WO2014206880A1 - Procede et dispositif de traitement de gaz par injection de compose pulverulent et de phase aqueuse - Google Patents

Procede et dispositif de traitement de gaz par injection de compose pulverulent et de phase aqueuse Download PDF

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Publication number
WO2014206880A1
WO2014206880A1 PCT/EP2014/063017 EP2014063017W WO2014206880A1 WO 2014206880 A1 WO2014206880 A1 WO 2014206880A1 EP 2014063017 W EP2014063017 W EP 2014063017W WO 2014206880 A1 WO2014206880 A1 WO 2014206880A1
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WIPO (PCT)
Prior art keywords
compound
aqueous phase
injection
powdery
gases
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.)
Ceased
Application number
PCT/EP2014/063017
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English (en)
French (fr)
Inventor
Xavier PETTIAU
Olivier NYSSEN
Alain Brasseur
Alain Laudet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lhoist Recherche et Developpement SA
Original Assignee
Lhoist Recherche et Developpement SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to CA2913240A priority Critical patent/CA2913240C/fr
Priority to EP14736324.6A priority patent/EP3013459B1/fr
Priority to KR1020157035463A priority patent/KR101644899B1/ko
Priority to BR112015030657-8A priority patent/BR112015030657B1/pt
Priority to JP2015563092A priority patent/JP6059828B2/ja
Priority to US14/898,293 priority patent/US9579601B2/en
Priority to ES14736324.6T priority patent/ES2615804T3/es
Priority to DK14736324.6T priority patent/DK3013459T3/en
Application filed by Lhoist Recherche et Developpement SA filed Critical Lhoist Recherche et Developpement SA
Priority to SG11201510356TA priority patent/SG11201510356TA/en
Priority to AU2014301338A priority patent/AU2014301338B2/en
Publication of WO2014206880A1 publication Critical patent/WO2014206880A1/fr
Priority to ZA2015/09110A priority patent/ZA201509110B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81Solid phase processes
    • B01D53/83Solid phase processes with moving reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/38Removing components of undefined structure
    • B01D53/40Acidic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • B01D53/501Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/504Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/80Semi-solid phase processes, i.e. by using slurries
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23JREMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00Arrangements of devices for treating smoke or fumes
    • F23J15/003Arrangements of devices for treating smoke or fumes for supplying chemicals to fumes, e.g. using injection devices
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23JREMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J7/00Arrangement of devices for supplying chemicals to fire
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/30Alkali metal compounds
    • B01D2251/304Alkali metal compounds of sodium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/40Alkaline earth metal or magnesium compounds
    • B01D2251/404Alkaline earth metal or magnesium compounds of calcium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/60Inorganic bases or salts
    • B01D2251/602Oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/60Inorganic bases or salts
    • B01D2251/606Carbonates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/102Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/106Silica or silicates
    • B01D2253/11Clays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/20Halogens or halogen compounds
    • B01D2257/204Inorganic halogen compounds
    • B01D2257/2045Hydrochloric acid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/20Halogens or halogen compounds
    • B01D2257/204Inorganic halogen compounds
    • B01D2257/2047Hydrofluoric acid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/60Heavy metals or heavy metal compounds
    • B01D2257/602Mercury or mercury compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/12Methods and means for introducing reactants
    • B01D2259/126Semi-solid reactants, e.g. slurries
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/02Separation 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
    • B01D53/06Separation 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
    • B01D53/10Separation 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23JREMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2219/00Treatment devices
    • F23J2219/50Sorption with semi-dry devices, e.g. with slurries

Definitions

  • the present invention relates to a gas treatment method having a predetermined direction of flow in a gas line comprising the steps
  • the treatment of gases requires the abatement of acid gases, especially HCl, S0 2 and / or HF, which abatement can be carried out dry, by injection of a substance, often mineral, dry and pulverulent in a stream of flue gas or through a filter comprising a fixed bed of solid particles or moving.
  • the powdery compound generally comprises a calco-magnesium compound, in particular lime, preferably quenched or hydrated or a sodium compound such as sodium carbonate or bicarbonate.
  • inorganic compounds may also be used, especially those used for the reduction of dioxins, furans and / or heavy metals, including mercury, such as, for example, those based on phyllosilicates, such as sepiolite or halloysite or the like.
  • the present invention relates more particularly to processes for reducing acid gases in gases, in particular flue gases, by injecting a powdery product having capturing acidic pollutants in the gas stream to improve the abatement efficiencies of the gaseous acid components of the treated gases.
  • Documents CN 2011 68568 and JP 10-216 572 each propose an alternative intended to solve clogging problems by carrying out the suspension of lime milk in situ during the injection.
  • a lance consisting of two concentric tubes, that is to say an inner tube and an outer tube.
  • the water is injected via the inner tube while the hydrated lime is injected via the outer tube.
  • the position of the inner tube can be adjusted with respect to the position of the outer tube and it is therefore possible to have an inner tube for the water having an outlet port projecting or recessed or at the same level relative to a hydrated lime outlet port of the outer tube.
  • the design of the spray lances requires the water spray tube to be internal to the pulverized hydrated lime spray tube.
  • the sprayed lime encounters an obstacle within the outer spray tube that resides in the inner water spray tube.
  • the moisture content of the hydrated lime induces a water / lime mass ratio of 5 to 6 to form a suspension in situ.
  • This suspension provides an adverse side effect for the treatment of flue gas in that the gas is furthermore significantly cooled with the injection of hydrated lime. This assumes that the fumes are hot enough for the depollution to be effective; however, this is not sought after today as industrialists have an increasing tendency to recover the heat of the flue gas at best for economic and environmental reasons.
  • the present invention aims to overcome the drawbacks of the state of the art by providing a process for the treatment of gases, in particular flue gas, with a powdery compound, preferably mineral, in particular hydrated lime, during which the risk of clogging is significantly reduced and the water consumption is minimized and without substantially cooling the gases, thus allowing not to interfere with the recovery of calories from these gases to be treated.
  • gases in particular flue gas
  • a powdery compound preferably mineral, in particular hydrated lime
  • a method as indicated at the beginning characterized in that said step of injecting aqueous phase, in the form of droplets, is carried out inside said gas pipe in said cloud or flow of particles of powdery compound, so as to moisten these particles of powdery compound inside the gas line, during their injection, in a weighted ratio between the aqueous phase injected in the form of droplets and the injected powdery compound greater than or equal to 0.05 and less than or equal to 1.2.
  • the humidification of the powdery compound is carried out at the point of injection of the powdery compound, and this in the conduit / gas stream to be treated.
  • the particles of the inorganic compound and the water phase droplets coexist very locally, and the powdery compound is moistened in situ and in a controlled manner.
  • a layer of droplets of aqueous phase is thus created on the surface of the particles of powdery compound and facilitates the transfer of pollutants, especially acids, to be slaughtered to the solid phase of the powdery compound.
  • the aqueous phase droplet layer is obtained via the controlled co-injection of powdery compound and aqueous phase particles according to said weight ratio and the in situ wetting of the powdery compound avoids the recurrent problem of clogging the compound injection lances. powder, in particular hydrated hydrated lime.
  • the aqueous phase is injected in an immediate vicinity with respect to the powder compound injection point.
  • the term "immediate vicinity" means that the distance between the point of injection of the aqueous phase and the injection point of the powdery compound is less than or equal to the diameter of the injection point. the powder compound injection tubing, in particular less than or equal to the radius.
  • the powdery compound is a mineral compound. It may comprise a calco-magnesium compound, in particular lime, preferably quenched or hydrated.
  • the mineral compound is chosen from those used for the abatement of dioxins, furans and / or heavy metals including mercury, for example those based on sepiolite or halloysite or the like.
  • the pulverulent compound used may also be organic, in particular carbon-based, in particular of the activated carbon or lignite coke type.
  • the powdery compound can also be a mixture of these compounds.
  • the aqueous phase is liquid water or an aqueous solution of alkaline compound selected from the group consisting of metal hydroxides, carbonates, bicarbonates, hydrogencarbonates, nitrates, phosphates, persulfates, and monocarboxylates.
  • alkali especially sodium, potassium and / or lithium, and mixtures thereof, or an aqueous solution of ammonia or urea-based compound, such as ammonium salts, or an aqueous solution of compound with base of alkali or alkaline-earth metal or ammonium halides, in particular chloride and / or bromide, especially sodium, potassium, calcium or magnesium.
  • the aqueous phase may also contain acids, especially organic acids, difunctional (di-basic acids) or not.
  • the aqueous phase is essentially monophasic.
  • the aqueous phase consists essentially of a liquid, in particular liquid water.
  • the temperature of the aqueous phase before injection into said flue gas duct is less than 100 ° C, preferably less than 40 ° C, particularly less than 30 ° C, more particularly less than 20 ° C.
  • the aqueous phase injection step is carried out in a neighborhood immediately downstream of said powder compound injection point with respect to said predetermined flow direction of the gases in said gas pipe.
  • neighborhborhood immediately downstream of the injection point of powdery compound is meant in the sense of the present invention, that, with respect to the flow direction of the gases, the aqueous phase droplets are pulverized just after the compound powder.
  • the injected powdery compound therefore first encounters the gases and immediately after the aqueous phase droplets formed, which thus makes it possible to moisten the powdery compound and not the gases to be treated.
  • the aqueous phase injection step is carried out in a neighborhood immediately upstream of said mineral compound injection point with respect to said predetermined flow direction of the flue gases in said gas pipe. of fumes.
  • said pulverulent compound injection step is carried out in the gas pipeline in an injection direction which forms an angle of 90 to 150 degrees, preferably less than or equal to 145 degrees, preferentially less than or equal to 40 degrees. degrees and in particular less than or equal to 135 degrees, with respect to the predetermined flow direction of the gases.
  • said aqueous phase droplets have an average droplet size of between 500 and 5000 ⁇ m, preferably between 500 and 5000 ⁇ m, depending on the injection conditions.
  • said powdery compound in particular powdered hydrated lime, has an average particle size d.sub.50 of less than 80 .mu.m, advantageously less than 50 .mu.m, preferably less than 35 .mu.m, preferably less than 25 .mu.m and in particular less than or equal to 10 ⁇ m, in particular less than or equal to 8 ⁇ m.
  • the powdery compound may be a powdery inorganic compound co-injected with another pulverulent compound, especially a carbon compound, in particular of the activated carbon or lignite coke type.
  • said pulverulent compound in particular hydrated lime, has a moisture (mass content of water) of between 0.2% and 10% before injection into said gas line. especially between 0.5 and 4%, preferably less than 2%, in particular less than 1.5%.
  • the weight ratio between said aqueous phase injected in the form of droplets and said injected powdery compound is greater than or equal to 0.1, preferably greater than or equal to 0.2, and less or equal to 1, and more particularly less than or equal to 0.8.
  • This weight ratio is relatively low in comparison with that reported in the previous documents CN 1 685 68 and JP 10-216 572 and does not cause any substantial cooling of the gases to be treated because, according to the present invention, the reduced proportion of water added allows the humidification of the powdery compound, in particular hydrated lime, without moistening and thus significantly cool the gases.
  • the high weight ratio between water and hydrated lime of between 5 and 6 is dictated by the fact that a suspension of hydrated lime (milk of lime) is sprayed into the gas to be treated.
  • the temperature of the gases is greatly reduced by the injection of a large quantity of water which consumes calories on evapo- ration.
  • said gases have, before injection of said powdery compound, a temperature of between 10 and 1100.degree. in particular between 10 and 100 ° C, especially between 15 and 80 ° C, in particular between 20 and 70 ° C or between 100 ° C and 300 ° C, preferably between 30 ° C and 250 ° C and preferably between 150 and 150 ° C. C. and 230 ° C., in particular between 160 ° C. and 220 ° C.
  • said gases have, before injection of said powdery compound, a temperature of between 300 ° C. and 500 ° C., preferably between 320 ° C. and 450 ° C., preferably between 330 ° C. and 400 ° C or between 850 and 1100 ° C, preferably between 900 and 1100 ° C and preferably between 950 ° C and 1050 ° C
  • the temperature of the gases is not significantly influenced by the small amount of water and the size of the droplets which according to the invention contribute substantially to moisten the powdery compound.
  • the aqueous phase injection taking place in the cloud of injected powdery compound especially in an immediate vicinity of the injection point of the powdery compound, the contact between the aqueous phase droplets and the particles of powdery compound is promoted and very fast, which allows an optimization of the reduction of acid pollutants, facilitated by the layer of water formed around the particles of powdery compound.
  • said gases have, after injection of said powdery compound and of said aqueous phase in the form of droplets, a temperature of between n and n-10 ° C., preferably between n and n-8 °. C, preferably between n and n - 5 ° C, in particular between n and n - 3 ° C, n being the temperature of the gases before injection of the powdery compound and the aqueous phase.
  • said injection of the aqueous phase is carried out through a spray pipe, preferably in the form of a fan plane jet, at a pressure of between 2 and 150 bar.
  • this pressure will be between 2 and 20 bar, preferably between 3 and 15 bar and preferably about 8 bar.
  • the pressure will be between 20 and 150 bar, in particular between 30 and 100 bar.
  • the invention also relates to a device for injecting pulverulent compound, preferably mineral, in particular powdered hydrated lime, into a gas pipe comprising a powder compound injection tubing, connected to a source of powdery compound and arranged to open into said gas line, said powdery substance injection tubing having an outer face and an inner face arranged to be in contact with said powdery compound, said powdery compound injection device further comprising at least one tubing aqueous phase injection in the form of droplets connected to an aqueous phase source.
  • pulverulent compound preferably mineral, in particular powdered hydrated lime
  • Such a device is known from the state of the art, such as, for example, documents CN 1 68568 and JP 10-26 572.
  • the water injection tubing is concentric to a larger hydrated lime injection tubing for hydrated lime slurry in situ.
  • CN 2011 68568 it is provided in some flue gas treatment devices by a lime pit that the position of the inner tube can be adjusted with respect to the position of the outer tube.
  • the inner tube for water has an outlet port projecting or recessed or at the same level with respect to a hydrated lime outlet port of the outer tube.
  • the concentric configuration and the desire to form a suspension of hydrated lime in situ has the effect that a water / lime ratio of 5 to 6 is required.
  • the device according to the documents CN 2011 68568 and JP 10-216 572 has the effect of cooling the flue gases, thus posing a new problem for industrial players increasingly having a tendency to recover the fumes. calories from flue gases to offer more economical and environmentally friendly processes.
  • the present invention aims to overcome the drawbacks of the state of the art by providing a device for the injection of pulverulent compound, preferably mineral, in particular hydrated lime, and the humidification of its particles in the treatment of gas whose risk of clogging is significantly reduced, and this without cooling the gases, thus allowing not to interfere with the recovery of calories from these gases to be treated.
  • pulverulent compound preferably mineral, in particular hydrated lime
  • a device as indicated above characterized in that said at least one aqueous phase injection nozzle is located in a peripheral space located around said outer face of the tubing injection of powdery compound.
  • said at least one aqueous phase tubing located in a peripheral space located around the outer face of the powder compound injection tubing is thus arranged to allow injection of droplets of aqueous phase, in particular liquid water. in an immediate vicinity with respect to the powder compound injection point.
  • immediate vicinity is intended to mean that the distance separating the outside diameters of the aqueous phase and powder compound injection pipes respectively is less than or equal to the diameter of the powder compound injection tubing, preferably less than the radius.
  • the particular configuration of said at least one aqueous phase injection pipe and said powder compound injection pipe makes it possible to treat the gases in quasi-dry manner, by only humidifying the powdery compound, in particular lime, and in the latter case, without forming a suspension of whitewash. This operation is carried out without significantly humidifying the gases, and thus without cooling the gases whose heat recovery is more and more desired.
  • This particular configuration does not require, unlike the state of the art disclosed in CN 201 68568 and JP 10-216 572, weight ratio high water lime and reduces the value from between 5 and 6 to a value less than or equal to 1, 2 preferably less than or equal to 1, more particularly less than or equal to 0.8.
  • a cloud of particles of powdery compound in particular of hydrated lime
  • aqueous phase in particular water
  • these droplets of aqueous phase meet the dense cloud of particles of powder compound and improve the abatement of pollutants, including acidic compounds of gases, without cooling the gases.
  • the device comprises a plurality of aqueous phase injection tubes in the form of droplets, each connected to a distributor connected to said source of aqueous phase, each manifold of said plurality of injection manifolds being located in said peripheral space, each pipe being further provided with a valve.
  • each aqueous phase injection tubing is arranged in a concentric tube, out of which the aqueous phase injection tubing is retractable.
  • each aqueous phase injection tubing has an outlet port in the form of a slot or spray nozzle.
  • the dispenser is connected to a pressurizing means arranged to give the aqueous phase a pressure of between 2 and 150 bar, in particular between 2 and 20 bar, preferably between 3 and 15 bar, and more preferably about 8 bar and in another variant between 20 and 150 bar, in particular between 30 and 100 bar.
  • a pressurizing means arranged to give the aqueous phase a pressure of between 2 and 150 bar, in particular between 2 and 20 bar, preferably between 3 and 15 bar, and more preferably about 8 bar and in another variant between 20 and 150 bar, in particular between 30 and 100 bar.
  • It can of course be a feed in the aqueous phase, in particular in liquid water, directly available at the aforementioned pressures.
  • the device comprises an outer envelope around said peripheral space.
  • the device according to the present invention comprises, in said peripheral space, at least one insulating layer between said outer face of said powder compound injection tubing and said outer casing.
  • the device further comprises a device for closing said peripheral space provided with a series of orifices, among which a powder compound orifice and at least one aqueous phase orifice, said orifice composition with a powder compound being arranged to house an outlet of said powder compound injection tubing, each aqueous phase port being arranged to house an outlet of each aqueous phase injection tubing.
  • said outer envelope has a diameter of between 100 and 250 mm, preferably less than 200 mm and more preferably between 0 and 170 mm, in particular between 25 and 150 mm.
  • said powder compound injection tubing has a diameter of between 75 and 150 mm, preferably between 80 and 125 mm and in particular about 100 mm.
  • each aqueous phase injection tubing has a diameter of between 5 and 30 mm, preferably between 6 and 20 mm and more preferably between 8 and 16 mm.
  • FIG. 1A is a schematic side view of a first embodiment of the gas treatment apparatus according to the present invention.
  • Figure 1B is a sectional view along the line 11 of Figure 1A.
  • Fig. 2A is a schematic side view of a second embodiment of the gas treatment apparatus according to the present invention.
  • Figure 2B is a sectional view along the line II-II of Figure 2A.
  • FIG. 3 is a schematic side view of the embodiment according to FIG. 1 of the gas treatment device according to the present invention, used for example in a flue gas duct, the injection direction of the powdery compound being here perpendicular to the flow direction of the flue gases.
  • FIG. 4 is a schematic side view of the second embodiment according to FIG. 2 of the flue gas treatment device according to the present invention, used in a flue gas duct, the injection direction of the powdery compound being here also perpendicular to the flow direction of the flue gases.
  • Figure 5 is a schematic side view of the embodiment according to Figure 2 of the flue gas treatment device according to the present invention, used in a flue gas duct.
  • the direction of injection of the powdery compound is located obliquely to the flow direction of the flue gas.
  • Figures 3 to 5 illustrate modes, among others, of coupling devices according to the invention to a flue gas duct.
  • the powdered compound injected is in the illustrated cases of mineral nature and the treated gases are flue gases.
  • the device according to the present invention is a device for injecting pulverulent inorganic compound 1 to be introduced into a flue gas line, comprising a pulverulent inorganic compound injection pipe 2 connected to a source of pulverulent inorganic compound (not shown).
  • the mineral compound injection tubing is arranged to open into said flue gas duct 3 (see FIG. 3) and to allow the exit of the inorganic compound via a mineral compound outlet port 14.
  • the compound injection tubing mineral 2 has an outer face 4 and an inner face 5. In operation, the inner face 5 is in contact with said powdery mineral compound during its feeding into the injection pipe 2.
  • the pulverulent inorganic compound injection device 1 comprises a plurality of aqueous phase injection tubes 6 in the form of droplets, each connected to a distributor 7 connected to an aqueous phase feed 8.
  • each tubing 6 of the plurality of injection tubings is located around the mineral compound injection tubing 2 in a space outside thereof, referred to herein as the peripheral space 9.
  • Each The aqueous phase injection tubing 6 further comprises a valve 0 situated between the distributor 7 and the aqueous phase outlet 1 of each aqueous phase injection tubing 6.
  • aqueous phase outlet 11 in the form of droplets of each tubing
  • the aqueous phase injection is advantageously carried out by an aqueous phase outlet orifice in the form of a slot or plane sprayer, using a nozzle. (not shown)
  • a pressurizing means 12 makes it possible to give the desired pressure to the incoming water via the water supply 8.
  • the pressure of the aqueous phase feed 8 is typically between 2 and 150 bar. In a variant, this pressure will rather be between 2 and 20 bar, preferably between 3 and 15 bar and more preferably about 8 bar. In another variant, the pressure will be between 20 and 150 bar, in particular between 30 and 100 bar.
  • the mineral compound injection device further comprises a flange 13 provided with through holes 18 for bolting or otherwise securing the flue gas treatment device to a flue gas duct.
  • the flue gas duct 3 to be treated comprises an orifice for the introduction of the device 1. It is introduced into this orifice and fixed to the duct in a current manner, by the flange 13 and fixing means 15.
  • the clamping of the flange 13 maintains a support on the outer face 16 of the flue gas duct 3, but also ensures the sealing of the connection of the device according to the present invention. invention.
  • a second flange 7 is present on the flue gas treatment device.
  • This flange 17 is provided with a series of through holes 19 arranged to receive fastening means.
  • the flange 17 is arranged to be connected to a current source of mineral compound (not shown).
  • an outer envelope 20 is present around said peripheral space 9.
  • the outer envelope 20 preferably has a diameter of between 100 and 250 mm, preferably less than 200 mm and more preferably between 10 and 170 mm, in particularly between 125 and 150 mm.
  • an insulating layer may be provided between the outer face 4 of said powdery mineral compound injection pipe and the outer shell 20.
  • the insulation may be simply air or any material insulation known to those skilled in the art. It avoids the cooling of the outer face 4 which is isolated from the tubing 6 which reduces the risk of agglomeration against the inner face 5 of the mineral compound circulating in the mineral compound injection tubing.
  • the device according to the present invention further preferably comprises a cap or closure device 21 of said peripheral space.
  • This cap is provided with a series of orifices, among which an outlet orifice for the mineral compound 14 and as many outlet orifices for the aqueous phase 11 as there are aqueous phase tubes 6 present.
  • the device according to the present invention comprises such a cylindrical mineral compound injection tube 2 which has been modified in such a way that at least one aqueous phase injection tubing 6 can be inserted along the length of the substantially cylindrical tube.
  • FIGS. 1A, 1B and 3 eight injection tubings of aqueous phase 6, in the form of droplets, have been placed around the mineral compound injection pipe 2, and the diameters of these tubing 6 were chosen so that the tubing 6 can integrate into the flange 13.
  • the powdery inorganic compound injection tubing 2 has a diameter of between 75 and 150 mm, preferably between 80 and 125 mm and in particular about 100 mm.
  • each water injection tubing 6 has a diameter of between 5 and 30 mm, preferably between 6 and 20 mm and more preferably between 8 and 16 mm.
  • the device according to the present invention When it is desirable to treat flue gas in a pipe with hydrated lime to cut acid pollutants among others, the device according to the present invention is positioned as illustrated for example in FIG. 3. Hydrated lime is then injected into the hydrated lime injection tubing 2 and leaves the tubing via the outlet orifice 14. At this moment, a cloud of hydrated lime, the particles of which typically have an average particle size d 50 of less than 80 ⁇ , advantageously less than 50 ⁇ , preferably less than 35 ⁇ m, preferably less than 25 ⁇ and in particular less than or equal to 0 ⁇ m, in particular less than or equal to 8 ⁇ m, is formed in the flue gas line to be treated. 3.
  • the hydrated lime before injection into the flue gases, has a moisture content of between 0.2 and 10% by weight, in particular between 0.5 and 4%. by weight, preferably less than 2%, in particular less than 1.5%.
  • the aqueous phase under pressure enters the distributor 7 via said feed 8 and then enters the water injection pipes 6 for which the valves 1 or some of them are in the open position.
  • the step of injecting the aqueous phase in the form of droplets is carried out in said cloud or stream of mineral compound in said flue gas pipe 3, in a neighborhood immediately downstream of said point of injection of the mineral compound with respect to the flow direction of the flue gas (indicated by a double arrow G in FIG. 3), and this, in said flue gas duct 3.
  • the injected powdery mineral compound is moistened and little or no flue gases to be treated.
  • the injection of droplets of aqueous solution into a neighborhood immediately downstream of the injected mineral compound particles, with respect to the direction of flow of the flue gas to be treated, is carried out in this embodiment by closing the valves 10 present on the water phase injection pipes 6 located upstream and opening those of downstream pipes.
  • only the pressurized aqueous phase droplet injection pipes situated in the part S of the flue gas treatment device according to the present invention may have their valves in the open position while the other pressurized droplet injection manifolds have valves in the closed position.
  • the injected aqueous phase droplets are introduced into a neighborhood immediately downstream of the point of injection of mineral compound particles, and the mineral compound particles are advantageously moistened.
  • the pollutants of the flue gases are then captured by said mineral compound and this in an improved manner by the presence of the particles of aqueous phase surrounding the particles of inorganic compound. Then, the mineral compound enriched in pollutant compounds and pollutant-depleted flue gases are recovered separately in the usual manner, in particular by filtration.
  • the mixed device for injecting mineral compound / aqueous phase according to the present invention is therefore a simple, easy and inexpensive concept that improves the capture of acid gases from flue gas.
  • the temperature of the flue gases is typically between 100 and 1100 ° C. In some installations, this temperature varies from 110 ° C. to 350 ° C., preferably from 130 ° C. to 250 ° C., and more preferably from 150 ° C. to 230 ° C., in particular 180 ° C. to 220 ° C.
  • the temperature of the flue gases is typically between 250 ° C and 500 ° C or between 850 and 1100 ° C further upstream ⁇ closer to the zone combustion), preferably between 300 ° C and 450 ° C or between 900 and 1100 ° C further upstream and preferably between 330 ° C and 400 ° C or between 950 ° C and 1050 D C further upstream.
  • the effect of the humidification of the mineral compound is of relatively short duration since the droplets of aqueous phase evaporate very quickly in the hot gases. Therefore, the contact between the mineral compound particles injected into the flue gases and the water droplets must be obtained as quickly as possible.
  • the size of the aqueous phase droplets is on average between 500 and 5000 ⁇ m, preferably between 500 and 1000 ⁇ m, or between 1000 and 5000 ⁇ m depending on the injection conditions, and is obtained in particular by using nozzle ports.
  • Flat outlet in the form of slits through which the aqueous phase droplets are formed.
  • the size of the droplets obtained also promotes the contact between the droplets of aqueous phase injected into the cloud of mineral compound particles and the mineral compound particles as soon as they are injected into the flue gas duct.
  • a mineral composition in particular a moist hydrated lime (containing more than 2% or even 4% water) or previously moistened because of the agglomeration of the particles. which occurs and clogs the injection tubing.
  • a hydrated moist or previously moistened lime is more easily subject to carbonation (fairly fast), which induces a reduction of the capture performance.
  • agglomerated particles of mineral compound, in particular hydrated hydrated lime have reduced capture capacities because of the decrease in accessibility to their pores. Typically, it is the fine particles that are sought to improve the capture performance.
  • the use of the device according to the present invention allows the fine particles of mineral compound injected into the flue gas line to be treated to be wetted as such, in situ, and react with the particular acidic gases in the cloud of droplets. water phase created directly and also dry in situ because the evaporation is very fast in the hot flue gases. As a result, evaporation of water occurs before the particles have time to agglomerate.
  • the amount of water injected is only the amount of water needed to humidify the mineral compound particles and to create a cloud formed of mineral compound particles and phase droplets.
  • aqueous aqueous.
  • the weight ratio between the said injected aqueous phase in the form of droplets and the said injected powdery mineral compound is less than or equal to 1, 2, preferably less than or equal to 1 and in particular less than or equal to 0.8.
  • the aforementioned weight ratio is also greater than or equal to 0.1 and particularly greater than or equal to 0.2. Consequently, the aqueous phase injected in the form of fine droplets has little impact on the temperature of the flue gas to be treated and does not disturb the subsequent potential stages of heat recovery.
  • the flue gases have, after injection of the mineral compound and of the aqueous phase in the form of droplets, a temperature of between n and n-0 ° C., preferably between n and n-8 ° C., preferably between n and n - 5 ° C, in particular n - 3 ° C, n being the temperature of the flue gases before injection of the inorganic compound and of said aqueous phase.
  • the two aqueous phase and mineral compound injection systems are typically attached to the same flue gas treatment device, it goes without saying that they operate independently of one another. . As a result, it is possible to work only by injecting droplets of aqueous phase or only the mineral compound, if the case requires it.
  • Figure 2 illustrates a variant of the flue gas treatment device according to the present invention.
  • the device 1 here comprises a powdery mineral compound injection tubing 2 connected to a source of powdery mineral compound (not shown).
  • the mineral compound injection tubing is arranged to open into said flue gas duct 3 (see FIGS. 4 and 5) and to allow the mineral compound to exit via an inorganic compound outlet orifice 14.
  • the injection manifold of mineral compound 2 has an outer face 4 and an inner face 5. In operation, the inner face 5 is in contact with said powder mineral compound which is injected into the injection pipe 2.
  • the pulverulent inorganic compound injection device 1 also comprises an aqueous phase injection pipe 6 in the form of droplets, which is connected to an aqueous phase feed 8, and which is located in a concentric tube located in the space 9.
  • the aqueous phase injection tubing although not shown here, may further include a stop valve 10.
  • the aqueous phase outlet port 11 in the form of droplets of the tubing.
  • Aqueous phase injection is in practice carried out in the form of a slot or a planar sprayer.
  • the pressure of the aqueous phase feed 8 is typically between 2 and 150 bar. In a variant, this pressure will rather be between 2 and 20 bar, preferably between 3 and 5 bar and more preferably about 8 bar. In an other alternatively, the pressure will be between 10 and 150 bar, in particular between 20 and 100 bar. These high pressures make it possible to prevent fouling of the spray pipe.
  • the mineral compound injection device further comprises a flange 13 provided with through openings 18 for bolting or otherwise securing the flue gas treatment device to a flue gas duct via a flange 23.
  • the flue gas duct 3 to be treated may comprise an introduction duct 22 for the device 1 according to the present invention.
  • the introduction duct 22 is provided with a flange 23 at its end.
  • the device according to the present invention 1 is introduced into this duct and fixed on it with the aid of the flanges 13 and 23.
  • the step of injecting the powdery mineral compound is carried out in the flue gas duct 3 at an angle of 90 to 150 degrees, preferably less than or equal to 145 degrees, preferably less than or equal to 140 degrees and in particular less than or equal to 135 degrees, with respect to the flow direction G of the flue gases.
  • This orientation of the tubular of the mineral compound with respect to the flow direction of the flue gases is in no way related to the embodiment of the device according to the invention.
  • the embodiment comprising a plurality of aqueous phase injection tubing shown in FIGS. 1 and 3 may also be inclined with respect to the wall of the flue gas duct.
  • the device according to the present invention in the version illustrated in FIGS. 1A, 1B, 2A and 2B, may be more or less inserted in the flue gas duct, depending on the desideratas and may typically penetrate a length between 0 and 40 cm in the gas line.
  • Technical considerations such as tubing length, operating parameters of the device according to the present invention, in this embodiment, vary in the same way as described for FIGS. 1A, 1B and 3.
  • a second flange 17 is present on the flue gas treatment device.
  • This flange 17 is provided with a series of through holes 19 arranged to receive a fixing means.
  • the flange 17 is arranged to be connected to a source of mineral compound (not shown).
  • an outer envelope 20 is present around said peripheral space 9.
  • the outer envelope 20 preferably has a diameter of between 100 and 250 mm, preferably less than 200 mm and more preferably between 110 and 170 mm, in particular between 125 and 50 mm.
  • an insulating layer may be provided between said outer face 4 of said powdery inorganic compound injection tubing and the outer shell 20.
  • the insulation may be simply air or any insulator known to those skilled in the art and makes it possible to avoid the cooling of the outer face 4, thus isolated from the aqueous solution tubing 6, which reduces the risks of agglomeration of the particles of the mineral compound, in particular hydrated lime, circulating in the injection pipe 2.
  • the device according to the present invention further preferably comprises a cap or closure device 21 of said peripheral space provided with a series of orifices among which a mineral compound outlet orifice 14 and an outlet port of the tube concentric with the tubing of aqueous phase injection 11.
  • the aqueous phase injection tubing 6 is arranged in a concentric tube, from which the aqueous phase injection tubing 25 is retractable. , which allows clean or change the injection tubing of the aqueous phase without stopping the injection of mineral compound.
  • the present invention provides a slight curvature in the mineral compound injection tubing, which remains as small as possible to avoid obstacles within the essentially cylindrical tube of supply of mineral compound 2 and thus reduce the agglomeration of mineral compound on the walls.
  • the main mineral compound injection pipe typically has a diameter of 100 mm and the concentric tube with the aqueous phase injection pipe has a diameter of 25 mm. mm. Both tubes are confined in an envelope 20 having a diameter of about 125 mm.
  • the first sample (Ech 1) was a hydrated lime obtained according to the teaching of the patent application WO 97/14650.
  • the second sample (Ech 2) was a hydrated lime obtained according to the teaching of the patent application WO 2007/000433.
  • the table shows the SO 2 abatement rates obtained by varying the humidity of the reagents tested by 0.7% by weight relative to the weight of hydrated lime at 4.1% by weight, for a stoichiometric factor of 2, 5 and a flow rate of Q absorbent.
  • the flow rate of absorbent Q corresponds to the flow of hydrated lime necessary for the neutralization of the flow rate of S0 2 , if the yield of the reaction was 100% (stoichiometric equilibrium), multiplied by a "stoichiometric" factor, taking into account that part of the injected absorbent does not actually participate in the reaction.
  • Q is 5.05 g / h.
  • the parameters of the flue gas are as follows:
  • a hydrated lime prepared according to the teaching of the patent application WO2007 / 000433 was injected upstream of a filter to sleeves for the reduction of S0 2 .
  • S0 2 content 1800 mg / Nm 3 upstream of the bag filter and 700 mg / Nm 3 at the outlet
  • a reduction of 15 to 20% in the consumption of lime was observed when the lime was moistened with water.
  • comparison of the situation when the lime was not humidified (17 dm 3 / h water or water / lime weight ratio of 0.25).
  • a lime conversion rate of 35% is observed when the lime is not moistened and 40% when it is moistened.
  • the device of Figure 1 according to the present invention has been used; it had an inclination of about 120 ° with respect to the direction of gas flow.
  • the parameters of the flue gas are as follows:
  • a hydrated lime prepared according to the teaching of the patent application WO 2007/000433 was injected upstream of a bag filter to study the effects of its humidification rate on the S0 2 abatement rates.
  • an SO 2 content at the filter outlet of respectively 134 mg / Nm 3 (equivalent to a lime conversion rate of 53%) when the lime is not moistened and 1 12 mg / Nm 3 (lime conversion rate of 67%) when the lime is moistened at a rate of 30 dm 3 / h of water (weight ratio water / lime 0.6). It is therefore observed that the moistened lime allows a reduction of SO 2 of 25% in comparison with the same non-moistened lime.
  • a standard hydrated lime was injected into the same plant and with the same flue gas parameters as the example 3 to study the effects of its rate of moistening the S0 2 abatement rate.
  • an SO 2 content at the outlet of the filter of respectively 336 mg / Nm 3 (equivalent to a lime conversion rate of 20%) when lime is not moistened, 266 mg / Nm 3 (lime conversion rate of 37%) when lime is moistened at a rate of 30 dm 3 / h of water (water / lime weight ratio of 0.25) and 241 mg / Nm 3 (lime conversion rate of 43%) when the lime is moistened at the rate of 20 dm 3 / h of water (water / lime mass ratio of 1). It is therefore observed that a lime moistened with 30 and 120 dm 3 / h of water allows a reduction of S0 2 reduction of respectively 85% and 10% in comparison with the same unhumidified lime.

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PCT/EP2014/063017 2013-06-25 2014-06-20 Procede et dispositif de traitement de gaz par injection de compose pulverulent et de phase aqueuse Ceased WO2014206880A1 (fr)

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ES14736324.6T ES2615804T3 (es) 2013-06-25 2014-06-20 Procedimiento y dispositivo de tratamiento de gas por inyección de compuesto pulverulento y fase acuosa
KR1020157035463A KR101644899B1 (ko) 2013-06-25 2014-06-20 분말 화합물 및 수성 상을 주입함으로써 가스를 처리하기 위한 방법 및 장치
BR112015030657-8A BR112015030657B1 (pt) 2013-06-25 2014-06-20 Método e dispositivo para tratamento de gás pela injeção de um composto em pó e de uma fase aquosa
JP2015563092A JP6059828B2 (ja) 2013-06-25 2014-06-20 粉末状化合物を噴射することによりガスを処理する方法及び装置
US14/898,293 US9579601B2 (en) 2013-06-25 2014-06-20 Method and device for treating gas by injecting a powdered compound and an aqueous phase
CA2913240A CA2913240C (fr) 2013-06-25 2014-06-20 Procede et dispositif de traitement de gaz par injection de compose pulverulent et de phase aqueuse
AU2014301338A AU2014301338B2 (en) 2013-06-25 2014-06-20 Method and device for treating gas by injecting a powdered compound and an aqueous phase
DK14736324.6T DK3013459T3 (en) 2013-06-25 2014-06-20 Method and apparatus for treating gas by injection of a powdered compound and an aqueous phase
SG11201510356TA SG11201510356TA (en) 2013-06-25 2014-06-20 Method and device for treating gas by injecting a powdery compound and an aqueous phase
EP14736324.6A EP3013459B1 (fr) 2013-06-25 2014-06-20 Procede et dispositif de traitement de gaz par injection de compose pulverulent et de phase aqueuse
ZA2015/09110A ZA201509110B (en) 2013-06-25 2015-12-14 Method and device for treating gas by injecting a powdered compound and an aqueous phase

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WO2018095553A1 (en) 2016-11-28 2018-05-31 S.A. Lhoist Recherche Et Developpement Process for pneumatically conveying a powdery material

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