EP2547420A2 - Procede de traitement de fumees riches en co2 - Google Patents
Procede de traitement de fumees riches en co2Info
- Publication number
- EP2547420A2 EP2547420A2 EP11712642A EP11712642A EP2547420A2 EP 2547420 A2 EP2547420 A2 EP 2547420A2 EP 11712642 A EP11712642 A EP 11712642A EP 11712642 A EP11712642 A EP 11712642A EP 2547420 A2 EP2547420 A2 EP 2547420A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- stream
- coolant
- water
- drying
- cooling
- 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- Withdrawn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
- B01D53/26—Drying gases or vapours
- B01D53/263—Drying gases or vapours by absorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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- 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
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- F23J15/00—Arrangements of devices for treating smoke or fumes
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
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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
- F25J3/04—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 for air
- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04527—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general
- 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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- 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
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- B01D2251/302—Alkali metal compounds of lithium
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- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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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
- B01D2256/22—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/104—Oxygen
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- B01D2257/10—Single element gases other than halogens
- B01D2257/11—Noble gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- B01D2257/602—Mercury or mercury compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- F23J2215/60—Heavy metals; Compounds thereof
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- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
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- F23J2219/70—Condensing contaminants with coolers
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- 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
- F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
- F25J2205/32—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes as direct contact cooling tower to produce a cooled gas stream, e.g. direct contact after cooler [DCAC]
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- 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
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- F25J2205/34—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes as evaporative cooling tower to produce chilled water, e.g. evaporative water chiller [EWC]
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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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- 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
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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
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
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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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- F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
- F25J2260/42—Integration in an installation using nitrogen, e.g. as utility gas, for inerting or purging purposes in IGCC, POX, GTL, PSA, float glass forming, incineration processes, for heat recovery or for enhanced oil recovery
- F25J2260/44—Integration in an installation using nitrogen, e.g. as utility gas, for inerting or purging purposes in IGCC, POX, GTL, PSA, float glass forming, incineration processes, for heat recovery or for enhanced oil recovery using nitrogen for cooling purposes
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- F25J2270/00—Refrigeration techniques used
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- 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
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- 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
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- 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
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- 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 invention relates to a CPU process for capturing and purifying C0 2 contained in combustion fumes, in particular oxy-fuel fumes or cement factory fumes, with pre-drying step carried out before compression, so as to eliminate, upstream of the process, at least part of the water and possibly mercury may be present in said fumes.
- Low value especially coal or liquid hydrocarbons such as oil, than those of higher "value", such as natural gas for example.
- CO 2 CPU processes CPU stands for Compression and Purification Unit
- CPU processes CPU stands for Compression and Purification Unit
- the acid gases are removed, for example by washing with alkaline absorbents, such as calcium carbonate, before compressing the smoke, which then causes a liquefaction of a part of the steam. water, then to dry the gas, by adsorption for example to remove the residual water.
- alkaline absorbents such as calcium carbonate
- a CPU process used to treat fumes from oxy-combustion usually comprises the following successive steps:
- This step is concomitant with the condensation of a good part of the water and the impurities contained in the smoke.
- the gas is at low pressure, that is to say less than 1.2 bar absolute, and more generally at a pressure below atmospheric pressure, that is to say under vacuum.
- a compression of the gas from b) to reach the desired final pressure for example a high pressure between 1 and 74 bar absolute, typically between 2 and 30 bar abs.
- the gas can not contain water which will solidify in ice and may clog some cryogenic material.
- the drying can be carried out in various ways, for example by means of an adsorbent capable of trapping the water present in a gas stream charged with CO 2 , for example with one (or more) bed of alumina-type adsorbent, gel silica or zeolite; or by cryogenic trapping.
- the resulting condensate is then a strong acid, in particular nitric and / or sulfuric acid mainly whose pH can easily be less than 1, which will cause accelerated corrosion of equipment if noble materials are not used. no or less easily corrosive to make them.
- the problem is to be able to eliminate more effectively not only the water vapor present in combustion fumes containing moreover C0 2 to recover by CPU process to prevent water from deteriorating the equipment used. , in particular compressor and associated refrigeration systems, but also one or more other harmful compounds, in particular mercury, which are likely to be found there, in particular it is desirable to be able to eliminate simply and simultaneously the water and mercury when present.
- the solution is a process, in particular a CPU type process, for treating a gas flow comprising a combustion smoke containing CO 2 in an initial proportion, water vapor, one or more volatile volatile compounds, and a or a plurality of additional impurities selected from oxygen, nitrogen and argon, comprising:
- step i characterized in that it comprises, prior to step i), a step of pre-drying the stream to remove at least a portion of the water vapor that it contains.
- the method of the invention may include one or more of the following features:
- step i) Prior to step i), an elimination of at least a portion of the volatile acid compound (s) present in the gas stream.
- step ii) the cooling of the gas stream to a temperature of between about -10 ° C. and about -100 ° C., preferably at a temperature of less than or equal to -80 ° C., preferably at a temperature of less than or equal to -60 ° C, more preferably at a temperature of less than or equal to about -56 ° C.
- the pre-drying of the stream is carried out by adsorption, by absorption / condensation or by permeation.
- volatile acidic compound or compounds are chosen in particular from NO x and
- the gas stream to be treated may comprise other volatile compounds, in addition to NO x and SO x , for example volatile organic compounds (VOCs).
- VOCs volatile organic compounds
- the pre-drying of the flow is operated by absorption / condensation.
- the pre-drying of the flow is carried out by bringing the gas stream into direct contact with a cooling liquid at a temperature below -20 ° C., preferably at a temperature below -30 ° C., and absorption / condensation of at least a portion of the water contained in the flow, within said coolant.
- the cooling liquid comprises a salt or a mixture of aqueous salts, in particular cooling liquid is a solution of calcium chloride or lithium chloride.
- the combustion smoke further contains mercury, at least a portion of the mercury being removed, during the pre-drying step, by the coolant.
- the temperature adjustment is cooling or heating;
- the stream prior to the pre-drying step, contains an initial proportion of water of between 1000 ppm by volume and 30% by volume;
- step i) the compression is carried out at an optimum pressure generally resulting from an overall optimum of the C0 2 purification process and depending in particular on the partially cryogenic temperatures and pressures in order to best separate the NOx and the incondensables that is, the residual air gases;
- the stream contains an intermediate proportion of water less than or equal to 1000 ppm by volume, preferably between 1 and 1000 ppm by volume;
- the stream contains a proportion of final water, that is to say at the cold box inlet, of less than or equal to 50 ppm vol;
- the gaseous flow contains an initial proportion of C0 2 of between 50% and 95% by volume, on a dry basis and a final proportion of C0 2 of between 80 and 100% by volume, on a dry basis;
- step ii) the flow is cooled to about -56 ° C. (triple point of CO 2 );
- step ii) at least one additional impurity selected from oxygen, nitrogen and argon is removed;
- the stream contains a proportion of mercury less than or equal to 0.1 g / Nm 3 ;
- the combustion smoke additionally contains arsenic and / or selenium, at least part of the arsenic and / or selenium present is removed during the pre-drying step by the cooling liquid; ;
- the adjustment of the concentration of said recovered coolant after coming into contact with the flow is carried out by drying said cooling liquid by contact with a dry gas and evacuation of a purge flow containing said dry gas and water vapor, preferably the dry gas is nitrogen from a cryogenic distillation unit;
- the smoke to be treated comes from a process or installation of oxy-fuel or cement manufacturing.
- the invention also relates to a gas flow treatment installation comprising:
- a source (8) of gas flow comprising a combustion smoke containing CO 2 and water vapor
- an absorption / condensation pre-drying unit 1 containing a cooling liquid capable of removing at least a portion of the water vapor from said stream
- the pre-drying unit 1 being supplied with a gas stream by the source 8 of gas flow and with cooling liquid by the unit 2 for supplying cooling liquid so as to make a direct contact with the gaseous flow / cooling liquid; within said pre-drying unit 1 and absorbing / condensing at least a portion of the water within said coolant, recycling means adapted to and designed to recover at least a portion of said water-loaded coolant and recycle it to the coolant supply unit 2, and
- a source of dry gas supplying dry gas to the cooling fluid supply unit 2 so as to make a direct dry gas / cooling liquid contact within said liquid supply unit 2 and to eliminate a gas from purge 7 formed of a mixture of dry gas and steam.
- the installation of the invention may include one or more of the following features:
- the source 8 of gas flow comprising a combustion smoke is an oxy-combustion or cement-making unit, and the source 3 of dry gas is a cryogenic distillation unit;
- At least one heat exchanger device 5 is arranged in the path of the cooling fluid circulating from the cooling liquid supply unit 2 to the pre-drying unit 1, and / or in the path of the gas flow coming from of the pre-drying unit 1;
- At least part of the gas stream coming from the pre-drying unit 1 is sent to at least one gas compression unit 4, a gas purification unit and a gas drying unit.
- removing a portion of the water vapor upstream of the CPU process also makes it possible to better manage the subsequent treatment of the gaseous flow, the composition of which is complex since it contains many different species, in particular metals, such as mercury, acid compounds, such as SOx and NOx, incondensables such as 0 2 , N 2 or Ar ... and a high proportion of C0 2 .
- metals such as mercury
- acid compounds such as SOx and NOx
- incondensables such as 0 2 , N 2 or Ar ... and a high proportion of C0 2 .
- any drying means suitable for drying condensable smoke that is to say containing water beyond the dew point, can be used, in particular pre-drying can be carried out by adsorption, by membrane permeation or by absorption / condensation (washing).
- pre-drying by absorption / condensation i.e. "washing”
- pre-drying by absorption / condensation i.e. "washing”
- washing is preferred because it has a number of advantages, including being already used in other industrial processes, so well controlled, and also be well suited to complex flows, for example to dusty gas streams.
- the gas flow should be treated by lowering its temperature sufficiently to effectively remove the water.
- the temperature of the gas stream that is to say the smoke to be treated, must be lowered by direct contact with a coolant until the dew point of the smoke to which the water is condense, so as to avoid unwanted or unwanted condensation in the "hot" part of the process (compressors, refrigerant system, etc.), whatever the pressure and temperature conditions implemented during each subsequent step of the process, the smoke remains wet.
- the pre-drying of the fumes can be achieved by washing (absorption / condensation) of the fumes. by direct contact smoke / cooling fluid and condensation of water therein, as shown in Figures 1 and 2 appended hereto.
- the flow of gas encounters a fluid cold enough to allow it to reach the desired dew point temperature.
- a liquid capable of remaining in the liquid state even at temperatures well below 0 ° C., preferably below -20 ° C., typically below -30 ° C.
- salts or mixtures of aqueous salts which make it possible to work at around -50 ° C., for example 30% by weight of titrated calcium chloride or 25% by weight of lithium chloride.
- a contactor of the column type packed to carry out the gas and liquid contact.
- a source of cold to cool the liquid that will be warmed in contact with the hot smoke for example a conventional cold ammonia cycle or the use of cold from the cryogenic stages of the CPU process.
- an injection of virgin solution is provided to the liquid inlet of the contactor and a purge output of the contactor liquid to keep a constant volume in the liquid recycle loop.
- means are provided for carrying out a recycling of the washing solution (cooling liquid) which, if not, would eventually saturate, namely to load enough water to stop nothing.
- an additional washing solution is continuously introduced into this recycling loop so that the entire cooling liquid remains always reactive, that is to say unsaturated in water.
- it is liquid (non-compressible) and the volume of the recycling loop is fixed it is necessary to purge the same flow (ie quantity) of liquid as that which enters the loop to avoid the accumulation of water and therefore "waterlogging".
- a notable advantage of eliminating impurities by direct contact with a suitable fluid lies in the possibility of achieving a simultaneous or concomitant removal of water and mercury very present in the fumes from the combustion of certain solid fossil fuels, especially coal.
- eliminating the mercury upstream of the CPU process is very beneficial because it is then avoided that mercury can come into contact with the aluminum materials commonly used in cryogenic equipment used in the cryogenic steps of the CPU process and not amalgam with aluminum. Thanks to the step of pre-drying the smoke by cooling and absorption, it is possible not only to eliminate a large proportion of water that is present in it, but also simultaneously to reduce the proportion of mercury that may be present in the smoke to obtain a residual mercury content acceptable by aluminum equipment, that is to say a maximum proportion of mercury of 0.1 ⁇ g / Nm 3 .
- the mercury thus eliminated can be found in several forms, namely at least in part:
- micelles such that their size keeps them suspended by Brownian motion
- Such micelles may have a shape of between 3 and 300 nanometers.
- the rather volatile arsenic and selenium compounds can also be trapped during this step of pre-drying the smoke by direct contact with a suitable cooling liquid, such as 30% titrated calcium chloride.
- the oxy-fuel smoke charged with water and which is at an elevated temperature is cooled upstream of the CPU process by means of a cooling fluid at a given temperature much lower than 0 ° C, generally below -20 ° C, so as to cause condensation of the water which is there find or even other impurities like mercury.
- the temperature difference between the hot fumes and the cold heat transfer fluid is large. Also, it may be interesting in some cases to gradually lower the temperature of the smoke. For example, industrial water can often be used at a temperature often between 10 and 25 ° C to pre-cool the fumes before operating the actual pre-drying by cooling with the cold heat transfer fluid. This results in an energy optimization of the entire process since the flow of heat transfer fluid at the lowest level of cold will be limited. It is then necessary to reduce the temperature of the fumes from 10-25 ° C to the negative temperature, which then causes a decrease in thermal stress on the contactors.
- the present invention has been implemented so as to improve a conventional CPU process for producing relatively pure C0 2 (ie purity> 95%) at a pressure compatible with a pipeline shipment to a storage location (typically 150-175).
- the feed stream is oxycombustion fumes of coal at a temperature typically between 100 and 250 ° C, here of the order of 150 ° C. This is pre-chilled in a wash tower with water to a temperature close to 40 ° C.
- these fumes enter the compressor.
- the high water content combined with the presence of NOx and SOx will promote the formation of acids, including nitric, nitrous, sulfuric, sulfurous ...
- the dew points of nitric and sulfuric acid are 40 ° C. From there, if these fumes are compressed and they are cooled to a temperature below 40 ° C, typically in an intermediate or final compression condenser, these acids will be condensed which will cause corrosion problems of the equipment and therefore require the use of noble materials, which are expensive.
- the water present in the fumes will be removed by condensing it before being compressed.
- the desired residual water content can be determined to avoid condensation of the acids upon cooling, as shown in Table 2.
- a tower 1 for cooling by direct contact of the fumes with a brine for example formed of water and CaCl 2 titrated at 30% by mass.
- a brine for example formed of water and CaCl 2 titrated at 30% by mass.
- Such brine has a eutectic point at about -51 ° C.
- the operating range is about 28% to about 32% by weight CaCl 2 and a much larger range at room temperature, i.e. at the outlet of the cooling tower. Condensation of the water will reduce the mass content of less than 1% by weight, by dilution effect. Thus, if we are at a 30% input, we can operate properly.
- warmer water if warmer water is available for cooling, it can be operated at -30 ° C. with an expanded operating range of about 25% to about 33% by weight of CaCl 2 .
- the vapor pressure of CaCl 2 is zero and therefore not found in vapor form in the pre-dried fumes sent to compression.
- FIG. 1 shows a diagram of an installation for implementing the method of the invention with cooling steps, condensation, and then cold compression. More specifically, a cooling liquid consisting of a brine 30% CaCl 2 is introduced at a temperature of the order of -40 ° C at the top of the tower 1 fumes / brine. The brine comes from a tower 2 and is cooled to the desired temperature in a cold source 5, that is to say a refrigeration unit. In the tank 11 of this tower 1, the fumes to be treated resulting from an oxy-fuel combustion 8 which are at a temperature of about 40 ° C., saturated with water following a preliminary washing in a water tower 9, are injected.
- a cooling liquid consisting of a brine 30% CaCl 2 is introduced at a temperature of the order of -40 ° C at the top of the tower 1 fumes / brine.
- the brine comes from a tower 2 and is cooled to the desired temperature in a cold source 5, that is to say a refrigeration unit.
- the brine is then sent to a brine / nitrogen tower 2, via a recycling loop as explained above, which will allow the brine to be brought back to its initial concentration by saturation of the dry waste nitrogen from a cryogenic unit 3. air separation or ASU, by excess water from the fumes.
- the nitrogen flow rate is adjusted so as to evaporate the amount of condensed water within the tower 1, typically 30% of the air flow of the unit 3.
- the nitrogen charged with water vapor is sent to the atmosphere (in 7).
- the brine was cooled to a level close to the wet bulb temperature of the dry nitrogen, that is to say approximately 10 ° C., and then returned to the cold source 5 and tower 2.
- the brine is conveyed within the installation, via fluid lines on which can be arranged compressors or pumps used to circulate the fluid.
- the fumes containing C0 2 but freed of at least part of the water they contain are sent to a compressor 4 which makes it possible to increase the pressure of the stream, prior to its treatment by a CPU 6 process in a conventional manner. in order to ultimately recover a gas stream rich in C0 2 , that is to say typically containing at least 95% C0 2 .
- the gas flow can undergo a temperature adjustment (at 12), after compression 4, so as to bring its temperature between 0 ° C and 100 ° C, typically at room temperature, particularly between 20 and 40 ° C.
- FIG. 2 represents a diagram of a variant of the installation for implementing the method of the invention of FIG. 1 comprising an additional heating step. More specifically, the installation of FIG. 2 comprises a heat recovery exchanger 5 which cools the brine by indirect contact with the cold fumes, which thus heats the fumes. The fumes, low water content, will therefore be compressed at room temperature, that is to say of the order of 20 to 25 ° C.
- the cold source 13 for cooling the brine further by heat exchange may be an independent refrigeration cycle, a combination with the cycle of the cryogenic unit 3, a combination with the cycle of the CPU process, a adsorption group, possibly with recovery of the heat of compression of the fumes, or partly of the gas resulting from a vaporization of the liquid oxygen purge of the vaporizer of the cryogenic unit 3.
- an intermediate fluid for example nitrogen
- an intermediate fluid may be used, which is maintained at a compatible minimum temperature, typically at -45 ° C. for our example of cooling the flue gases. about -40 ° C.
- the regeneration of the brine that is the evacuation of the condensed water, can be done in the brine / nitrogen tower 2 fed with residual nitrogen from the cryogenic unit 3. "new" brine and a purge to control the content of impurities (closed system).
- the regeneration of the brine can also be done by heating
- Another advantage provided by the present invention is that it allows the use of non-noble materials, such as carbon steel for example, in a large part of the downstream equipment, mainly compressors and associated cooling systems, in particular. place and place of stainless steel for example, which leads to a significant reduction in the overall investment cost.
- non-noble materials such as carbon steel for example
- Another advantage is the immediate elimination of minor compounds that pose problems in the CPU process, such as mercury which can amalgam with aluminum conventionally used in the cryogenic parts of equipment.
- Yet another advantage is the reduction, simplification or even elimination of the drying system after compression and before the cryogenic cold box.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1051820A FR2957269B1 (fr) | 2010-03-15 | 2010-03-15 | Procede et installation de traitement de fumees riches en co2 |
PCT/FR2011/050393 WO2011114035A2 (fr) | 2010-03-15 | 2011-02-25 | Procede et installation de traitement de fumees riches en co2 |
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EP2547420A2 true EP2547420A2 (fr) | 2013-01-23 |
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EP11712642A Withdrawn EP2547420A2 (fr) | 2010-03-15 | 2011-02-25 | Procede de traitement de fumees riches en co2 |
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US (1) | US9067173B2 (fr) |
EP (1) | EP2547420A2 (fr) |
JP (1) | JP2013522019A (fr) |
CN (1) | CN102905771B (fr) |
CA (1) | CA2789089A1 (fr) |
FR (1) | FR2957269B1 (fr) |
WO (1) | WO2011114035A2 (fr) |
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KR101391282B1 (ko) * | 2012-04-13 | 2014-05-02 | 한국에너지기술연구원 | 분리막을 이용한 수분회수장치를 가지는 연소배가스 처리시스템 |
CN104034049A (zh) * | 2014-05-30 | 2014-09-10 | 葛士群 | 一种节能减排自动化控制锅炉 |
MX2017008683A (es) * | 2015-02-27 | 2017-10-11 | Exxonmobil Upstream Res Co | Reduccion de carga de refrigeracion y deshidratacion para una corriente de alimentacion que entra a un proceso de destilacion criogenica. |
EP3570950A4 (fr) * | 2017-01-19 | 2021-02-24 | Sustainable Energy Solutions, LLC | Procédé et appareil pour l'élimination continue de vapeurs de gaz |
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SE455767B (sv) * | 1986-06-02 | 1988-08-08 | Erik Lindahl | Forfarande och anordning for avskiljning av kvicksilver fran rok- eller processgaser innehallande vattenanga |
GB9105478D0 (en) * | 1991-03-15 | 1991-05-01 | Air Prod & Chem | Carbon dioxide and acid gas removal and recovery process for fossil fuel fired power plants |
US6804964B2 (en) * | 2002-09-19 | 2004-10-19 | Siemens Westinghouse Power Corporation | Water recovery from combustion turbine exhaust |
US7416716B2 (en) * | 2005-11-28 | 2008-08-26 | Air Products And Chemicals, Inc. | Purification of carbon dioxide |
US8088196B2 (en) * | 2007-01-23 | 2012-01-03 | Air Products And Chemicals, Inc. | Purification of carbon dioxide |
US8535417B2 (en) * | 2008-07-29 | 2013-09-17 | Praxair Technology, Inc. | Recovery of carbon dioxide from flue gas |
-
2010
- 2010-03-15 FR FR1051820A patent/FR2957269B1/fr active Active
-
2011
- 2011-02-25 WO PCT/FR2011/050393 patent/WO2011114035A2/fr active Application Filing
- 2011-02-25 EP EP11712642A patent/EP2547420A2/fr not_active Withdrawn
- 2011-02-25 JP JP2012557584A patent/JP2013522019A/ja not_active Withdrawn
- 2011-02-25 CN CN201180013696.6A patent/CN102905771B/zh not_active Expired - Fee Related
- 2011-02-25 US US13/634,276 patent/US9067173B2/en not_active Expired - Fee Related
- 2011-02-25 CA CA2789089A patent/CA2789089A1/fr not_active Abandoned
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Also Published As
Publication number | Publication date |
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CN102905771A (zh) | 2013-01-30 |
FR2957269A1 (fr) | 2011-09-16 |
FR2957269B1 (fr) | 2015-11-13 |
CN102905771B (zh) | 2015-09-16 |
WO2011114035A3 (fr) | 2012-11-22 |
US9067173B2 (en) | 2015-06-30 |
JP2013522019A (ja) | 2013-06-13 |
CA2789089A1 (fr) | 2011-09-22 |
WO2011114035A2 (fr) | 2011-09-22 |
US20130055891A1 (en) | 2013-03-07 |
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