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WO2024235563A1 - Method and apparatus for separating co2 by partial condensation and/or distillation - Google Patents

Method and apparatus for separating co2 by partial condensation and/or distillation Download PDF

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Publication number
WO2024235563A1
WO2024235563A1 PCT/EP2024/060655 EP2024060655W WO2024235563A1 WO 2024235563 A1 WO2024235563 A1 WO 2024235563A1 EP 2024060655 W EP2024060655 W EP 2024060655W WO 2024235563 A1 WO2024235563 A1 WO 2024235563A1
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Prior art keywords
gas
water
dried
distillation
upstream
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French (fr)
Inventor
Félix PERE
Mathieu LECLERC
Martin Raventos
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication of WO2024235563A1 publication Critical patent/WO2024235563A1/en
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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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
    • B01D53/002—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 condensation
    • 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
    • B01D53/005—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 heat treatment
    • 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
    • B01D53/26—Drying gases or vapours
    • B01D53/261—Drying gases or vapours by adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/265—Drying gases or vapours by refrigeration (condensation)
    • 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
    • C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/0605—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
    • F25J3/0625—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0655—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/067—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of carbon dioxide
    • 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
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—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 absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/02—Multiple feed streams, e.g. originating from different sources
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F25J2220/82—Separating low boiling, i.e. more volatile components, e.g. He, H2, CO, Air gases, CH4
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30—Compression of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/02—Internal refrigeration with liquid vaporising loop

Definitions

  • the present invention relates to a method and apparatus for separating CO2 by partial condensation and/or distillation.
  • it relates to such a method supplied by a CO2-enriched gas originating from a CO2 separation process by absorption.
  • CO2 removal is already widely deployed on an industrial scale, mainly with absorption processes. These processes, whether physical, chemical or physicochemical, all use a liquid solvent to remove one or more compounds (here CO2) from a gas stream.
  • the rich solvent is then regenerated and releases the captured compounds. This regeneration is generally done by expansion and heat input.
  • a blower may be required to increase the pressure of the CO2-enriched gas from the absorption process to the correct pressure. Such a device might also be required if the two processes are not close to each other.
  • the most relevant solution is therefore to cool the CO2-enriched wet flow coming from the absorption process to condense as much water as possible, before mixing it with the PSA H2 waste.
  • the water level can be desaturated to a level that allows the two gases to be compressed together.
  • the compressor and the partial condensation and/or distillation separation apparatus will be larger to be able to handle the two mixed gases.
  • WO2010/066972 describes a CO2 separation process in which a gas mixture comprising hydrogen, carbon monoxide, carbon dioxide, methane and water is separated using a H2 PSA producing a dry waste, the water having been removed by a CO2 PSA.
  • a method for separating CO2 by partial condensation and/or distillation in which: i) a first gas containing hydrogen, water and carbon dioxide is compressed in a compressor, dried in an adsorption drying unit and then separated by partial condensation and/or distillation to produce a CO2-enriched fluid ii) a second gas, containing carbon dioxide, hydrogen and/or nitrogen as well as water and optionally carbon monoxide and/or methane, originating from an absorption separation process, is cooled to condense at least part of the water it contains, the water is separated from the gas forming a dried gas and the dried gas is mixed with the first gas upstream of the adsorption drying unit and optionally upstream of the compressor.
  • the dried gas is mixed with the first gas upstream of the adsorption drying unit and downstream of the compressor.
  • the second gas is compressed upstream of the cooling to a pressure which is that of the first gas upstream of the adsorption drying unit.
  • the second gas is compressed upstream of the cooling to a pressure which is that at the entrance to the adsorption drying unit.
  • the second gas is cooled by indirect heat exchange with a fluid, possibly enriched with CO2, produced by partial condensation and/or distillation, possibly at a temperature below 0°C.
  • the first gas is a waste gas from an adsorption separation process producing a hydrogen-enriched gas and a hydrogen-depleted gas which is the waste gas.
  • the CO2 and/or water content of the first gas is lower than that of the second gas.
  • the CO2 content of the mixture formed by mixing the dried gas with the first gas is higher than that of the first gas.
  • an apparatus for separating CO2 by partial condensation and/or distillation comprising a compressor, an adsorption drying unit, a partial condensation and/or distillation separation unit, means for sending a first gas containing hydrogen, water and carbon dioxide to be compressed in the compressor, means for sending the first compressed gas to be dried in the adsorption drying unit and means for sending the first compressed and dried gas to be separated by partial condensation and/or distillation to produce a CO2-enriched fluid, a cooler, a phase separator, means for sending a second gas, containing carbon dioxide, hydrogen and/or nitrogen as well as water and optionally carbon monoxide and/or methane, coming from an absorption separation process to the cooler to be cooled to condense at least part of the water it contains, means for removing the water separated from the gas from the phase separator, means for removing a dried gas from the phase separator and means for sending the dried gas to mix with the first gas upstream of the adsorption drying unit and possibly upstream of the compressor.
  • the absorption separation process is a CO2-selective physicochemical process.
  • the absorption separation process is an amine washing process.
  • the apparatus may include means for sending the dried gas to mix with the first gas upstream of the adsorption drying unit and downstream of the compressor.
  • Figure 1 represents a method according to the invention.
  • Figure 2 shows a method according to the invention.
  • Figure 3 shows a method according to the invention.
  • Figure 4 shows a method according to the invention.
  • a flow 3 of an absorption unit A contains carbon dioxide, water, hydrogen and/or nitrogen and possibly carbon monoxide and/or methane.
  • Flow 3 typically contains between 6 and 7 mol% water.
  • the absorption unit may use a CO2-selective physicochemical process and for example may use an amine wash, a hot potassium carbonate wash, a Purisol® type wash with NMP wash) and produces flow 3 at substantially atmospheric pressure or higher pressures. In some cases, it is therefore necessary to boost flow 3 with a blower B in order to bring its pressure to approximately 1.5 bar abs or more.
  • Flow 3 is then cooled by indirect heat exchange with water 11 in cooler K to condense at least a portion 7 of the water it contains.
  • the dried gas 9 exits the separator S used to remove the water 7 and is sent to mix with the waste gas 1 from a pressure swing adsorption hydrogen separation process P.
  • This first gas 1 contains carbon dioxide, hydrogen and water and usually has a lower carbon dioxide content than the flow 3.
  • the first gas 1 usually has a lower water content than the flow 3.
  • the flow rate of the first gas 1 is preferably higher than that of the second gas 3.
  • the mixture 15 is then treated in a separation unit C. It is compressed to a pressure above 9 bar abs, or even above 20 bar, dried by adsorption to remove the remaining water and then cooled and separated by partial condensation and/or distillation to obtain at least one gas and/or at least one liquid enriched in CO2 containing for example at least 90 mol%, or even at least 95 mol% CO2 and a gas enriched in hydrogen.
  • Blower B if present, can compress gas 9 to the pressure of gas 1 or to the pressure at the inlet of dryer 19 of Figure 4.
  • the flow 3 is cooled in a cooler R upstream of the cooler K and downstream of the absorption unit A and possibly the blower B.
  • This cooler R allows indirect heat exchange between the dried gas 9 coming from the separator S and the flow to be cooled 3.
  • the gas cooled in the cooler R is mixed with the first gas 1 as in Figure 1. This reduces the water consumption 11.
  • flow 3 is available at higher pressure than the first gas 1 and therefore flow 9 can be mixed with the residual 3 after compression of the residual 3 in at least one stage of the compressor of unit C.
  • the flow 3 is cooled to condense water at least from a liquid 15 enriched in CO2 relative to the mixture coming from at least one phase separator of the unit C where the mixture 13 separates.
  • the liquid is sent to the cooler K at a temperature below 0°C and vaporizes in the cooler K.
  • the liquid 15 can otherwise constitute a part of the tank liquid of a distillation column, this liquid comprising at least 90 mol% CO2. The use of such a flow makes it possible to reduce the consumption of water 11 and in addition achieves the vaporization necessary to produce the liquid 15 in gaseous form to be sent to the customer.
  • FIG 4 shows a version of Figure 1 with unit C illustrated in more detail.
  • Unit C comprises a compressor 17, an adsorption drying unit (TSA) 19, an exchange line 21 for cooling the compressed and dried mixture and a separation part 23 by partial condensation and/or distillation producing at least one fluid enriched in CO2 25 relative to the mixture 13.
  • TSA adsorption drying unit
  • the invention is of most interest when the flow rate of gas 3 is lower than the flow rate of gas 1 because mixing flow rates 1, 9 requires oversizing unit C.
  • the invention is particularly applicable to the case where the ratio between the flow rate of gas 3 and that of flow rate 1 is less than 0.1, the exact ratio depending on economic factors.
  • flow 3 is often richer in CO2 than flow 1
  • adding flow 9 to gas 1 increases the molecular weight of gas 1 and makes the compression in unit C more efficient. Separation by partial condensation and/or distillation is also more efficient when the flow to be separated is richer in CO2.
  • the PSA H2 waste gas undergoes composition fluctuations due to the cyclicity of the PSA process. Mixing it with a fixed composition gas helps to mitigate the effect of these composition variations on the compressor and the downstream separation process.
  • unit C allows the elimination of impurities remaining in flow 3, for example nitrogen and/or hydrogen, carbon monoxide and methane, while absorption does not allow them to be removed.
  • unit C allows the production of good quality CO2 with the CO2-rich gas from an absorption unit.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Drying Of Gases (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

In a method for separating CO2 by partial condensation and/or distillation - a first gas (1) containing hydrogen, water and carbon dioxide is compressed in a compressor (17), dried in an adsorption drying unit (19) and then separated by partial condensation and/or distillation to produce a CO2-enriched fluid (25) and - a second gas (3), containing carbon dioxide, hydrogen and water, originating from an absorption separation process (A), is cooled in order to condense at least a portion (7) of the water that it contains, the water is separated from the gas forming a dried gas (9) and the dried gas is mixed with the first gas upstream of the adsorption drying unit and optionally upstream of the compressor.

Description

Procédé et appareil de séparation de CO2 par condensation partielle et/ou distillation Process and apparatus for separation of CO2 by partial condensation and/or distillation

La présente invention est relative à un procédé et à un appareil de séparation de CO2 par condensation partielle et/ou distillation. En particulier il concerne un tel procédé alimenté par un gaz enrichi en CO2 provenant d’un procédé de séparation de CO2 par absorption. The present invention relates to a method and apparatus for separating CO2 by partial condensation and/or distillation. In particular, it relates to such a method supplied by a CO2-enriched gas originating from a CO2 separation process by absorption.

L'élimination du CO2 est déjà largement déployée à l'échelle industrielle, principalement avec des procédés d'absorption. Ces procédés, qu'ils soient physiques, chimiques ou physico-chimiques, utilisent tous un solvant liquide pour éliminer un ou plusieurs composés (ici le CO2) d'un flux gazeux. CO2 removal is already widely deployed on an industrial scale, mainly with absorption processes. These processes, whether physical, chemical or physicochemical, all use a liquid solvent to remove one or more compounds (here CO2) from a gas stream.

Le solvant riche est alors régénéré et libère les composés captés. Cette régénération se fait généralement par détente et apport de chaleur. The rich solvent is then regenerated and releases the captured compounds. This regeneration is generally done by expansion and heat input.

Appliqués à l'élimination du CO2, ces procédés produisent tous du CO2 depuis la pression presque atmosphérique jusqu'à ~3 bara, selon le schéma de procédé. De plus, de nombreux procédés d'absorption (lavage aux amines, lavage chaud au potassium, Purisol ®...) utilisent des solvants aqueux, et libèrent ainsi du CO2 humide. Applied to CO2 removal, these processes all produce CO2 from near atmospheric pressure up to ~3 bara, depending on the process flowsheet. In addition, many absorption processes (amine scrubbing, hot potassium scrubbing, Purisol ®...) use aqueous solvents, and thus release wet CO2.

Cette production de CO2 humide à basse pression n'est pas gênante lorsque l'élimination du CO2 est justifiée par les spécifications du procédé aval (synthèse, traitement cryogénique...). Cependant, les spécifications du CSC (Capture et Séquestration de Carbone, en anglais « CCS ») exigent généralement du CO2 sec, sous pression ou liquéfié. Le CO2 provenant des processus d'absorption doit donc être comprimé, séché et éventuellement liquéfié pour être intégré dans les schémas de CSC. Cela nécessite des équipements supplémentaires et des dépenses de fonctionnement. This low-pressure wet CO2 production is not problematic when CO2 removal is justified by the specifications of the downstream process (synthesis, cryogenic treatment, etc.). However, CCS (Carbon Capture and Sequestration) specifications generally require dry, pressurized or liquefied CO2. CO2 from absorption processes must therefore be compressed, dried and possibly liquefied to be integrated into CCS schemes. This requires additional equipment and operating expenses.

Il est connu de séparer du CO2 d’un gaz résiduaire d’un PSA produisant de l’hydrogène. Le gaz résiduaire est comprimé et séparé par condensation partielle et/ou distillation. Alors que le gaz résiduaire contient de l’eau, celle-ci est en état peu saturé et donc le gaz résiduaire peut être comprimé sans que l’eau se condense en amont de la séparation par condensation partielle et/ou distillation. Un sécheur est donc nécessaire en amont de la condensation partielle et/ou la distillation. Il est également connu de WO2015/075071 de mélanger un gaz enrichi en CO2 provenant d’un lavage aux amines au gaz résiduaire d’un PSA H2 et de séparer le mélange par condensation partielle et/ou distillation. It is known to separate CO2 from a waste gas of a PSA producing hydrogen. The waste gas is compressed and separated by partial condensation and/or distillation. While the waste gas contains water, this is in a low-saturated state and therefore the waste gas can be compressed without the water condensing upstream of the separation by partial condensation and/or distillation. A dryer is therefore necessary upstream of the partial condensation and/or distillation. It is also known from WO2015/075071 to mix a CO2-enriched gas from an amine wash with the waste gas of a PSA H2 and to separate the mixture by partial condensation and/or distillation.

Il est aussi connu de US2013/9156686 d’utiliser un lavage aux amines pour produire un fluide enrichi en CO2 et un fluide appauvri en CO2, de séparer le fluide appauvri en CO2 par PSA produisant de l’hydrogène et un autre gaz appauvri en hydrogène, l’autre gaz étant séparé à basse température pour récupérer le CO2 qu’il contient. Le CO2 humide généré par les procédés d'absorption peut être directement intégré au procédé de séparation du résiduaire du PSA H2 par condensation partielle et/ou distillation. Etant (dans la plupart des cas) humide et disponible à basse pression, il est idéalement injecté dans le procédé de séparation à l'entrée du compresseur du résiduaire du PSA H2. It is also known from US2013/9156686 to use an amine wash to produce a CO2-enriched fluid and a CO2-depleted fluid, to separate the CO2-depleted fluid by PSA producing hydrogen and another hydrogen-depleted gas, the other gas being separated at low temperature to recover the CO2 it contains. The wet CO2 generated by the absorption processes can be directly integrated into the separation process of the PSA H2 waste by partial condensation and/or distillation. Being (in most cases) wet and available at low pressure, it is ideally injected into the separation process at the inlet of the PSA H2 waste compressor.

Les gaz enrichis en CO2 provenant du procédé d’absorption étant généralement disponibles à environ 1,3 bara, une soufflante peut être nécessaire pour augmenter la pression du gaz enrichi en CO2 du procédé d'absorption à la bonne pression. Un tel dispositif pourrait également être nécessaire si les deux procédés ne sont pas proches l'un de l'autre. Since the CO2-enriched gases from the absorption process are typically available at around 1.3 bara, a blower may be required to increase the pressure of the CO2-enriched gas from the absorption process to the correct pressure. Such a device might also be required if the two processes are not close to each other.

L'injection d'un flux humide venant du procédé d’absorption dans le résiduaire gazeux du PSA pourrait être très préjudiciable au procédé de condensation partielle et/ou distillation, car elle augmente la température du point de rosée du résiduaire gazeux du PSA H2, et donc réduit la pression atteignable sans condensation. Le séchage doit alors être réalisé à pression plus basse, ce qui est coûteux à la fois en investissement et en coûts opératoires. The injection of a wet stream from the absorption process into the PSA gaseous waste could be very detrimental to the partial condensation and/or distillation process, because it increases the dew point temperature of the PSA H2 gaseous waste, and therefore reduces the pressure achievable without condensation. Drying must then be carried out at lower pressure, which is expensive both in investment and operating costs.

La solution la plus pertinente est donc de refroidir le flux humide enrichi en CO2 venant du procédé d’absorption pour condenser le plus d'eau possible, avant de le mélanger avec le résiduaire du PSA H2. The most relevant solution is therefore to cool the CO2-enriched wet flow coming from the absorption process to condense as much water as possible, before mixing it with the PSA H2 waste.

En refroidissant le flux humide pour condenser l’eau qu’il contient, le niveau d’eau peut être désaturé à un niveau permettant de comprimer les deux gaz ensemble. Evidemment le compresseur et l’appareil de séparation par condensation partielle et/ou distillation seront plus grands pour pouvoir traiter les deux gaz mélangés.By cooling the wet stream to condense the water it contains, the water level can be desaturated to a level that allows the two gases to be compressed together. Obviously the compressor and the partial condensation and/or distillation separation apparatus will be larger to be able to handle the two mixed gases.

WO2010/066972 décrit un procédé de séparation de CO2 dans lequel un mélange gazeux comprenant de l’hydrogène, du monoxyde de carbone, du dioxyde de carbone, du méthane et de l’eau est séparé utilisant un PSA H2 produisant un résiduaire sec, l’eau ayant été enlevée par un PSA CO2. Selon un objet de l’invention, il est prévu un procédé de séparation de CO2 par condensation partielle et/ou distillation dans lequel : i) un premier gaz contenant de l’hydrogène, de l’eau et du dioxyde de carbone est comprimé dans un compresseur, séché dans une unité de séchage par adsorption et ensuite séparé par condensation partielle et/ou distillation pour produire un fluide enrichi en CO2 ii) un deuxième gaz, contenant du dioxyde de carbone, de l’hydrogène et/ou de l’azote ainsi que de l’eau ainsi qu’éventuellement du monoxyde de carbone et/ou du méthane, provenant d’un procédé de séparation par absorption, est refroidi pour condenser au moins une partie de l’eau qu’il contient, l’eau est séparée du gaz formant un gaz séché et le gaz séché est mélangé au premier gaz en amont de l’unité de séchage par adsorption et éventuellement en amont du compresseur.WO2010/066972 describes a CO2 separation process in which a gas mixture comprising hydrogen, carbon monoxide, carbon dioxide, methane and water is separated using a H2 PSA producing a dry waste, the water having been removed by a CO2 PSA. According to one subject of the invention, there is provided a method for separating CO2 by partial condensation and/or distillation in which: i) a first gas containing hydrogen, water and carbon dioxide is compressed in a compressor, dried in an adsorption drying unit and then separated by partial condensation and/or distillation to produce a CO2-enriched fluid ii) a second gas, containing carbon dioxide, hydrogen and/or nitrogen as well as water and optionally carbon monoxide and/or methane, originating from an absorption separation process, is cooled to condense at least part of the water it contains, the water is separated from the gas forming a dried gas and the dried gas is mixed with the first gas upstream of the adsorption drying unit and optionally upstream of the compressor.

Selon d’autres caractéristiques facultatives : According to other optional features:

• le gaz séché est mélangé au premier gaz en amont de l’unité de séchage par adsorption et en aval du compresseur. • the dried gas is mixed with the first gas upstream of the adsorption drying unit and downstream of the compressor.

• le deuxième gaz est comprimé en amont du refroidissement jusqu’à une pression qui est celle du premier gaz en amont de l’unité de séchage par adsorption. • the second gas is compressed upstream of the cooling to a pressure which is that of the first gas upstream of the adsorption drying unit.

• le deuxième gaz est comprimé en amont du refroidissement jusqu’à une pression qui est celle à l’entrée de l’unité de séchage par adsorption. • the second gas is compressed upstream of the cooling to a pressure which is that at the entrance to the adsorption drying unit.

• le deuxième gaz est comprimé en amont du refroidissement jusqu’à une pression d’au moins 9 bars abs • the second gas is compressed upstream of the cooling to a pressure of at least 9 bars abs

• le deuxième gaz est refroidi par échange de chaleur indirect avec de l’eau.• the second gas is cooled by indirect heat exchange with water.

• le deuxième gaz est refroidi par échange de chaleur indirect avec un fluide, éventuellement enrichi en CO2, produit par la condensation partielle et/ou la distillation, éventuellement à une température en dessous de 0°C. • the second gas is cooled by indirect heat exchange with a fluid, possibly enriched with CO2, produced by partial condensation and/or distillation, possibly at a temperature below 0°C.

• le deuxième gaz séché est réchauffé par échange de chaleur avec le deuxième gaz en amont du refroidissement. • the second dried gas is reheated by heat exchange with the second gas upstream of the cooling.

• le premier gaz est un gaz résiduaire d’un procédé de séparation par adsorption produisant un gaz enrichi en hydrogène et un gaz appauvri en hydrogène qui est le gaz résiduaire. • the first gas is a waste gas from an adsorption separation process producing a hydrogen-enriched gas and a hydrogen-depleted gas which is the waste gas.

• la teneur en CO2 et/ou en eau du premier gaz est plus basse que celle du deuxième gaz. • la teneur en CO2 du mélange formé en mélangeant le gaz séché au premier gaz est supérieure à celle du premier gaz. • the CO2 and/or water content of the first gas is lower than that of the second gas. • the CO2 content of the mixture formed by mixing the dried gas with the first gas is higher than that of the first gas.

• le débit du premier gaz est supérieur à celui du deuxième gaz. • the flow rate of the first gas is greater than that of the second gas.

• le rapport entre les débits du premier et du deuxième gaz est au moins égal à 10. • the ratio between the flow rates of the first and second gases is at least equal to 10.

• le deuxième gaz provient d’une unité de lavage aux amines ou au carbonate de potassium. • the second gas comes from an amine or potassium carbonate washing unit.

• des fumées sont séparées par le procédé d’absorption pour produire le deuxième gaz. • fumes are separated by the absorption process to produce the second gas.

• un gaz de synthèses est séparé par le procédé d’absorption pour produire le deuxième gaz. • a synthesis gas is separated by the absorption process to produce the second gas.

Selon un autre objet de l’invention, il est prévu un appareil de séparation de CO2 par condensation partielle et/ou distillation comprenant un compresseur, une unité de séchage par adsorption, une unité de séparation par condensation partielle et/ou distillation, des moyens pour envoyer un premier gaz contenant de l’hydrogène, de l’eau et du dioxyde de carbone être comprimé dans le compresseur, des moyens pour envoyer le premier gaz comprimé être séché dans l’unité de séchage par adsorption et des moyens pour envoyer le premier gaz comprimé et séché être séparé par condensation partielle et/ou distillation pour produire un fluide enrichi en CO2, un refroid isseur, un séparateur de phases, des moyens pour envoyer un deuxième gaz, contenant du dioxyde de carbone, de l’hydrogène et/ou de l’azote ainsi que de l’eau ainsi qu’éventuellement du monoxyde de carbone et/ou du méthane, provenant d’un procédé de séparation par absorption au refroidisseur pour être refroidi pour condenser au moins une partie de l’eau qu’il contient, des moyens pour sortir l’eau séparée du gaz du séparateur de phases, des moyens pour sortir un gaz séché du séparateur de phases et des moyens pour envoyer le gaz séché se mélanger au premier gaz en amont de l’unité de séchage par adsorption et éventuellement en amont du compresseur. According to another object of the invention, there is provided an apparatus for separating CO2 by partial condensation and/or distillation comprising a compressor, an adsorption drying unit, a partial condensation and/or distillation separation unit, means for sending a first gas containing hydrogen, water and carbon dioxide to be compressed in the compressor, means for sending the first compressed gas to be dried in the adsorption drying unit and means for sending the first compressed and dried gas to be separated by partial condensation and/or distillation to produce a CO2-enriched fluid, a cooler, a phase separator, means for sending a second gas, containing carbon dioxide, hydrogen and/or nitrogen as well as water and optionally carbon monoxide and/or methane, coming from an absorption separation process to the cooler to be cooled to condense at least part of the water it contains, means for removing the water separated from the gas from the phase separator, means for removing a dried gas from the phase separator and means for sending the dried gas to mix with the first gas upstream of the adsorption drying unit and possibly upstream of the compressor.

De préférence, le procédé de séparation par absorption est un procédé physicochimique sélectif au CO2. Preferably, the absorption separation process is a CO2-selective physicochemical process.

De préférence, le procédé de séparation par absorption est un procédé de lavage aux amines. L’appareil peut comprendre des moyens pour envoyer le gaz séché se mélanger au premier gaz en amont de l’unité de séchage par adsorption et en aval du compresseur. Preferably, the absorption separation process is an amine washing process. The apparatus may include means for sending the dried gas to mix with the first gas upstream of the adsorption drying unit and downstream of the compressor.

L’invention sera décrite de manière plus détaillée en se référant aux figures où : La figure 1 représente un procédé selon l’invention. The invention will be described in more detail with reference to the figures where: Figure 1 represents a method according to the invention.

La figure 2 représente un procédé selon l’invention. Figure 2 shows a method according to the invention.

La figure 3 représente un procédé selon l’invention. La figure 4 représente un procédé selon l’invention. Figure 3 shows a method according to the invention. Figure 4 shows a method according to the invention.

Dans la Figure 1, un débit 3 d’une unité d’absorption A contient du dioxyde de carbone, de l’eau, de l’hydrogène et/ou de l’azote et éventuellement du monoxyde de carbone et/ou du méthane. Le débit 3 contient typiquement entre 6 et 7% mol d’eau. L’unité d’absorption peut utiliser un procédé physico-chimique sélectif au CO2 et par exemple peut utiliser un lavage aux amines, un lavage chaud au carbonate de potassium, un lavage de type Purisol ® avec lavage du NMP) et produit le débit 3 à sensiblement la pression atmosphérique ou des pressions plus élevées. Dans certains cas, il est donc nécessaire de surpresser le débit 3 avec une soufflante B afin d’amener sa pression à environ 1 ,5 bars abs ou plus. Le débit 3 est ensuite refroidi par échange de chaleur indirect avec de l’eau 11 dans le refroidisseur K pour condenser au moins une partie 7 de l’eau qu’il contient. Le gaz séché 9 sort du séparateur S utilisé pour enlever l’eau 7 et est envoyé se mélanger avec le gaz résiduaire 1 d’un procédé de séparation d’hydrogène par adsorption à bascule de pression P. Ce premier gaz 1 contient du dioxyde de carbone, de l’hydrogène et de l’eau et habituellement a une teneur en dioxyde de carbone moins élevée que le débit 3. Le premier gaz 1 habituellement a une teneur en eau moins élevée que le débit 3. Le débit du premier gaz 1 est de préférence supérieur à celui du deuxième gaz 3. In Figure 1, a flow 3 of an absorption unit A contains carbon dioxide, water, hydrogen and/or nitrogen and possibly carbon monoxide and/or methane. Flow 3 typically contains between 6 and 7 mol% water. The absorption unit may use a CO2-selective physicochemical process and for example may use an amine wash, a hot potassium carbonate wash, a Purisol® type wash with NMP wash) and produces flow 3 at substantially atmospheric pressure or higher pressures. In some cases, it is therefore necessary to boost flow 3 with a blower B in order to bring its pressure to approximately 1.5 bar abs or more. Flow 3 is then cooled by indirect heat exchange with water 11 in cooler K to condense at least a portion 7 of the water it contains. The dried gas 9 exits the separator S used to remove the water 7 and is sent to mix with the waste gas 1 from a pressure swing adsorption hydrogen separation process P. This first gas 1 contains carbon dioxide, hydrogen and water and usually has a lower carbon dioxide content than the flow 3. The first gas 1 usually has a lower water content than the flow 3. The flow rate of the first gas 1 is preferably higher than that of the second gas 3.

La séparation d’un tel débit est bien connue et est décrite par exemple dans US8021464. The separation of such a flow is well known and is described for example in US8021464.

Le mélange 15 est ensuite traité dans une unité de séparation C. Il est comprimé jusqu’à une pression au-dessus de 9 bars abs, voire au-dessus de 20 bars, séché par adsorption pour enlever les restants d’eau et ensuite refroidi et séparé par condensation partielle et/ou distillation pour obtenir au moins un gaz et/ou au moins un liquide enrichi en CO2 contenant par exemple au moins 90% mol, voire au moins 95% mol CO2 et un gaz enrichi en hydrogène. La soufflante B, si présente, peut comprimer le gaz 9 jusqu’à la pression du gaz 1 ou jusqu’à la pression à l’entrée du sécheur 19 de la figure 4. The mixture 15 is then treated in a separation unit C. It is compressed to a pressure above 9 bar abs, or even above 20 bar, dried by adsorption to remove the remaining water and then cooled and separated by partial condensation and/or distillation to obtain at least one gas and/or at least one liquid enriched in CO2 containing for example at least 90 mol%, or even at least 95 mol% CO2 and a gas enriched in hydrogen. Blower B, if present, can compress gas 9 to the pressure of gas 1 or to the pressure at the inlet of dryer 19 of Figure 4.

Dans la figure 2, le débit 3 est refroidi dans un refroidisseur R en amont du refroidisseur K et en aval de l’unité d’absorption A et éventuellement de la soufflante B. Ce refroidisseur R permet l’échange de chaleur indirect entre le gaz 9 séché provenant du séparateur S et du débit à refroidir 3. Le gaz refroidi dans le refroidisseur R est mélangé avec le premier gaz 1 comme pour la figure 1. Ceci permet de réduire la consommation d’eau 11 . In Figure 2, the flow 3 is cooled in a cooler R upstream of the cooler K and downstream of the absorption unit A and possibly the blower B. This cooler R allows indirect heat exchange between the dried gas 9 coming from the separator S and the flow to be cooled 3. The gas cooled in the cooler R is mixed with the first gas 1 as in Figure 1. This reduces the water consumption 11.

Dans certains cas, le débit 3 est disponible à plus haute pression que le premier gaz 1 et donc le débit 9 peut être mélange avec le résiduaire 3 après la compression du résiduaire 3 dans au moins un étage du compresseur de l’unité C. In some cases, flow 3 is available at higher pressure than the first gas 1 and therefore flow 9 can be mixed with the residual 3 after compression of the residual 3 in at least one stage of the compressor of unit C.

Dans la figure 3, le débit 3 est refroidi pour condenser l’eau au moins d’un liquide 15 enrichi en CO2 par rapport au mélange provenant d’au moins un séparateur de phases de l’unité C où se sépare le mélange 13. Le liquide est envoyé au refroidisseur K à une température inférieure à 0°C et se vaporise dans le refroidisseur K. Le liquide 15 peut autrement constituer une partie du liquide de cuve d’une colonne de distillation, ce liquide comprenant au moins 90% mol CO2. L’usage d’un tel débit permet de réduire la consommation d’eau 11 et en plus réalise la vaporisation nécessaire pour produire le liquide 15 sous forme gazeuse pour être envoyé au client. In Figure 3, the flow 3 is cooled to condense water at least from a liquid 15 enriched in CO2 relative to the mixture coming from at least one phase separator of the unit C where the mixture 13 separates. The liquid is sent to the cooler K at a temperature below 0°C and vaporizes in the cooler K. The liquid 15 can otherwise constitute a part of the tank liquid of a distillation column, this liquid comprising at least 90 mol% CO2. The use of such a flow makes it possible to reduce the consumption of water 11 and in addition achieves the vaporization necessary to produce the liquid 15 in gaseous form to be sent to the customer.

La Figure 4 montre une version de la Figure 1 avec l’unité C illustrée de manière plus détaillée. L’unité C comprend un compresseur 17, une unité de séchage par adsorption (TSA) 19, une ligne d’échange 21 pour refroidir le mélange comprimé et séché et une partie de séparation 23 par condensation partielle et/ou distillation produisant au moins un fluide enrichi en CO2 25 par rapport au mélange 13. L’invention présente le plus d’intérêt quand le débit du gaz 3 est plus faible que le débit du gaz 1 car mélanger le débits 1 , 9 oblige à surdimensionner l’unité C. L’invention s’applique particulièrement au cas où le rapport entre le débit du gaz 3 et celui du débit 1 est inférieur à 0,1 , le rapport exact état dépendant de facteurs économiques. Figure 4 shows a version of Figure 1 with unit C illustrated in more detail. Unit C comprises a compressor 17, an adsorption drying unit (TSA) 19, an exchange line 21 for cooling the compressed and dried mixture and a separation part 23 by partial condensation and/or distillation producing at least one fluid enriched in CO2 25 relative to the mixture 13. The invention is of most interest when the flow rate of gas 3 is lower than the flow rate of gas 1 because mixing flow rates 1, 9 requires oversizing unit C. The invention is particularly applicable to the case where the ratio between the flow rate of gas 3 and that of flow rate 1 is less than 0.1, the exact ratio depending on economic factors.

Néanmoins en termes d’investissement, l’équipement pour comprimer et traiter les débits 1 , 3 ensemble est moins cher que celui pour les séparer séparément. However, in terms of investment, the equipment to compress and process flows 1, 3 together is cheaper than that to separate them separately.

De plus comme le débit 3 est souvent plus riche en CO2 que le débit 1 , le fait de rajouter le débit 9 au gaz 1 augmente le poids moléculaire du gaz 1 et rend la compression dans l’unité C plus efficace. La séparation par condensation partielle et/ou par distillation est aussi plus efficace quand le débit à séparer est plus riche en CO2. Furthermore, since flow 3 is often richer in CO2 than flow 1, adding flow 9 to gas 1 increases the molecular weight of gas 1 and makes the compression in unit C more efficient. Separation by partial condensation and/or distillation is also more efficient when the flow to be separated is richer in CO2.

D’autre part, le gaz résiduaire du PSA H2 subit des fluctuations de composition du fait de la cyclicité du procédé PSA. Le mélanger avec un gaz à composition fixe permet d’atténuer l’effet de ces variations de compositions sur le compresseur et le procédé de séparation en aval. On the other hand, the PSA H2 waste gas undergoes composition fluctuations due to the cyclicity of the PSA process. Mixing it with a fixed composition gas helps to mitigate the effect of these composition variations on the compressor and the downstream separation process.

Enfin l’unité C permet d’éliminer des impuretés restantes dans le débit 3 par exemple l’azote et/ou l’hydrogène, le monoxyde de carbone et le méthane, alors que l’absorption ne permet pas de s’en débarrasser. Ainsi l’unité C permet de produire un CO2 de bonne qualité avec le gaz riche en CO2 d’une unité d’absorption. Finally, unit C allows the elimination of impurities remaining in flow 3, for example nitrogen and/or hydrogen, carbon monoxide and methane, while absorption does not allow them to be removed. Thus, unit C allows the production of good quality CO2 with the CO2-rich gas from an absorption unit.

Claims

Revendications Claims 1. Procédé de séparation de CO2 par condensation partielle et/ou distillation dans lequel i) un premier gaz (1) contenant de l’hydrogène, de l’eau et du dioxyde de carbone est comprimé dans un compresseur (17), séché dans une unité de séchage par adsorption (19) et ensuite séparé par condensation partielle et/ou distillation pour produire un fluide enrichi en CO2 (25), ii) un deuxième gaz (3), contenant du dioxyde de carbone, de l’hydrogène et/ou de l’azote ainsi que de l’eau ainsi qu’éventuellement du monoxyde de carbone et/ou du méthane, provenant d’un procédé de séparation par absorption (A), est refroidi pour condenser au moins une partie (7) de l’eau qu’il contient, l’eau est séparée du gaz formant un gaz séché (9) et le gaz séché est mélangé au premier gaz en amont de l’unité de séchage par adsorption et éventuellement en amont du compresseur. 1. A process for separating CO2 by partial condensation and/or distillation, in which i) a first gas (1) containing hydrogen, water and carbon dioxide is compressed in a compressor (17), dried in an adsorption drying unit (19) and then separated by partial condensation and/or distillation to produce a CO2-enriched fluid (25), ii) a second gas (3), containing carbon dioxide, hydrogen and/or nitrogen as well as water and optionally carbon monoxide and/or methane, originating from an absorption separation process (A), is cooled to condense at least a portion (7) of the water it contains, the water is separated from the gas forming a dried gas (9) and the dried gas is mixed with the first gas upstream of the adsorption drying unit and optionally upstream of the compressor. 2. Procédé selon la revendication 1 dans lequel le deuxième gaz (3) est comprimé (B) en amont du refroidissement jusqu’à une pression qui est celle du premier gaz en amont de l’unité de séchage par adsorption (21). 2. Method according to claim 1 in which the second gas (3) is compressed (B) upstream of the cooling to a pressure which is that of the first gas upstream of the adsorption drying unit (21). 3. Procédé selon l’une des revendications précédentes dans lequel le deuxième gaz (3) est refroidi par échange de chaleur indirect avec de l’eau (11). 3. Method according to one of the preceding claims, in which the second gas (3) is cooled by indirect heat exchange with water (11). 4. Procédé selon l’une des revendications précédentes dans lequel le deuxième gaz (3) est refroidi par échange de chaleur indirect avec un fluide, éventuellement enrichi en CO2 (15), produit par la condensation partielle et/ou la distillation, éventuellement à une température en dessous de 0°C. 4. Method according to one of the preceding claims, in which the second gas (3) is cooled by indirect heat exchange with a fluid, optionally enriched with CO2 (15), produced by partial condensation and/or distillation, optionally at a temperature below 0°C. 5. Procédé selon l’une des revendications précédentes dans lequel le deuxième gaz séché (9) est réchauffé par échange de chaleur avec le deuxième gaz (3) en amont du refroidissement (K). 5. Method according to one of the preceding claims, in which the second dried gas (9) is reheated by heat exchange with the second gas (3) upstream of the cooling (K). 6. Procédé selon l’une des revendications précédentes dans lequel le premier gaz (1) est un gaz résiduaire d’un procédé de séparation par adsorption (P) produisant un gaz enrichi en hydrogène et un gaz appauvri en hydrogène qui est le gaz résiduaire. 6. Method according to one of the preceding claims in which the first gas (1) is a residual gas from an adsorption separation process (P) producing a hydrogen-enriched gas and a hydrogen-depleted gas which is the residual gas. 7. Procédé selon l’une des revendications précédentes dans lequel la teneur en CO2 et/ou en eau du premier gaz (1) est plus basse que celle du deuxième gaz (3). 7. Method according to one of the preceding claims, in which the CO2 and/or water content of the first gas (1) is lower than that of the second gas (3). 8. Procédé selon l’une des revendications précédentes dans lequel la teneur en CO2 du mélange (13) formé en mélangeant le gaz séché (9) au premier gaz est supérieure à celle du premier gaz (1). 8. Method according to one of the preceding claims, in which the CO2 content of the mixture (13) formed by mixing the dried gas (9) with the first gas is greater than that of the first gas (1). 9. Procédé selon l’une des revendications précédentes dans lequel le rapport entre les débits du premier et du deuxième gaz est au moins égal à 10. 9. Method according to one of the preceding claims in which the ratio between the flow rates of the first and second gases is at least equal to 10. 10. Appareil de séparation de CO2 par condensation partielle et/ou distillation comprenant un compresseur (17), une unité de séchage par adsorption (19), une unité de séparation par condensation partielle et/ou distillation (C), des moyens pour envoyer un premier gaz (1) contenant de l’hydrogène, de l’eau et du dioxyde de carbone être comprimé dans le compresseur (17), des moyens pour envoyer le premier gaz comprimé être séché dans l’unité de séchage par adsorption (19) et des moyens pour envoyer le premier gaz comprimé et séché être séparé par condensation partielle et/ou distillation pour produire un fluide enrichi en CO2 (25), un refroidisseur (K), un séparateur de phases, des moyens pour envoyer un deuxième gaz (3), contenant du dioxyde de carbone, de l’hydrogène et/ou de l’azote ainsi que de l’eau ainsi qu’éventuellement du monoxyde de carbone et/ou du méthane, provenant d’un procédé de séparation par absorption (A), au refroidisseur pour être refroidi pour condenser au moins une partie (7) de l’eau qu’il contient, des moyens pour sortir l’eau séparée du gaz du séparateur de phases, des moyens pour sortir un gaz séché (9) du séparateur de phases et des moyens pour envoyer le gaz séché se mélanger au premier gaz en amont de l’unité de séchage par adsorption et éventuellement en amont du compresseur. 10. Apparatus for separating CO2 by partial condensation and/or distillation comprising a compressor (17), an adsorption drying unit (19), a partial condensation and/or distillation separation unit (C), means for sending a first gas (1) containing hydrogen, water and carbon dioxide to be compressed in the compressor (17), means for sending the compressed first gas to be dried in the adsorption drying unit (19) and means for sending the compressed and dried first gas to be separated by partial condensation and/or distillation to produce a CO2-enriched fluid (25), a cooler (K), a phase separator, means for sending a second gas (3), containing carbon dioxide, hydrogen and/or nitrogen as well as water and optionally carbon monoxide and/or methane, coming from an absorption separation process (A), to the cooler to be cooled to condense at least a portion (7) of the water it contains, means for removing the separated water gas from the phase separator, means for removing a dried gas (9) from the phase separator and means for sending the dried gas to mix with the first gas upstream of the adsorption drying unit and possibly upstream of the compressor. 11 . Appareil selon la revendication 10 où le procédé de séparation par absorption (A) est un procédé physico-chimique sélectif au CO2. 11. Apparatus according to claim 10, wherein the absorption separation process (A) is a CO2-selective physicochemical process. 12. Appareil selon la revendication 11 où le procédé de séparation par adsorption (A) est un procédé de lavage aux amines. 12. Apparatus according to claim 11 wherein the adsorption separation process (A) is an amine washing process.
PCT/EP2024/060655 2023-05-17 2024-04-19 Method and apparatus for separating co2 by partial condensation and/or distillation Pending WO2024235563A1 (en)

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US8021464B2 (en) 2004-11-16 2011-09-20 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method and installation for combined production of hydrogen and carbon dioxide
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