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WO2010130781A1 - Procede et systeme de separation de co2 d'un gaz de synthese ou d'un gaz de carneau - Google Patents

Procede et systeme de separation de co2 d'un gaz de synthese ou d'un gaz de carneau Download PDF

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Publication number
WO2010130781A1
WO2010130781A1 PCT/EP2010/056541 EP2010056541W WO2010130781A1 WO 2010130781 A1 WO2010130781 A1 WO 2010130781A1 EP 2010056541 W EP2010056541 W EP 2010056541W WO 2010130781 A1 WO2010130781 A1 WO 2010130781A1
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Prior art keywords
stream
gas stream
liquid phase
gas
compressed
Prior art date
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PCT/EP2010/056541
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English (en)
Inventor
Eva Marfilia Van Dorst
Gerard De Nazelle
Hendrik Jan Van Der Ploeg
Rick Van Der Vaart
Evert Wesker
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority to US13/320,298 priority Critical patent/US20120167620A1/en
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP10718227A priority patent/EP2429683A1/fr
Priority to CN2010800211430A priority patent/CN102427868A/zh
Priority to JP2012510291A priority patent/JP2012526962A/ja
Priority to AU2010247399A priority patent/AU2010247399B2/en
Priority to CA2760602A priority patent/CA2760602A1/fr
Publication of WO2010130781A1 publication Critical patent/WO2010130781A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/50—Carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2900/00—Special arrangements for conducting or purifying combustion fumes; Treatment of fumes or ashes
    • F23J2900/15061—Deep cooling or freezing of flue gas rich of CO2 to deliver CO2-free emissions, or to deliver liquid CO2
    • 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
    • F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
    • 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
    • F25J2210/70—Flue or combustion exhaust 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
    • 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
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/80—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being 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
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/80—Hot exhaust gas turbine combustion engine
    • 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
    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/80—Integration in an installation using carbon dioxide, e.g. for EOR, sequestration, refrigeration etc.
    • 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
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • 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
    • F25J2270/12—External refrigeration with liquid vaporising loop
    • 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
    • F25J2270/60—Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-hydrocarbons
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/32—Direct CO2 mitigation
    • 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 and system for separating at least CO2 from a synthesis gas stream or a flue gas stream.
  • Flue gas comprises for instance N2, CO2 and other combustion products.
  • Synthesis gas streams are gaseous streams mainly comprising carbon monoxide and hydrogen. Synthesis gas streams are for instance produced via partial oxidation or steam reforming of hydrocarbons including natural gas, coal bed methane, distillate oils and residual oil, and by gasification of solid fossil fuels such as coal or coke. Reference is made "The Shell Middle Distillate Synthesis Process, Petroleum Review Apr. 1990 pp. 204- 209" by Maarten van der Burgt et al . for a general description on the preparation of synthesis gas.
  • solid or very heavy (viscous) fossil fuels which may be used as feedstock for generating synthesis gas, including solid fuels such as anthracite, brown coal, bituminous coal, sub-bituminous coal, lignite, petroleum coke, peat and the like, and heavy residues, for instance hydrocarbons extracted from tar sands, residues from refineries such as residual oil fractions boiling above 360 0 C, directly derived from crude oil, or from oil conversion processes such as thermal cracking, catalytic cracking, hydrocracking etc. All such types of fuels have different proportions of carbon and hydrogen, as well as different substances regarded as contaminants.
  • the synthesis gas may comprise contaminants such as carbon dioxide (CO2), hydrogen sulphide, carbonyl sulphide and carbonyl disulphide while also containing nitrogen, nitrogen-containing components (e.g. HCN and NH3) , metals, metal carbonyls (especially nickel carbonyl and iron carbonyl) , steam and in some cases mercaptans .
  • CO2 carbon dioxide
  • hydrogen sulphide hydrogen sulphide
  • carbonyl sulphide and carbonyl disulphide while also containing nitrogen, nitrogen-containing components (e.g. HCN and NH3)
  • metals metal carbonyls (especially nickel carbonyl and iron carbonyl)
  • steam in some cases mercaptans .
  • the synthesis gas stream may be treated to remove contaminants and/or to adjust the H2/CO ratio.
  • 2008/068305 describes subjecting part of a synthesis gas stream comprising contaminants to a water gas shift reaction and using a combination of bulk contaminants removal followed by polishing to remove contaminants to a predetermined level.
  • WO-2008/153379 provides a method for separating CO2 from a flue gas or synthesis gas mixture.
  • the method includes cooling the gas mixture in a heat exchanger, and subsequently expanding the gas mixture adiabatically to cool the gas to a temperature and pressure at which the CO2 in the mixture is at least partially in the liquid phase.
  • the gas mixture may be pressurized to increase the temperature drop during expansion.
  • the liquid fraction, including CO2 is subsequently separated from the cooled and expanded mixture .
  • the present invention aims to provide an improved method and system for separating CO2 from a gas stream.
  • the invention accordingly provides a method for separating CO2 from a synthesis gas stream or a flue gas stream, the method comprising the steps of:
  • the present invention however teaches to first compress the gas stream, to be able to provide product streams at an increased pressure relative to the input gas stream. As the pressure of the product streams is increased relative to the initial pressure, the product streams can be directly supplied for further processing. The pressure of one product stream may be for instance suitable for injecting CO2 in a subterranean reservoir. Additionally, the method of the present invention removes more CO2 in a single process step than prior art methods, rendering the method more efficient.
  • the initial pressure is in the range of 20 to 65 bar, preferably about 35 to 60 bar.
  • the method is thus suitable for directly handling synthesis gas from a plant.
  • the synthesis gas may be of varying or predetermined composition.
  • the H2/CO ratio of the synthesis gas can be determined by including the water gas shift reaction in the method of the invention.
  • the output pressure of the liquid phase is above 75 bar, or preferably in the range of 100 to 200 bar.
  • the liquid phase stream can be directly processed, thus obviating the need to pump or otherwise treat the product stream.
  • the liquid phase stream can for instance be directly injected in a subterranean reservoir.
  • the overall process is relatively efficient. If the output pressure of the liquid phase is not sufficiently high to allow for direct injection in a reservoir, then a pump may be added to the system to increase the pressure of the liquid phase stream sufficiently to allow for direct reservoir inj ection .
  • the output pressure is in the range of 140 to 160 bar. At this pressure, which is determined by the compression of the gas stream, the efficiency of the CO2 removal process is relatively high.
  • the capture rate is for instance above 85%, or in the order of 90%.
  • the gas stream is a synthesis gas stream, which is subjected to a water shift reaction, to provide a shifted synthesis gas stream having an increased H2 and CO2 content. By increasing the H2 and CO2 content, the efficiency of the process increases.
  • the shifted synthesis gas stream mainly comprises H2 and CO2. Mainly herein indicates for instance more than 40 to 50 mol% H2 and more than 40 mol% CO2.
  • the CO2 can be captured and stored in a reservoir.
  • the H2 rich gaseous stream can be used as fuel for several applications, for instance for fuelling a generator for generating electrical power.
  • the output pressure of the gaseous phase is substantially similar to the output pressure of the liquid phase.
  • the pressurized and H2 rich gaseous phase can for instance be used to fuel an electrical generator.
  • the present invention provides a system for separating C02 from a gas stream containing C02, the system comprising:
  • At least one cooling device for cooling the compressed gas stream, wherein the compressed and cooled gas stream has a pressure and temperature at which the CO2 in the gas stream is at least partially converted to the liquid phase;
  • Figure 1 schematically shows an embodiment of a system according to the present invention
  • Figure 2 schematically shows another embodiment of a system according to the present invention
  • Figure 3 schematically shows yet another embodiment of a system according to the present invention
  • Figure 4 schematically shows yet another embodiment of a system according to the present invention
  • Figure 5 schematically shows an alternate design of the system shown in Figure 4; and Figure 6 shows an exemplary phase diagram of a gas stream containing C02.
  • a feed gas stream 100 is supplied to the system 102 of the present invention ( Figures 1-3) .
  • the system 102 includes a compressor 104 to compress the gas stream and provide a compressed gas stream 106.
  • Compressor 104 may also further comprise an after cooler to pre-cool the compressed gas stream 106.
  • the system 102 includes one or more, for instance three, heat exchangers 108, 110, 112 for cooling the compressed gas stream.
  • a cooled and compressed gas stream 114 is directed to a separator 116.
  • the separator provides a gaseous stream 118 and a liquid phase stream 120.
  • the gaseous stream 118 may optionally be directed to the first heat exchanger 108 (Fig. 1) or the second heat exchanger (Fig. 2) for cooling the compressed gas stream.
  • the liquid phase stream 120 may optionally be directed to the second heat exchanger 110 (Fig. 1) or the first heat exchanger (Fig. 2) for further cooling the compressed gas stream.
  • the first heat exchanger 108 may use air, or (sea) water 122 to pre-cool the compressed gas stream 106 (Fig. 3) .
  • a multi-stream heat exchanger 109 may be used in place of heat exchangers 108 and 110.
  • the respective heat exchangers supply a gas phase stream 124 and/or liquid phase stream 126 having an increased temperature relative to streams 118, 120.
  • the pressure drop after the heat exchangers is for instance in the order of 0.5 to 10 bar, typically in the order of 1 to 5 bar.
  • Separation of C02, and possibly other contaminants such as H2S, from H2 and CO in a (shifted) synthesis gas stream is achieved by phase change.
  • the composition of the synthesis gas stream may be adjusted using a shift reaction, such that the synthesis gas stream has a predetermined H2/CO ratio.
  • the synthesis gas may then be compressed to a pressure that is required for injection of C02 in a reservoir.
  • the reservoir is for instance a subterranean reservoir, such as a (partially depleted) gas field and/or a sub-sea reservoir.
  • Synthesis gas comprises for instance about 25-35 mol% H2, 60-70 mol% CO, some CO2 and contaminants. Part of the CO is converted in a gas mixture comprising 50-60 mol% H2, 35-50 mol% CO2, and for instance some CO and H2S.
  • the synthesis gas is typically provided at a pressure in the range of 25 to 60 bar, say for instance about 35-40 bar or about 60 bar. This initial pressure is raised to about 100 to 200 bar, or preferably about 140 to 160 bar. The pressure drop after each heat exchanger is relatively small, in the range of about 0,5 to 5 bar.
  • the CO2 (and optionally the other contaminants) are removed by cooling down the compressed synthesis gas to a temperature at which the CO2 at least partially shifts to the liquid phase .
  • the cooling may be done in one or more steps, for instance three steps as shown in Figures 1 to 3.
  • the product stream may be directed to a first and second heat exchanger respectively (Fig. 1 and 2), to cool the compressed gas stream.
  • a third heat exchanger using additional cooling power may be included.
  • the third heat exchanger may use for instance ethane and/or propane as refrigerant.
  • the cooling power required from the third heat exchanger can be diminished with for instance about 40 to 60% by using the latent cold of the product streams to cool the compressed gas.
  • FIG 4 shows an alternative embodiment in which a feed gas stream 100 is supplied to compressor 104.
  • a multi- stream heat exchanger 109 is used that performs the function of heat exchangers 108 and 110.
  • the heat exchanger 109 may also use additional propane from an external cooling system as additional refrigerant, to minimise the size of heat exchanger 112.
  • a feed gas stream 100 is also supplied to compressor 104; however, the compressed gas stream 106 is split into at least two separate streams 106A and 106B.
  • heat exchangers 108 and 110 are arranged in parallel and streams 106A and 106B are fed into heat exchanger 108 and 110, respectively.
  • the cooled and compressed output streams are then recombined and directed to separator 116 via the heat exchanger 112.
  • the separator 116 provides a gaseous stream 118 and a liquid stream 120.
  • two streams 106A and 106B are shown in Figure 5, if desired, the compressed gas stream 106 may be split into more than two streams and fed into the respective number of heat exchangers.
  • the gaseous stream 118 in Figure 4 may optionally be directed to the multi-stream exchanger 109 or, in the embodiment of Figure 5, to first heat exchanger 108 or the second heat exchanger 110 for cooling the compressed gas stream; similarly, the liquid phase stream 120 may optionally be directed to the second heat exchanger 110 or the first heat exchanger 108 for further cooling the compressed gas stream in the case of the embodiment of Figure 5 or to multi-stream heat exchanger 109 in the case of the embodiment of Figure 4.
  • the embodiments shown in Figures 4 and 5 allow heat exchanger 112 to be made smaller thus achieving savings in capital costs and energy usage.
  • the embodiment shown in Figure 4 is preferred.
  • the system shown in Figures 1-5 removes 75% to 80% of the CO2 from the feed gas stream 100. If an even greater level of CO2 removal is desired, a further treatment of gas phase stream 124 may be performed, using for example commercially available CO2 removal processes, such as absorption processes using physical solvent or amine solvents, or adsorption processes using pressure swing or temperature swing regeneration. Such further treatment results in the removal of up to 100% of the CO2 from the feed gas stream. Also, as shown in Figures 4 and 5, an expander 125 may be used to provide power recovery and additional cooling of gas phase stream 124, if desired, which may be applied in heat exchanger 109 (Fig. 4) or heat exchanger 110 (Fig. 5) for additional cooling of stream 106.
  • a further treatment of gas phase stream 124 may be performed, using for example commercially available CO2 removal processes, such as absorption processes using physical solvent or amine solvents, or adsorption processes using pressure swing or temperature swing regeneration. Such further treatment results in the removal of up to 100% of the CO2 from the feed
  • Figure 6 shows an exemplary phase diagram of synthesis gas having a certain composition.
  • the x-axis indicates temperature T (in 0 C) and the y-axis indicates pressure P (in bar) .
  • the separate phases are indicated with liquid L, vapour V, gas G, solid S, and respective mixtures thereof (GL, VL, GS, VS) .
  • Lines 400, 402 indicate boundaries of the respective phase mixtures.
  • Gaseous phase as used herein refers to gas as well as vapour .
  • the gas stream is for example cooled to a temperature within the range of about -30 to -60 0 C to obtain a mixture that is partly comprised of gas or vapour, and partly of liquid.
  • the gas is cooled to about -55 0 C.
  • the method and system of the present invention can capture a larger percentage of the CO2 in a single process step. This can be recognized using the following, non-limiting example. A triple point will for instance be at about a pressure of 15 bar, and temperature of -55 0 C.
  • the partial pressure p x of component i of the gas relates to the total pressure P, molar percentage V 1 , volume percentage X 1 , and pressure of the volume percentage P x v as :
  • the CO2 capture rate ⁇ C o 2 at the downstream end can hence be formulated as:
  • the C02 capture may be in the order of 90 mol% (for ideal gas) :
  • the feed synthesis gas is for instance supplied, preferably after shifting the gas using a water gas shift reaction.
  • the shifted synthesis gas comprises mainly H2 and CO2, for instance in the order of 40-45 mol% CO2, 50- 55 mol% H2.
  • the shifted synthesis gas includes for instance about 2 mol% CO and/or 1 mol% H2S.
  • the synthesis gas supplied to the process of the present invention has for instance an initial temperature in the range of 45 to 55 0 C, and/or an initial pressure in the order of 35 to 40 bar.
  • the gaseous product stream may include for instance
  • the liquid phase product stream may include about 90 to 98 mol% CO2, ⁇ 5 mol% H2, and/or ⁇ 1 mol% CO.
  • a refrigeration machine using for instance ethane and/or propane as working fluid, may be included in one or more stages. If the refrigeration machine is for instance used in the last step, the final cooling device may operate at for instance 0.25 MW/kg CO2.
  • kg CO2 indicates a kilogram of CO2 in the liquid phase stream.
  • the cold, H2 rich gas phase stream and/or the CO2 rich liquid phase stream may be directed to one of the heat exchangers--for instance to the first and/or second heat exchanger to provide another part of the required duty, for instance about 0.21 MW/kg CO2.
  • the compressed gas stream 106 may be thus cooled in subsequent steps, to for instance 1-10 0 C after the first heat exchanger 108, -15 to -25 0 C after the second heat exchanger 110, and/or -55 to -30 0 C after the third heat exchanger 112.
  • the separation technology used is not critical to the method of the invention and conveniently a proven gas/liquid separation technology may be used to capture the liquid CO2 droplets.
  • Such technology includes for instance a demister mat or vane pack as used in an interstage cooler of a compressor, a swirl tube or cyclone .
  • the product streams are supplied at pressures and temperatures that are suitable for further practical use, possibly without further treatment.
  • the method and device of the present invention provide an efficient and cost effective improvement for removing CO2 from a gas stream.
  • the gaseous product stream comprising a relatively high mol% H2, for instance about or more than 90 mol% H2, can be readily used in subsequent process steps. These process steps include for instance fuelling a generator for generating electricity.
  • the H2 rich stream may also be directed to a refinery, to introduce the stream in a hydrotreater or hydrocracker, or similar devices for reducing the length of hydrocarbons.
  • the method and system of the present invention are specifically suited to capture CO2 from a synthesis gas stream or a flue gas stream.
  • the method seems unsuitable for treating natural gas, as a significant fraction of the methane would condense together with the CO2 upon pressurizing and cooling the gas.
  • the synthesis gas or flue gas lack methane but include H2 or N2 respectively. The latter will not condense at the pressures and temperatures involved in the method of the invention.
  • cooling synthesis gas or flue gas according to the method of the invention turns out to be more efficient than cooling by expansion. On the contrary, natural gas can be more effectively cooled by expansion to relatively low pressures, below 35 bar.

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  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
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  • Physics & Mathematics (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Gas Separation By Absorption (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Treating Waste Gases (AREA)
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Abstract

L'invention concerne un procédé et un système de séparation de CO2 d'un flux gazeux contenant du CO2. Un flux gazeux présentant une pression initiale est comprimé puis refroidi. Le flux gazeux comprimé et refroidi présente une pression accrue et une température réduite auxquelles le CO2 contenu dans le flux gazeux est au moins partiellement converti en phase liquide. La phase liquide est séparée du flux gazeux comprimé et refroidi, de sorte à obtenir un flux en phase liquide et un flux en phase gazeuse, la pression de sortie du flux en phase liquide étant supérieure à la pression initiale du flux gazeux.
PCT/EP2010/056541 2009-05-15 2010-05-12 Procede et systeme de separation de co2 d'un gaz de synthese ou d'un gaz de carneau Ceased WO2010130781A1 (fr)

Priority Applications (6)

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US13/320,298 US20120167620A1 (en) 2009-05-15 2010-04-12 Method and system for separating co2 from synthesis gas or flue gas
EP10718227A EP2429683A1 (fr) 2009-05-15 2010-05-12 Procede et systeme de separation de co2 d'un gaz de synthese ou d'un gaz de carneau
CN2010800211430A CN102427868A (zh) 2009-05-15 2010-05-12 从合成气或烟道气中分离co2的方法和系统
JP2012510291A JP2012526962A (ja) 2009-05-15 2010-05-12 合成ガス又は燃焼排ガスからｃｏ２を分離するための方法及びシステム
AU2010247399A AU2010247399B2 (en) 2009-05-15 2010-05-12 Method and system for separating CO2 from synthesis gas or flue gas
CA2760602A CA2760602A1 (fr) 2009-05-15 2010-05-12 Procede et systeme de separation de co2 d'un gaz de synthese ou d'un gaz de carneau

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EP09160338.1 2009-05-15
EP09160338 2009-05-15

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CA (1) CA2760602A1 (fr)
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WO2012123752A3 (fr) * 2011-03-16 2015-02-19 Costain Oil, Gas & Process Limited Procédé et appareil pour la séparation de dioxyde de carbone et d'hydrogène
EP2895245A4 (fr) * 2012-09-17 2016-06-15 Gas Liquids Engineering Ltd Procédé pour l'optimisation de l'élimination de composants condensables d'un fluide
IT201600081328A1 (it) * 2016-08-02 2018-02-02 Saipem Spa Recupero di anidride carbonica da gas di sintesi in impianti per la produzione di ammoniaca per mezzo di separazione gravimetrica
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KR102212137B1 (ko) 2016-04-21 2021-02-03 퓨얼 셀 에너지, 인크 이산화탄소 포획을 위해 용융 탄산염 연료 전지 애노드 배기를 후가공처리하는 방법
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KR102807758B1 (ko) * 2017-01-19 2025-05-14 한화오션 주식회사 휘발성 유기 화합물 회수 시스템 및 회수 방법
KR102717676B1 (ko) * 2017-02-09 2024-10-15 한화오션 주식회사 휘발성 유기 화합물 회수 시스템 및 회수 방법
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JP7258144B2 (ja) 2018-11-30 2023-04-14 フュエルセル エナジー， インコーポレイテッド Ｃｏ２利用率を向上させて動作させる燃料電池のための改質触媒パターン
US12355085B2 (en) 2018-11-30 2025-07-08 ExxonMobil Technology and Engineering Company Cathode collector structures for molten carbonate fuel cell
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EP4066303A1 (fr) 2019-11-26 2022-10-05 ExxonMobil Technology and Engineering Company Ensemble pile à combustible à collecteur externe pour écoulement parallèle
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EP4118029B1 (fr) 2020-03-11 2025-11-05 Fuelcell Energy, Inc. Unité de reformage de méthane à la vapeur pour la capture de carbone
EP4176218A1 (fr) * 2020-07-02 2023-05-10 BLANK, Christian Appareil de séparation de mélange gazeux et procédé pour séparer au moins un fluide principal à partir d'un mélange gazeux
KR102851873B1 (ko) * 2021-02-26 2025-08-28 삼성중공업 주식회사 유증기 회수장치

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CA2760602A1 (fr) 2010-11-18
JP2012526962A (ja) 2012-11-01
US20120167620A1 (en) 2012-07-05
EP2429683A1 (fr) 2012-03-21
CN102427868A (zh) 2012-04-25
AU2010247399A1 (en) 2011-11-24

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