adsorbing property to carbon monoxide.
  • Adsorption columns C, D and F are evacuated to 100 Torr, preferably 30 Torr by means of vacuum pump 41.
  • Valve 16 is open.
  • the first stage product gas is introduced into adsorption column C.
  • the rate of increase in pressure of column C is adjusted by valve 15.
  • valves 17 and 18 are open and at the same time, is closed.
  • Introduction of the first stage product gas is continued.
  • Carbon monoxide is adsorbed on or in the adsorbent and more poorly adsorbable component, for example nitrogen is passed through column C.
  • Some of the component passing through column C is used as a gas for purge in the first adsorption stage.
  • the remainder of the component can be used as fuel, because it contains considerable amount of CO.
  • the remainder of the component is stored in tank 43.
  • Adsorption step is continued by passing definite amount of the first stage product gas through column C for a given time. Valves 17 and 18 are closed and valve 19 is open. Pressure of column C is reduced to one atmospheric pressure and the gas withdrawn from column C is introduced into column D. Then valve 20 is open and part of the second stage product gas is introduced from product 42 for purging the gas remaining in the portion between the absorbent particles. The gas withdrawn in the purging step is utilized for pressurizing the other column.
  • valves 19 and 20 are closed and valve 21 is open. So, column is evacuated by vacuum pump to desorb carbon monoxide from the adsorbent.
  • the pressure of column C is reduced to less than 300 Torr, preferably 300-30 Torr.
  • the flow between or among said columns is switched so as to repeat the above steps in the columns.
  • Tank for waste gas is shown at 43.
  • Carbon monoxide can be separated from a mixture comprising CO, CO 2 and more poorly adsorbable component, N 2 by combining the first adsorption stage and the second adsorption stage.
  • the waste gas of the second adsorption stage can be used as a gas for purge of the first adsorption stage.
  • the product gas, CO separated according to the present invention contains CO 2 of less than 0.5% and N 2 of less than 1%.
  • FIGS. 4 and 5 relate to separation of CO from the first stage product gas and another feed gas comprising carbon monoxide and more poorly adsorbable component, such as nitrogen.
  • the embodiment shown in FIG. 4 is explained in the following.
  • Adsorption columns A and B contain absorbent exhibiting selective adsorbing property to carbon monoxide.
  • Columns A and B are evaporated to 30 Torr, preferably 60 Torr by means of vacuum pump 111.
  • Valve 101 is open and valves 102-110 are closed.
  • Column A is pressurized by introducing feed gas thereinto.
  • Column B is still maintained at a pressure close to vacuum.
  • Valve 103 is open. Introduction of feed gas into column A is continued at a pressure of 0.1-3.0 kg/cm 2 .G, preferably 0.2-1.0 kg/cm 2 .G.
  • valve 101 is closed.
  • Valve 103 is open and part of the gas remaining in proportion around exit of column A is discharge to 0.1-0.75 kg/cm 2 .G outside all of the columns.
  • valve 103 is open and valve 105 is closed to connect column A to column B.
  • the gas discharged from column A is introduced to column B until pressure of column is reduced to near one atmospheric pressure.
  • the valve 105 is closed and valve 107 is open, so part of the product gas is passed through column A from tank 112 for product gas to purge poorly adsorbable component, N 2 remaining in column A.
  • CO concentration of gas withdrawn in the purging step is higher than that in feed gas. So, the gas withdrawn in the purging step can be utilized for pressurizing the other column.
  • valve 107 is closed and valve 109 is open, so column A is evaculated by means of vacuum pump to recover product gas, CO from the adsorbent of column A.
  • pressure of column A is reduced to less than 300 Torr, preferably 300-30 Torr.
  • Tank for waste gas is shown at 113.
  • FIG. 5 is a flowsheet for another embodiment of the continuous process for removing poorly adsorbable components (e.g. N 2 and H 2 ) from a converter off-gases and concentrating the easily adsorbable component (i.e. CO).
  • Adsorption columns A, B, C and D are packed with an adsorbent selective for the easily adsorbable component.
  • the four columns are evacuated to 300 Torr or less, preferably 30 Torr or less, with a vacuum pump 220.
  • valve 202 When a feed gas supply valve 202 is opened, the feed gas is drawn into the adsorption column A to bring its pressure equal to the pressure in a feed gas buffer tank 201. In this mode, valves 203 to 219 are all closed, and adsorption columns B, C and D remain under vacuum. When the pressure in the adsorption column increases to a level equal to the pressure in the buffer tank (500-700 mm Hg), valve 204 is opened, whereupon the feed gas is caused to pass through the adsorption column A by being drawn with a blower 222 on the exit side of the column or by being pumped with a pumping means 224 on the entry side of the column.
  • the easily adsorbable component of the feed gas is adsorbed on the adsorbent whereas the poorly adsorbable components are drawn by the blower into a gas holder 223.
  • the feed valves 202 and 204 are closed, and at the same time, valves 206 and 208 are opened to purge the column A of the poorly adsorbable components between adsorbent particles by recycling the product gas from a product gas tank 221 through the valve 206 to the bottom of the adsorption column A.
  • the purged gas is fed through valves 206 and 208 into adsorption column B that has completed evacuation for recovery of the product gas.
  • valves 206 and 208 are closed and a valve 210 at the bottom of adsorption column A is opened to evacuate it to 300 Torr or less, preferably 30 Torr or less, with a vacuum pump 220 for desorbing the easily adsorbable component (CO) from the adsorbent and recovering the same as the product gas.
  • a vacuum pump 220 for desorbing the easily adsorbable component (CO) from the adsorbent and recovering the same as the product gas.
  • PSA consisting of adsorption, depressurization, evacuation, purge, and pressurization by product, pressurization by feed gas was used in the first adsorption stage.
  • PSA consisting of pressurization by first stage product gas, adsorption, depressurization, purge, evacuation and pressurization by gas withdrawn from the other column was used in the second adsorption stage.
  • the product gas had the following components: CO: 98.6% CO 2 : 0.5% N 2 : 0.9% H 2 : 0 O 2 : 0
  • Example 1 The procedure of Example 1 was repeated except that the following off-gas from convert furnace was used and the following conditions were used.
  • Feed gas had the following components: CO: 85.3% N 2 : 5.7% CO 2 : 0.15% H 2 : 8.55%
  • Adsorption cycle was in the following:
  • Example 3 The procedure of Example 3 was repeated except that pressurization (7) by gas discharged in depressurization (4) was not used. Amount of feed gas fed was 50.5 NM 3 and amount of CO recovered was 10.8 NM 3 . Yield was 25.09%. Purity of CO was 99.9%.
  • adsorption was effected at one atmospheric pressure.
  • the adsorption cycle was in the following: 1. Pressurization by feed gas 2. Adsorption at one atmospheric pressure 3. Purge by product gas 4. Evacuation 5. Pressurization by purge gas in other column
  • Feed gas had the following: CO: 88% CO 2 : 0.5% N 2 : 5.5% H 2 : 5.9% O 2 : 0.1%
  • Adsorbent activated zeolite (ZE-501) (156 kg 1/16 pellet) Temperature: 25° C. Adsorption pressure: 100 mm Aq Adsorption speed: 3 cm/sec. Column: steel column (I.D. 14 B ⁇ 2.3 m)
  • Amount of feed gas was 43 NM 3 /hour and amount of CO recovered was 19 NM 3 /hour. Yield was 49.45%. Power employed was 2.9 KWH. Purity of CO was 97.8%. It contained CO 2 (0.3%) and N 2 (1.9%).
  • Time sequence of the best process of this invention is as follows:

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US06/922,323 1983-06-20 1986-10-23 Methods for obtaining high-purity carbon monoxide Expired - Lifetime USRE32590E (en)

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JP58-110616 1983-06-20
JP58110616A JPS605012A (ja) 1983-06-20 1983-06-20 吸着法を使用して一酸化炭素を含む混合ガスより一酸化炭素を精製する方法
JP58-187479 1983-10-06
JP58187479A JPS6078612A (ja) 1983-10-06 1983-10-06 吸着法を使用して一酸化炭素を含む混合ガス中の一酸化炭素を濃縮する方法
JP58188117A JPS6078615A (ja) 1983-10-07 1983-10-07 吸着法を使用して少なくとも一酸化炭素を含む混合ガス中の一酸化炭素を精製する方法
JP58-188117 1983-10-07

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US4915711A (en) 1989-05-18 1990-04-10 Air Products And Chemicals, Inc. Adsorptive process for producing two gas streams from a gas mixture
US5002591A (en) * 1988-10-14 1991-03-26 Vbm Corporation High efficiency PSA gas concentrator
US5293449A (en) * 1990-11-23 1994-03-08 Comsat Corporation Analysis-by-synthesis 2,4 kbps linear predictive speech codec
US5531809A (en) * 1994-09-14 1996-07-02 Air Products And Chemicals, Inc. Pretreatment layer for CO-VSA
US6045603A (en) 1998-08-21 2000-04-04 The Boc Group, Inc. Two phase pressure swing adsorption process
US6083299A (en) 1999-01-21 2000-07-04 The Boc Group, Inc. High pressure purge pressure swing adsorption process
US6113672A (en) 1999-01-21 2000-09-05 The Boc Group, Inc. Multiple equalization pressure swing adsorption process
CN108977234A (zh) * 2018-07-25 2018-12-11 戴乐亭 一种焦炉煤气与转炉和/或高炉煤气的脱碳方法

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US4705541A (en) * 1987-02-12 1987-11-10 Air Products And Chemicals, Inc. Production of mixed gases of controlled composition by pressure swing adsorption
FR2624759B1 (fr) * 1987-12-22 1990-05-04 Air Liquide Procede de traitement d'un melange gazeux par adsorption
JPH02129014A (ja) * 1988-11-04 1990-05-17 Mitsui Eng & Shipbuild Co Ltd 一酸化炭素ガス製造法
US4914218A (en) * 1989-02-17 1990-04-03 Ravi Kumar Adsorptive process for separating multicomponent gas mixtures
US4913709A (en) * 1989-02-17 1990-04-03 Ravi Kumar Adsorption process for recovering two high purity gas products from multicomponent gas mixtures
CN100340324C (zh) * 2004-06-11 2007-10-03 成都天立化工科技有限公司 一种两段全回收变压吸附气体分离方法
DK2989233T3 (da) * 2013-03-26 2020-10-12 Haldor Topsoe As Fremgangsmåde til fremstilling af carbonmonoxid (CO) ud fra carbondioxid (CO2) i en fastoxidelektrolysecelle
ES2583903T3 (es) 2013-07-30 2016-09-22 Haldor Topso¿E A/S Procedimiento para producir CO de alta pureza mediante purificación con membrana de CO producido mediante SOEC
KR101986632B1 (ko) * 2017-08-10 2019-06-07 울산과학기술원 고로가스 운영시스템
KR102059068B1 (ko) * 2019-04-11 2019-12-24 한국화학연구원 철강산업의 부생가스로부터 일산화탄소의 분리 및 회수공정
WO2025172953A1 (en) 2024-02-16 2025-08-21 Dioxycle Separators for gaseous products in oxocarbon electrolyzers

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US5002591A (en) * 1988-10-14 1991-03-26 Vbm Corporation High efficiency PSA gas concentrator
US4915711A (en) 1989-05-18 1990-04-10 Air Products And Chemicals, Inc. Adsorptive process for producing two gas streams from a gas mixture
US5026406A (en) * 1989-05-18 1991-06-25 Air Products And Chemicals, Inc. Adsorptive process for producing two gas streams from a gas mixture
US5293449A (en) * 1990-11-23 1994-03-08 Comsat Corporation Analysis-by-synthesis 2,4 kbps linear predictive speech codec
US5531809A (en) * 1994-09-14 1996-07-02 Air Products And Chemicals, Inc. Pretreatment layer for CO-VSA
US6045603A (en) 1998-08-21 2000-04-04 The Boc Group, Inc. Two phase pressure swing adsorption process
US6083299A (en) 1999-01-21 2000-07-04 The Boc Group, Inc. High pressure purge pressure swing adsorption process
US6113672A (en) 1999-01-21 2000-09-05 The Boc Group, Inc. Multiple equalization pressure swing adsorption process
CN108977234A (zh) * 2018-07-25 2018-12-11 戴乐亭 一种焦炉煤气与转炉和/或高炉煤气的脱碳方法

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