Classifications

• • 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
  • 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
  • B01D53/02—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
  • B01D53/06—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 moving adsorbents, e.g. rotating beds
  • B01D53/10—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 moving adsorbents, e.g. rotating beds with dispersed adsorbents
  • B01D53/12—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 moving adsorbents, e.g. rotating beds with dispersed adsorbents according to the "fluidised technique"
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/50—Carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/10—Inorganic adsorbents
  • B01D2253/102—Carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • 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
  • B01D2257/10—Single element gases other than halogens
  • B01D2257/102—Nitrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/10—Single element gases other than halogens
  • B01D2257/104—Oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/10—Single element gases other than halogens
  • B01D2257/11—Noble gases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/20—Halogens or halogen compounds
  • B01D2257/204—Inorganic halogen compounds
  • B01D2257/2045—Hydrochloric acid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/20—Halogens or halogen compounds
  • B01D2257/204—Inorganic halogen compounds
  • B01D2257/2047—Hydrofluoric acid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/20—Halogens or halogen compounds
  • B01D2257/206—Organic halogen compounds
  • B01D2257/2064—Chlorine
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/30—Sulfur compounds
  • B01D2257/302—Sulfur oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/30—Sulfur compounds
  • B01D2257/304—Hydrogen sulfide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/40—Nitrogen compounds
  • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/40—Nitrogen compounds
  • B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
• • 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
  • B01D2257/60—Heavy metals or heavy metal compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
  • B01D2257/708—Volatile organic compounds V.O.C.'s
• • 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
  • 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
  • B01D53/0462—Temperature 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
  • B01D53/02—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
• • 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
  • F25J2205/00—Processes or apparatus using other separation and/or other processing means
  • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
• • 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
  • F25J2205/00—Processes or apparatus using other separation and/or other processing means
  • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
• • 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
  • 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
  • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
  • F25J2230/80—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being carbon dioxide
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency
  • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• • 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
• • 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
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

• the invention relates to a method for purifying a flow of feed gas containing at least CO2 and at least one impurity characterized by the integration of a purification step, allowing at least partial elimination of the water.
• the combustion gases of fossil fuels and / or biomass or incineration of waste or gases from glass furnaces mainly contain heavy metals such as mercury arsenic, iron, nickel ..., organic pollutants and SOx or NOx compounds.
• EP-A-1332786 discloses a process for purifying a gas stream by removing NOx, SOx, Hg and HgO by oxidation with ozone.
• a problem is to provide an improved method for purifying a CO2-containing gas stream, i.e. a process which ensures a thorough removal of treated pollutants, in particular a thorough elimination of the water.
• the solution of the invention is then a process for purifying a feed gas stream containing CO2 and at least one impurity selected from water, nitrogen, oxygen, argon, rare gases , SOx, CS 2 H 2 S, NOx, HCN, HCl, CHCl 3 , HF, volatile organic compounds and the following metals: mercury, arsenic, iron, nickel, tin, lead, cadmium, vanadium, molybdenum and selenium, and the compounds derived from these metals, comprising the following successive steps: a) pretreatment step of the feed gas stream for at least partially removing one of the impurities; b) step of compressing the pretreated gas flow at a pressure of between 10 and 50 bar; c) step of removing at least one impurity at a temperature
• the pretreatment step a) may be any purification for removing at least one solid, liquid or gaseous component. This purification is located upstream of at least one compression phase; and if the feed gas stream is an oxy-fuel smoke, this purification is also located downstream of the oxy-fuel combustion boiler.
• separators both gas / liquid separators of various types
• the method according to the invention may have one of the following characteristics: after step d), the gas flow is in the liquid state and stored, or in the supercritical state and transported and / or stored, or in the gaseous state and transported;
• the purification step makes it possible to eliminate at least partially at least one other impurity chosen from nitrogen, oxygen, argon, rare gases, SOx, CS2, H2S, NOx, HCN, HCl and CHCl3; , HF, volatile organic compounds, the following metals: mercury, arsenic, selenium, cadmium, iron and carbonyl nickel, and compounds derived therefrom, preferably at least partially SOx;
• step a) the purification step is carried out between step a) and step b);
• step b) the purification step is carried out between step b) and step c);
• the compression step b) comprises successive compression phases and in that the purification step is carried out between two successive compression phases of said compression step b);
• the purification step is carried out at a pressure of between 2 bar absolute and 25 bar absolute, preferably between 3 and 9 bar absolute, more preferably between 3.5 and 6 bar absolute; in the purification step, one or more organic or inorganic materials are used to at least partially remove the water contained in the gas stream; in the purification step, one or more organic or inorganic materials, which are identical or different from those for removing water, are also used to at least partially eliminate at least one impurity chosen from nitrogen, oxygen and , argon, rare gases, SOx, CS 2 , H 2 S, NOx, HCN, HCl, CHCl 3 , HF, volatile organic compounds, the following metals: mercury, arsenic, selenium, cadmium, iron and nickel, and compounds derived from these metals, preferably at least partially SOx;
• the organic or inorganic materials are adsorbent materials
• the adsorbent materials are used in at least one fluidized bed reactor; the adsorbent materials are used in at least one fixed-bed reactor;
• each fluidized bed reactor in the adsorption phase corresponds to at least one fluidized-bed or falling-bed reactor in the regeneration phase;
• At least one of the reactors is subjected to a TSA cycle and at least one of the reactors is subjected to a PSA cycle;
• At least one reactor is subjected to both a TSA cycle and a PSA cycle
• At least one waste gas is recovered during the purification step
• a first waste gas having a content of NOx Tl and a second waste gas having a content of NOx T2 such as T2 ⁇ T1 are recovered; the first waste gas is recycled in an oxy-boiler;
• the recycled waste gas can be recycled anywhere upstream of the last liquid water outlet.
• This liquid water outlet can be in the low-pressure wash (s) of the pretreatment stage, in the condensers located between two compression phases or in an eventual high-pressure washing tower, located downstream of the compression;
• the second waste gas is either released directly to the atmosphere, or treated and then released into the atmosphere;
• the second waste gas is treated by washing and / or refrigeration followed by a gas-liquid separation; at least a portion of the stream of CO2-enriched gas resulting from the purification step makes it possible to regenerate at least part of the adsorbent materials of the purification unit;
• the volatile organic compounds are chosen from formaldehyde, acetaldehyde, formic acid, acrolein and acetic acid;
• the pretreatment step comprises at least one of the following treatments: catalysis, filtration, washing and desulfurization, with the washing being able to be coupled with a cooling of the feed gas.
• oxygen is understood to mean combustion during which the coal is burned in a fluid that is low in nitrogen, which may range from pure oxygen (> 95%) to a fluid containing the same quantity of oxygen as air (about 21%) obtained by mixing pure oxygen (> 95%) with recycled fumes rich in CO2.
• a TSA process for purifying a gaseous mixture can comprise the following steps:
• FIG. 1 represents a device making it possible to carry out a method according to the present invention characterized by the location of the purification step at the end of the compression cycle, that is to say between steps b) and c).
• the first step a) of the present invention aims at treating the fumes using known methods forming part of the state of the art. Washing is commonly found, which uses different liquids (or solvents) such as water, alcohols
• a washing in particular a washing with water, may be coupled with the partial cooling of the feed gas stream, thus ensuring the triple function of condensation of the heavier compounds, adsorption of the most soluble compounds and retention of solid particles, in particular containing metal compounds.
• the gas resulting from step a) may in general contain: a large majority of CO2 (generally greater than 80%); nitrogen oxides, called NOx, such as NO, NO2, N2O4 ...; - sulfur oxides, called SOx, such as SO2, SO3, H2SO4 ...; water at saturation (at the conditions of temperature and pressure of the flow).
• NOx nitrogen oxides
• SOx sulfur oxides
• the treatment processes in the first stage almost all require the contact of the gas with an aqueous solution; oxygen up to a few percent (derived from the excess compared to the stoichiometry necessary to ensure a good combustion efficiency); CO (unburnt combustion); incondensables vis-à-vis CO2: nitrogen, argon, oxygen and rare gases, mainly from the air inlets on the oxy-combustion boiler and the purity of oxygen; - heavy metals such as mercury, arsenic, iron, nickel, tin, lead, cadmium, vanadium, molybdenum, selenium and compounds derived from these metals; volatile organic compounds (VOCs), and unburned hydrocarbons.
• VOCs volatile organic compounds
• step b the gas flow is compressed to a sufficient pressure level to be able firstly to separate a part of the undesirable compounds in doing so (separators generally located immediately after each compression step followed a heat exchange to cool the flow of gas to remove the condensables that appeared during this cooling (water for example) and on the other hand to bring the gas under the right conditions (temperature and pressure) to prepare the elimination of other impurities in the following steps.
• a penultimate step c) will see the elimination of incondensable compounds.
• This third step can be optimized if it is carried out at low temperature, that is to say at a temperature ⁇ 5 ° C., preferably at a negative temperature, more preferably between -20 ° C. and -60 ° C. using exchangers combined with separators in a cold cycle.
• the fourth step d) then aims to recover a stream of purified gas, enriched in CO 2 .
• the generally used temperature level below 0 ° C. requires a reduction in the water content, and possibly some other compounds not sufficiently retained during the pre-treatment stage or during successive compressions and condensations. Indeed, the presence of water or these other compounds likely to be deposited in equipment such as heavy hydrocarbons, sulfur compounds or nitrogen compounds ... would prohibit reaching in the penultimate step c) the temperature levels sufficiently cold, preferably between -20 ° C and -60 ° C, to effectively produce a flow of CO 2 content in accordance with current standards. Producing efficiently means a global cost encompassing investment and energy related to this industrially acceptable production, aligned with the expectations of international organizations.
• the purification step (or so-called polishing) is required between the first step a) which pretreat the flow of feed gas for their subsequent processing and the third step c) which allows to to separate the incondensable compounds from the CO2 contained in the gas flow.
• This purification step may be placed throughout the second step b) which aims to gradually compress the gases from around atmospheric pressure to the pressure required mainly to separate the inert from the majority CO2.
• the choice of the location of the purification step will be a function of a number of criteria such as the investment, the type of materials in the second step b), the nature and the concentration of the impurities.
• the first possibility is to place the purification step at the beginning of step b), that is to say to carry out the purification at low pressure.
• this position has two disadvantages, namely:
• the position of the purification stage upstream of the compressor train constituting the second step b) makes it possible to envisage removing the impurities that are detrimental to the rest of the process: that is to say water, organic compounds volatile, metal-based compounds ... also, it may result in a certain advantage as to the nature of the materials to be used in the following, particularly in the steps of compressions.
• the second possibility is to place the purification step between two compression stages of the second step b).
• This second possibility makes it possible to dispose of the gas at an intermediate pressure between that which is close to the atmospheric (beginning of the second step b) and that which is required in the third step c) of the process. This necessarily results in a significant reduction in the installed volume and therefore the cost of the unit compared to an installation upstream of the compression step. This is all the more true that we move the purification step towards the end of the second step.
• the water may be the key element in the design of the purification unit implemented in step e) (in the case of cyclic adsorption for example).
• the compression step (s) upstream of the purification step make it possible to condense water, thereby decreasing the quantity of water to be stopped at the level of the purification step and therefore the volume adsorbent of said purification.
• the increase in pressure makes it possible to reduce the volume real gas to be treated and allows to optimize flow section and / or pressure losses compared to a low pressure purification.
• the compression step b) makes it possible to bring the flow of feed gas to a pressure such that at least one of the condensable gases can be removed.
• This pressure is between 10 and 50 bar depending on the amount of incondensable and the impurity specification of the CO2 produced.
• the pressure upstream of the compression step is close to atmospheric pressure.
• the compression step b) comprises successive compression phases and where the purification step is placed between two successive compression stages
• said purification will be carried out between 2 and 25 bar abs, preferably between 3 and 9 bar abs still preferably between 3.5 and 6 bar abs.
• the type or types of compressors will be chosen according to the flow rate and the pressures among the types of conventional compressors.
• the exact staging of the pressures, the systematic presence or not of refrigerant after each stage of compression will be optimized according to the type of the machines and the local economic conditions.
• the purification step for removing water from the feed gas stream is located between two compression stages, it is always possible to add additional purification means, preferably downstream of said purification step, for example a means for trapping at least one heavy metal or a compound derived from a heavy metal at the final pressure of compression.
• the third possibility is to place the purification step at the end of the second step b).
• the volume of the purification unit implemented in the purification step will be minimal but the whole of the second compression step b) will be performed with the flow of unpurified gas.
• the choice of the location of the purification step will then be made taking into account the impurities (largely related to the raw material involved in the oxycombustion, ie for example the nature of the coal), the efficiency of the meadow. - treatment, their possible impact on step b) of the process (compression) and the volume of the process to be installed.
• impurities largely related to the raw material involved in the oxycombustion, ie for example the nature of the coal
• the efficiency of the meadow. - treatment their possible impact on step b) of the process (compression) and the volume of the process to be installed.
• the purification process will be chosen according to the impurity (s) to be stopped, its quantity and economic considerations that may be specific to the project (existence of utilities, synergy with neighboring units, etc.).
• the most conventional methods for removing impurities from a gas that will be subjected to a low temperature treatment are washes (absorption), refrigeration / condensation and / or crystallization at room temperature, catalysis, chemistry-sorption and adsorption.
• the purification step consists of several sub-steps, a sub-step being for example based on an adsorption process.
• the first technology lies in the implementation of a fixed bed adsorption.
• the gas to be purified passes through a stack of adsorbent grains, also called fixed bed, which will gradually retain molecules and in doing so, purify the gas.
• adsorbent grains also called fixed bed
• Several types or grades of adsorbents may be used in a mixture or in superposed layers, depending on the impurities to be removed and their proportions, so as to best use the adsorption / desorption properties of each adsorbent. It remains only after regenerating the adsorbent, that is to say to remove the retained molecules so that it can adsorb again.
• all processes that utilize adsorption have an inherently cyclic nature; the two stages of adsorption and regeneration constituting the two main stages of the cycle.
• adsorbent regeneration means The means of regeneration is generally imposed by the nature of the bonds that will establish between the molecules and the adsorbent. The stronger they are, the more energy they must bring to break it. Thus, among the adsorption processes, we find:
• the desorption engine is the pressure difference between the adsorption phase and the regeneration phase. The pressure of the latter is then above atmospheric pressure.
• VSA vacuum Swing Adsorption
• TSA Transmission Adsorption Temperature
• These different gas flow adsorption processes preferably comprise at least two adsorbers, operating alternately, that is to say that one of the adsorbers is in the production phase, while the other is in phase of production. regeneration.
• the TSA process is generally the safest way to perfectly regenerate a polluted adsorbent and remains a fairly simple process.
• the PSA and VSA methods can be complicated and, in doing so, optimized at will.
• the cycles are generally provided with many complementary steps all known to those skilled in the art (such as balancing between bottles ). Their modulation and their concatenation make it possible to optimize any type of process.
• the PSA and VSA processes can even be combined since we can talk about VPSA.
• the "driving force" of the process is increased by increasing the pressure on adsorption P and decreasing that of regeneration by using vacuum V.
• a high temperature may be essential to regenerate an adsorbent polluted with water.
• polar or little volatile molecules will strongly adsorb on the adsorbents which are specific to them; for example, the hydrogen bonds that will be established to retain water on an adsorbent such as alumina or silica gel, or the interaction of water with the cations in the case of a zeolite can only be broken by a significant energy input; it will be the objective of a hot gas so high temperature that will be sent against the current. Nevertheless, the other molecules may not require this temperature and then, the pressure alone is sufficient.
• a hot gas so high temperature that will be sent against the current.
• the first solution consists in implementing at least one adsorber subjected to a TSA cycle and at least one adsorber subjected to a PSA cycle.
• the main advantage lies in the use of two different modes of regeneration. Thus, since only TSA will be regenerated at temperature, the energy expended for the entire separation will be minimized. On the other hand, this will be done to the detriment of the investment costs related to the implementation of two different processes, and the operation which will be more delicate since they are two independent processes.
• the second solution is to implement at least one adsorber subjected to both a TSA cycle and both a PSA cycle.
• the adsorbent material or materials contained in said adsorber will be regenerated at the same time by the pressure (depressurization) and by the temperature (hot elution).
• the main drawback will come from the energy expended to regenerate all of the adsorbent beds (and not just the one that would require it to adsorb the water).
• Another disadvantage comes from the obligation to use adsorbents all capable of withstanding the high temperature of regeneration.
• the advantages in terms of investment and operation are undeniable.
• a possible variant of this second solution consists in dividing said adsorber into two parts and regenerating one of the parts according to the TSA mode and regenerating the other part according to the PSA mode.
• the second technology lies in the implementation of a fluidized bed adsorption.
• the gas to be purified passes through a fluidized bed, that is to say a bed in which the adsorbent is in constant motion. Then, the constant renewal of the molecules on the surface of the adsorbent grains makes it possible to maximize the gradients and, in doing so, to maximize the fluxes of material and heat transfer.
• the adsorbent grains must have physical characteristics sufficiently advanced to be moved relatively easily and to prevent them from being worn out by generating dust of adsorbent material.
• the fluidized bed technique is similar to the homogeneous reactor which has a transfer function different from a fixed bed reactor, in particular as regards its ability to lead to a very pure gas.
• the third technology lies in the implementation of at least one adsorber containing at least one fluidized bed and at least one regeneration reactor.
• each adsorber in the adsorption phase corresponds a reactor in the regeneration phase.
• the rate of circulation of the adsorbent makes it possible to regulate the purity of the gas.
• the reactor in the regeneration phase may contain a simple falling bed.
• the adsorbent material falls and regenerates on contact with the regeneration gas.
• the advantage of the falling bed lies in the simplicity of the regeneration.
• the residence time for regeneration will be limited by the size of the device. From there, we observe a limited performance for this type of bed.
• Another possibility is to implement a reactor in the fluidized bed regeneration phase.
• the fluidized bed makes it possible to control the residence time for the regeneration and to increase the performance.
• the regeneration gas itself after removing impurities trapped in the purification unit, may be recycled in whole or in part in the overall process.
• the purification unit is a TSA adsorption unit, that is to say for which the preponderant effect to ensure the regeneration of the adsorbent is a temperature rise.
• said regeneration will comprise a heating step, very generally a cooling step and optionally a depressurization step if the regeneration is carried out at a pressure lower than that of the purification phase.
• these conventional steps can be added complementary steps such as for example a scanning of the adsorbent bed at room temperature.
• the final heating temperature can be reached gradually via successive stages or a ramp.
• the final temperature (HT) will be a priori in the range 120/200 0 C and preferably between 140 and 175 ° C.
• the regeneration step in the case of an ASD will last from one to a few hours, probably at least 4 hours in the majority of cases.
• the impurities arrested during the purification phase will be more or less easily desorbed and preferentially exit during a period of the regeneration phase.
• the water stopped on silica gel will only be evacuated in large quantities when the heat front has flowed counter-current most of the adsorbent bed (from the shape of the water front in the adsorber, the most of the trapped water is near the inlet side adsorption).
• the less strongly adsorbed impurities will be released before or simultaneously with the beginning of the exit of the water.
• the most adsorbed impurities such as certain acids that may be formed during the entrapment of water (sulfuric acid for example) may exit after water when the regeneration gas becomes dry and approaches the inlet temperature (HT).
• HT inlet temperature
• a fraction of the regeneration gas if initially CO2 cleaned, can be recycled into the main flow of CO2. This flow will be recycled at a suitable point given its pressure, its temperature and its content of impurities.
• a fraction rich in impurities can be recycled for example upstream of the pretreatment while a fraction without impurity can be reinjected to the compression stage corresponding to its pressure.
• the regeneration pressure or pressures may be adapted to make the best use of the different possibilities offered by the compression step, for example to carry out the cooling - or a part of the cooling - at a higher pressure than the heating.
• non-oxidized species or intermediate oxidation stage such as CO
• CO can be reintroduced into the boiler to be oxidized during combustion.
• the organic compounds concentrated in the purification unit are for the most part toxic, mutagenic and carcinogenic.
• the adsorbents that stop the organic compounds must be treated after use. A common treatment for this purpose is incineration. From there, a possibility is to implement in the purification step a succession of adsorption beds including a bed of coal. A fraction of the trace components: heavy metals, organic and organometallic compounds present in the fumes are stopped there. After having served as an adsorbent, the coal used is then periodically mixed with the fuel in the oxy-combustion boiler and thus recovered as a fuel.

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