EP2438378A2 - Procede et appareil de production d'au moins un fluide enrichi en argon et au moins un fluide enrichi en oxygene a partir d'un fluide residuaire - Google Patents
Procede et appareil de production d'au moins un fluide enrichi en argon et au moins un fluide enrichi en oxygene a partir d'un fluide residuaireInfo
- Publication number
- EP2438378A2 EP2438378A2 EP10731773A EP10731773A EP2438378A2 EP 2438378 A2 EP2438378 A2 EP 2438378A2 EP 10731773 A EP10731773 A EP 10731773A EP 10731773 A EP10731773 A EP 10731773A EP 2438378 A2 EP2438378 A2 EP 2438378A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon dioxide
- oxygen
- enriched
- argon
- flow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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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
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- 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
- F23J15/006—Layout of treatment plant
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- 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
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- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
- F23L7/00—Supplying non-combustible liquids or gases, other than air, to the fire, e.g. oxygen, steam
- F23L7/007—Supplying oxygen or oxygen-enriched air
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- 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
- F25J3/0257—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 nitrogen
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- 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
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- F25J3/028—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 noble gases
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- F25J3/04533—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the direct combustion of fuels in a power plant, so-called "oxyfuel combustion"
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- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04563—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating
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- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
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- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
- F25J3/0489—Modularity and arrangement of parts of the air fractionation unit, in particular of the cold box, e.g. pre-fabrication, assembling and erection, dimensions, horizontal layout "plot"
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/10—Nitrogen
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- 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
- B01D2256/12—Oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/18—Noble gases
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- 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
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- F23J2215/00—Preventing emissions
- F23J2215/50—Carbon dioxide
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- 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
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- 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
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- F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
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- F25J2270/00—Refrigeration techniques used
- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
- F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
Definitions
- the present invention relates to a process for producing at least one argon-enriched fluid and at least one oxygen-enriched fluid from a waste fluid from a process for purifying a waste gas containing carbon dioxide. carbon and either argon or oxygen or both.
- a particular example would be the production of argon from the incondensables of a low temperature separation process of a waste gas produced by an oxygen consuming facility, the residual gas being oxycombustion fumes.
- Thermal power plants make it possible, by combustion of fuels, to release usable heat to produce water vapor and mechanical or electrical energy. Combustion fumes release significant amounts of CO2 into the atmosphere.
- the current solution consists in carrying out combustion within the boiler in the presence of a gas rich in oxygen and especially depleted in nitrogen. This combustion produces combustion fumes with a high concentration of CO2, which is advantageous because current technologies for the removal of CO2 from combustion fumes make it possible to remove CO2 more easily from fumes with a high concentration of CO2 than fumes. low concentration of CO2. This CO2 must then be purified and compressed before being sequestered.
- the object of the present invention is to propose a method for producing argon and oxygen from a carbon dioxide-rich waste gas also containing argon and / or oxygen which are incondensable from a unit for cleaning fumes with CO2 at a low temperature.
- the cryogenic treatment of the low carbon dioxide flow comprises a step of cooling in at least one exchanger, optionally a reboiler, optionally a condenser, optionally a reversible or regenerative exchanger, and a distillation step in a column; distill;
- the purification process preferably operates at a low temperature but other known purification methods can be substituted therein (for example, amine washing);
- the flow rate that is low in carbon dioxide is substantially free of carbon dioxide, which may contain, for example, a few ppm of carbon dioxide); air is separated in an air separation apparatus, preferably by cryogenic distillation, to produce a flow rich in oxygen containing at most 99% oxygen, preferably at most 98% oxygen, or even plus 97 mol% oxygen, and argon, preferably at least 2 mol%. argon, at least 3% mol. argon and the oxygen-rich flow is sent to the oxygen consuming plant, preferably the oxycombustion;
- the fraction enriched with oxygen is used for the oxyfuel combustion of the fuel and / or the pretreatment of the waste gas depleted in carbon dioxide; the treatment also makes it possible to recover an enriched or even nitrogen-rich fraction;
- one or more fluid (s) originating from an air gas separation unit or from the air gas separation unit providing at least one part of oxygen for oxycombustion;
- the low carbon dioxide flow rate is cooled upstream of the cryogenic treatment, the low carbon dioxide flow rate being substantially free of carbon dioxide;
- the low carbon dioxide flow rate is cooled upstream of the cryogenic treatment and at the same time is purified to carbon dioxide, the low carbon dioxide flow rate containing carbon dioxide;
- the low carbon dioxide flow rate is cooled in at least one reversible heat exchanger or in a regenerator type exchanger and the flow rate is sent to a column of the cryogenic treatment unit;
- one of these fluids is a nitrogen-rich liquid which at least partially keeps cold the cryogenic treatment of the low carbon dioxide flow rate
- the flow rate that is low in carbon dioxide is sent to a first column, optionally having a bottom reboiler, separated to form an oxygen-enriched fluid and a nitrogen-enriched fluid, an intermediate flow is withdrawn from the first column and sent to the first column; tank of a second column where it is enriched in argon to form a fraction enriched in argon;
- an argon-enriched fraction is withdrawn from the second column and sent to a denitrogenation column to form an argon-rich fraction; in the treatment of the low carbon dioxide flow rate, one or more fluid (s) originating from an air gas separation unit or from the air gas separation unit providing at least one part of the oxygen for the oxygen fed plant, for example oxycombustion;
- At least one column of the air gas separation unit and at least one column of the treatment unit are in a single cold box;
- one of these fluids is a gas rich in nitrogen which will serve as a cycle gas for at least one reboiler and / or at least one condenser of the cryogenic treatment;
- pretreatment removes at least 50%, or even substantially 100%, of the carbon dioxide in the waste gas before the cryogenic treatment. at least partly by antisublimation / sublimation of carbon dioxide in several exchangers in parallel;
- the sublimation of the carbon dioxide is done in the presence of the enriched oxygen fraction so as to constitute a mixture of carbon dioxide / oxygen for the oxyfuel combustion of the fuel; the pretreatment is done at least in part by a method of the TSA type,
- PSA or VPSA to produce a fraction enriched in carbon dioxide and a fraction depleted of carbon dioxide but enriched in argon;
- the pretreatment is done at least in part by an absorption process;
- the absorption process uses an aqueous solution of basic pH;
- the basic pH is obtained by injection of NaOH and / or Na 2 CO 3 and / or NH 3 ;
- the pretreatment is done at least partly by an adsorption process
- the pretreatment is done at least partly by permeation; the flow rate enriched with carbon dioxide produced by the pretreatment is recycled to the boiler, preferably to the combustion chamber.
- an installation for producing at least one fluid enriched in argon and at least one oxygen-enriched fluid from a waste fluid originating from a purification process comprising: - a unit for purifying the waste gas, constituted by fumes from a furnace for the oxyfuel combustion of a fuel by means of a gas rich in oxygen and carbon dioxide, the unit purification unit which can be a low temperature purification unit, so as to produce a carbon dioxide enriched fluid and a carbon dioxide depleted waste fluid,
- a pre-treatment unit for the residual fluid to obtain a flow enriched in carbon dioxide and a flow rate that is low in carbon dioxide
- cryogenic low carbon dioxide flow treatment unit for extracting an argon-enriched fraction, an oxygen-enriched fraction and a depleted argon and / or oxygen fraction.
- the cryogenic treatment unit of the low carbon dioxide flow comprises at least one exchanger and at least one distillation column; at least one exchanger is a reboiler;
- At least one exchanger is a condenser
- the treatment unit makes it possible to recover an enriched or even rich fraction in argon and an enriched or even rich fraction in oxygen;
- the installation comprises means for sending the fraction enriched in oxygen to the boiler and / or the pretreatment unit;
- the treatment also makes it possible to recover a fraction enriched in nitrogen
- the installation comprises means for sending one or more fluid (s) coming from the air gas separation unit supplying at least a portion of the oxygen for the oxygen powered installation, for example oxycombustion, at the unit of cryogenic treatment of the low carbon dioxide flow rate;
- one of these fluids is a liquid rich in nitrogen for keeping the treatment cold;
- one of these fluids is a nitrogen-rich gas which will serve as a cycle gas for at least one reboiler and / or at least one condenser of the cryogenic treatment unit of the low carbon dioxide flow rate;
- the pretreatment unit is / comprises a carbon dioxide antisublimation / sublimation unit comprising a plurality of exchangers in parallel;
- the sublimation unit is connected to a conduit for supplying the fraction enriched with oxygen so as to constitute a mixture of carbon dioxide and oxygen and possibly means for sending the mixture to the oxy-fuel combustion unit of the combustible ;
- the pretreatment unit is / comprises an installation of the TSA, PSA or VPSA type which produces a fraction enriched in carbon dioxide and a fraction depleted of carbon dioxide but enriched with argon;
- the preprocessing unit is / comprises an absorption installation; the absorption process uses an aqueous solution of basic pH;
- the basic pH is obtained by injection of NaOH, Na 2 CO 3 , NH 3 ;
- the absorption process is a methanol washing process
- the preprocessing unit is / comprises a permeation unit
- the installation comprises means for recycling the carbon dioxide enriched flow of the pre-treatment unit into the boiler.
- the oxygen delivered by the air separation apparatus to the oxycombustion comprises at most 98 mol%, oxygen, preferably at most 97 mol%. of oxygen, see at most 96 mol%. oxygen.
- the oxygen supplied by the air separation apparatus to the plant comprises at least 1 mol%. argon, preferably at least 2 mol%. argon, or at least 3 mol%. argon.
- the argon-enriched gas produced by the apparatus comprises at least 50 mol% argon, preferably at least 70 mol%. argon, or even at least 90 mol% of argon.
- the invention will be described in more detail with reference to the Figures.
- Figure 1 shows an oxycombustion plant with flue gas purification units
- Figure 2 shows the flue gas purification units in more detail
- Figure 3 shows a flue gas purification unit for CO 2 at low temperature
- Figure 4 shows a nitrogen recovery apparatus and / or of oxygen and / or argon from a waste gas of the unit of Figure 4
- Figure 5 shows a variant of Figure 4.
- FIG. 1 is a schematic view of an oxycombustion plant.
- An air separation apparatus 2 produces a flow rate of oxygen at a typical purity of 95 mol. % to maximize its argon content and a waste nitrogen flow 13.
- the apparatus also produces nitrogen gas 13 and liquid nitrogen 159 for the treatment of incondensables.
- the flow rate of oxygen 10 is divided into two fractions 11 and 12.
- the main flow of flue gas recycle 15 passes through the units 3 where the coal 14 is converted into powder.
- the fraction 11 is mixed with the recycle flow downstream of the unit 3 and the mixture is sent to the combustion chamber of the boiler 1.
- Fraction 12 is mixed with a secondary flue gas recirculation flow rate 16 which provides ballast to the burners to maintain temperatures at acceptable levels.
- Water 17 is sent to the boiler 1 to produce steam 18 which is expanded in a turbine 8.
- Unit 4 removes NOx for example by catalysis.
- the unit 5 removes the dust and after the unit 6 is a desulfurization system to remove SO2 and / or SO3.
- Units 4 and 6 may be redundant depending on the composition of the required product.
- the purified flow 24 from unit 6 (or 5 if 6 is not present) is sent to a compression and scrubber unit 7 to produce a relatively pure CO 2 flow rate and a residual flow rate 26.
- FIG. 2 is a schematic view of the compression and purification unit 7 of FIG. 1.
- a flow 110 (corresponding to flow 24 of FIG. 1) enters a unit 101 where it is prepared upstream of the compression. in unit 102.
- flow 110 may be purified to dust, SO2, and / or SO3 and / or cooled.
- the residual flow rate 111 produced by unit 101 may be condensed water, dust or H 2 SO 4 , HNO 3, Na 2 SO 4 , CaSO 4 , Na 2 CO 3 , CaCO 3 , etc.
- the compression unit 102 compresses the flow 112 from the unit 101 from a pressure close to atmospheric to a high pressure between 15 and 60 bar abs, preferably to 30 bar abs. This compression can be carried out in several stages with intermediate cooling. In this case, condensates 113 may be produced. The heat of compression can be recovered to preheat the water 17. A hot flow 114 leaves the compression unit 102 and enters the unit 103. This unit cools the flow 114, the drying and possibly the mercury treatment. producing waste 115, 116 and 117.
- Unit 104 is a low temperature purification unit.
- low temperature means a minimum temperature in the cycle of the purification process below 0 ° C. and preferably below -20 ° C., or as close as possible to the triple point of pure CO2 at - 56.6 0 C.
- the flow 118 is cooled and partially condensed in one or more steps.
- One or more CO2-enriched flow rates are expanded and vaporized to obtain a CO 2 -rich product 119.
- a high-pressure incondensable flow 120 is recovered from unit 104 and sent to a pretreatment unit 122.
- the pre-processed flow 123 is sent to a treatment unit 124 where one or more fluids is produced which may be liquid and / or gaseous nitrogen 125 and / or liquid and / or gaseous oxygen 126 and / or argon gas and / or liquid 127.
- a treatment unit 124 where one or more fluids is produced which may be liquid and / or gaseous nitrogen 125 and / or liquid and / or gaseous oxygen 126 and / or argon gas and / or liquid 127.
- the CO2-rich product 119 is compressed in a compression unit 105.
- the compressed flow 121 is condensed and can be pumped.
- FIG. 3 shows a low temperature purification apparatus which corresponds to the unit 104 of FIG. 2.
- the flow 1 18 comprising fumes at approximately 30 bar and at a temperature of between 15 ° C. and 43 ° C.
- the flow 118 includes mainly carbon dioxide as well as NO 2 , oxygen, argon and nitrogen. It can be produced directly at high pressure by the unit 103 or can be compressed by a compressor (dashed).
- the flow 5 cools in an exchange line 9 and is partially condensed. Part 7 of the flow 5 is not cooled in the exchange line 9 but is mixed with the remainder of the flow 5 downstream of the exchange line in order to vary the temperature of the mixture.
- the partially condensed flow is fed to a first phase separator 11 and separated into a gaseous phase 13 and a liquid phase 17.
- the gaseous phase 13 is divided in two to form a flow 15 and a flow 21.
- the flow 21 is used to to reboil column 43 in the exchanger 25 and is then sent to a second phase separator 22.
- the flow 15 bypasses the reboilers to regulate the reboiling.
- the liquid 17 of the first phase separator 11 is expanded in a valve 19 and the liquid flow 29 of the second phase separator 22 is expanded in a valve 31, the two expanded flows then being sent to the top of the column 43.
- the column 43 serves primarily to remove the non-condensable components (oxygen, nitrogen and argon) from the feed rate 118.
- a depleted flow of carbon dioxide 33 is withdrawn at the top of the column 43 and sent to the compressor 35.
- the compressed flow 37 thus produced is recycled at flow 5.
- a flow enriched or rich in carbon dioxide 67 is withdrawn in the bottom of the column 43 and divided into two.
- a portion 69 is pumped by the pump 71 to form a flow 85, then pumped into the pump 87 and removed from the system.
- the flow 85 corresponds to the flow rate 25 of FIG. 1.
- the remainder 73 of the flow 67 serves to keep the apparatus cold.
- Incondensables can be separated before or after separation of NO 2 .
- This column may have a head condenser and a bottom reboiler, the flow 73 being sent to an intermediate point. Otherwise, if there is no tank reboiler, the flow is sent to the tank.
- a low NO2 flow 79 is withdrawn from the column 105 and returned to the exchange line 9.
- This flow 79 is heated, compressed in the compressors 75, 77, sent to the exchanger 65, removed as the flow 78, cooled in the exchangers 81, 83 and mixed with the flow 69 to form the flow 85.
- the exchanger 81 can be used to heat the water for a boiler.
- the exchanger 83 is cooled by a refrigerant flow 185 which can be R134a, ammonia, water etc., the heated refrigerant is designated 187.
- An enriched flow NO2 84 is withdrawn from the bottom of the column 105. This flow 84 is recycled to a point upstream of the filters 3.
- the overhead gas 32 of the second phase separator 22 is cooled in the exchanger 55 and sent to the third phase separator 133.
- Part of the liquid of the third phase separator 133 is sent to the column 43 and the remainder, as the flow at intermediate purity 45, is divided into two flow rates 47, 141.
- the flow 47 is vaporized in the exchanger 55 and sent to the top of the column 43 or mixed with the flow 33.
- the flow 141 is expanded in a valve, heated in the exchangers 55, 9, compressed in the compressor 59, cooled as a flow 91 in the exchanger 60 and mixed with the compressed flow 5.
- the valve which serves to relax the flow 141 can be replaced by a liquid turbine.
- the overhead gas of the third phase separator 133 is cooled in a heat exchanger 55, optionally after compression in a compressor 134 and sent to a fourth phase separator 143.
- the carbon dioxide-poor overhead gas 157 of the fourth separator of phase 143 is heated in a heat exchanger 55, then in the exchanger 9, heated in the exchanger 65 and expanded as flow 23 in the exchanger 63, coupled to the compressor 35.
- the carbon dioxide-poor gas 157 comprises between 30 and 45% of carbon dioxide and between 30 and 45% of nitrogen. It also includes substantial amounts of oxygen and argon.
- the tank liquid 51 of the phase separator 143 is sent to the column 43 with the flow 47.
- the flow rate expanded in the turbine 63 is mixed with the flow 115 which does not pass into the turbine and then reheated at 89.
- a portion 97 of the heated flow rate is expanded in the turbine 61 and sent to the atmosphere as flow 99.
- a flow 120 rich in incondensable (oxygen and / or argon and / or nitrogen) and containing CO2 is recovered in unit 104 to recover at least one of its components as a product.
- This flow 120 may be a part of the flow 101 from the turbine 61 and / or a part of the overhead gas 157 of the fourth phase separator 143 upstream of the exchanger 55 and / or a part of the flow expanded in the turbine 63 and / or part of the flow 157 downstream of the exchanger 9.
- FIG. 4 shows a pre-treatment apparatus and a cryogenic distillation separation apparatus of the flow 120.
- This flow 120 is first pretreated in the pretreatment unit 122.
- This pretreatment unit removes at least 50 mol%. carbon dioxide in the waste gas 120 prior to the cryogenic treatment producing a CO 2 enriched flow rate that can be recycled to the unit 104 with the flow rate 118.
- the pretreatment can be carried out by antisublimation / sublimation of carbon dioxide in several exchangers in parallel.
- the pretreatment can be carried out by absorption (for example methanol washing), adsorption, permeation or several of these techniques.
- Sublimation of carbon dioxide occurs, for example, in the presence of an oxygen-enriched fraction so as to constitute a mixture of carbon dioxide and oxygen for the oxyfuel combustion of the fuel. Thanks to anti-sublimation, the temperature of the treated gas drops from -56.6 ° C (triple point of CO2) to -170 ° C / -175 ° C, a temperature at which cryogenic distillation of gas can be carried out. the air.
- the pretreatment can be done by a process of the TSA, PSA or VPSA type so as to produce a fraction enriched in carbon dioxide and a fraction depleted of carbon dioxide but enriched in argon.
- the pretreatment can be done by an absorption process, using for example an aqueous solution of basic pH.
- the basic pH is optionally obtained by injection of NaOH and / or Na 2 CO 3 and / or NH 3 .
- the absorption process may also use a non-aqueous fluid such as methanol. In this case, the absorption will be carried out at low temperature and preferably under pressure.
- the pretreatment is by permeation or a combination of the various methods mentioned.
- the depleted flow rate of carbon dioxide 123 is sent to a cryogenic distillation unit 124 as shown in FIG. 4.
- the flow 123 is cooled to a cryogenic temperature in an exchanger 130 and sent to the middle of a column 131 having a tank reboiler 133.
- the flow 123 could be cooled by expansion in a turbine with production of work (isentropic expansion).
- Oxygen gas GOX is withdrawn above the tank of column 131, heated in exchanger 130 and serves as product 126 and / or is recycled to pretreatment 122 and / or boiler 1.
- Oxygen liquid 136 can be withdrawn in the bottom of column 131, for example as a product.
- An argon-enriched flow 141 is sent from column 131 to column 137 and a flow of impure argon 145 is withdrawn under condenser 155 of this column 137.
- a flow of vessel liquid 143 is returned to column 131.
- L Impure argon 145 is purified in a denitrogenation column 139 having a top condenser 153 and a bottom reboiler 151.
- Liquid argon 127 is produced in the bottom of the denitrogenation column 139.
- the apparatus is kept cold at room temperature. least partially by liquid nitrogen injection 159 from the air separation apparatus 2 feeding the oxyconnbustion. The liquid nitrogen 159 is sent to the top of the column 131.
- This air separation unit 2 also supplies nitrogen gas 13 which cools in the exchanger 130, heats the bottom reboiler 133 of the column 131 to form a condensed flow.
- the condensed flow is sent in part 147 after expansion to the top condenser 153 of the denitrogenation column 139, in part 165 to the top condenser 155 of the column 137 and in part 157 after expansion at the head of the column 131.
- the nitrogen 163 vaporized in the condenser 153 is mixed with the overhead gas 135 of the column 131, heated in the subcooler 160 and the exchanger 130 and forms the nitrogen gas 165.
- the nitrogen 161 vaporized in the condenser 155 forms the nitrogen flow 161.
- At least one column of the apparatus 124 may possibly be in the same cold box as at least one column of the apparatus 2.
- the transfers of nitrogen 13 and / or 159 can be done without having to heat and cool the nitrogen.
- Figure 5 shows a variant of the cold part of Figure 4 in which the cold mixture 123 from the exchanger 130 is sent to an intermediate level of a column 163 without reboiler or overhead condenser.
- the overhead gas 171 of the column 163 is nitrogen gas and the vessel liquid 173 is fed to a column 165 in the intermediate position. Gas 175 is returned from the intermediate position of the column 165 to the tank of the column 163.
- the column 165 has a bottom reboiler 175 and a top condenser 177.
- Oxygen gas 126 and / or liquid 136 is recovered in the tank of the column 165 and the overhead liquid 145 is sent to a denitrogenation column 167, the liquid argon being formed 127 in the vessel thereof.
- the denitrogenation column has a bottom reboiler 151 and a top condenser 153.
- Liquid nitrogen 159 from the air separation unit 2 is sent to the top of the column 163.
- the column 163 has a top condenser which, like all the reboilers and condensers of FIG. nitrogen gas cycle from the air separation apparatus 2, a cycle which has not been illustrated but resembling that of Figure 4.
- the sending of liquid nitrogen 159 may be the only source of cold for the process.
- Other ways of separating the flow 123 by cryogenic distillation can obviously be envisaged as those illustrated in FIGS. 4 and 5.
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Applications Claiming Priority (2)
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FR0953648A FR2946417A1 (fr) | 2009-06-03 | 2009-06-03 | Procede et appareil de production d'au moins un fluide enrichi en argon et/ou au moins un fluide enrichi en oxygene a partir d'un fluide residuaire |
PCT/FR2010/051031 WO2010139884A2 (fr) | 2009-06-03 | 2010-05-28 | Procédé et appareil de production d'au moins un fluide enrichi en argon et au moins un fluide enrichi en oxygène à partir d'un fluide résiduaire |
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EP10731773A Withdrawn EP2438378A2 (fr) | 2009-06-03 | 2010-05-28 | Procede et appareil de production d'au moins un fluide enrichi en argon et au moins un fluide enrichi en oxygene a partir d'un fluide residuaire |
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US (1) | US20120067082A1 (zh) |
EP (1) | EP2438378A2 (zh) |
CN (1) | CN102695935A (zh) |
AU (1) | AU2010255559A1 (zh) |
CA (1) | CA2762237A1 (zh) |
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WO (1) | WO2010139884A2 (zh) |
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2009
- 2009-06-03 FR FR0953648A patent/FR2946417A1/fr active Pending
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2010
- 2010-05-28 EP EP10731773A patent/EP2438378A2/fr not_active Withdrawn
- 2010-05-28 AU AU2010255559A patent/AU2010255559A1/en not_active Abandoned
- 2010-05-28 US US13/375,256 patent/US20120067082A1/en not_active Abandoned
- 2010-05-28 WO PCT/FR2010/051031 patent/WO2010139884A2/fr active Application Filing
- 2010-05-28 CN CN2010800247790A patent/CN102695935A/zh active Pending
- 2010-05-28 CA CA2762237A patent/CA2762237A1/fr not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CN102695935A (zh) | 2012-09-26 |
FR2946417A1 (fr) | 2010-12-10 |
WO2010139884A3 (fr) | 2012-11-15 |
US20120067082A1 (en) | 2012-03-22 |
CA2762237A1 (fr) | 2010-12-09 |
WO2010139884A2 (fr) | 2010-12-09 |
AU2010255559A1 (en) | 2011-12-22 |
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