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  • B01D53/34—Chemical or biological purification of waste gases
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  • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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  • B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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  • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
  • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
  • B01J20/3204—Inorganic carriers, supports or substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3234—Inorganic material layers
  • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/16—Clays or other mineral silicates
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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  • B01J35/615—100-500 m2/g
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/10—Inorganic adsorbents
  • B01D2253/106—Silica or silicates
• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01D2253/116—Molecular sieves other than zeolites
• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01D2257/602—Mercury or mercury compounds

Definitions

• the present invention relates to a composition for reducing heavy metals and dioxins in flue gases comprising a solid sorption material which is a mineral compound, preferably non-functionalized, chosen from phyllosilicates of the "palygorskite-sepiolite" group. , according to Dana's classification.
• Dioxins and furans as well as heavy metals, in particular mercury are toxic compounds, present in flue gas, especially in the gaseous state and whose emission is in general strictly regulated.
• the word "dioxin” will be used in the generic sense, including dioxins and furans and, optionally, other analogous compounds, especially the precursors of dioxins and furans, such as polycyclic aromatic hydrocarbons ( PAH).
• standards in this field generally include all dioxins (75 species) and furans (135 species) in a single "equivalent toxic” (TEQ) concentration, expressed relative to the most toxic dioxin molecule.
• heavy metals refers mainly to metals having a density greater than 5000 kg / m 3 , in particular the most common heavy metals, which are generally regulated, namely lead, chromium, copper, manganese, antimony, arsenic, cobalt, nickel, vanadium, cadmium, thallium and mercury, preferably lead, thallium, cadmium and Mercury, in particular mercury.
• These metals can be in the elemental state or in ionic form.
• the reduction of dioxins and heavy metals present in the flue gases is generally in the state of the art operated by means of carbon compounds, such as activated carbons, lignite cokes or the like.
• carbon compounds such as activated carbons, lignite cokes or the like.
• the choice of the type or types of carbon compounds depends on the predominance of the dioxins, on the one hand or heavy metals, on the other hand, in the pollutants to be cut down and the respective regulations to be satisfied for these two types of pollutants.
• WO 2006/099291 discloses the mercury reduction of flue gases using a catalytic adsorbent in the form of a carbon compound doped with halogenated compounds. More particularly, a halide salt is dispersed on activated charcoal and the catalytic oxidation activity of the activated carbon promotes the formation of mercury halide. An oxidant oxidizes the mercury and the anion of the doping compound provides a counterion for the mercury ion oxidized by the oxidant. As can be seen, the presence of an oxidant is therefore essential in this type of compound.
• the initial emissions of dioxins and certain heavy metals are higher, sometimes largely, than the regulations in force, so it is essential to cut down sometimes considerably, these two types of pollutants.
• the same well-chosen carbon compound may then be suitable for the simultaneous observance of the regulations in force for discharges of heavy metals and for the discharge of dioxins. It can be carried out either as such, or in admixture with a basic reagent, in a fixed bed in granular form or by injection into the gas in powder form; the solid particles are then trapped downstream, for example in a textile filter, where their action is prolonged.
• the effectiveness of carbon compounds in cutting down heavy metals and dioxins is widely recognized. Nevertheless, the use of these carbon compounds in the flue gases has two major drawbacks:
• the carbon compounds are generally expensive compounds and the step using said carbon compounds is difficult to integrate into a complete flue gas treatment process, which must often also eliminate nitrogen pollutants.
• the elimination of catalytic nitrogen oxides is generally carried out at a gas temperature above 200 ° C., which is incompatible with the use of carbon compounds.
• Sulfur is deposited on a mineral support, such as natural silicates.
• a mineral support such as natural silicates.
• the silicate is considered as an inert support with respect to the pollutant to be slaughtered; the latter is trapped by reaction with the sulfur compound to form in general a sulphide.
• silicates functionalized with sulfur compounds are the subject of a dangerous, heavy and expensive manufacture which penalizes its use.
• the document ES 8704428 discloses a sulfurization of a silicate by a hydrogen sulphide oxidation reaction at a well-defined molar proportion for the purpose of adsorbing elemental sulfur on said silicate.
• the handling of hydrogen sulfide, highly toxic and extremely flammable, is dangerous and the strict molar proportion necessary to avoid any subsequent oxidation reaction is very restrictive.
• the document "ES 2136496" provides a similar teaching, describing a process for the sulfidation of natural silicates to retain metal vapors.
• compositions which are alternatives to the carbon compounds as mentioned at the beginning, are described for the reduction of dioxins, in particular the use of sepiolite-type mineral or a non-functionalized analogue (see in particular JP 2000140627, JP 2001276606 and JP 2003024744).
• JP 2000140627, JP 2001276606 and JP 2003024744 not all phyilosilicates exhibit good sorption solids for dioxins.
• JC Japanese Acid Clay montmorillonite
• K10 montmorillonite K10 montmorillonite
• China clay kaolin do not capture much or little of the chlorobenzene or other model molecules used because of their dioxin analogies (Chemosphere, 56). 8, 745-756 (2004)).
• Document FR 1481646 also discloses siliceous adsorbent compositions obtained by reaction, in particular with high-concentration hydrochloric acid, intended for the adsorption of gases or liquids.
• the starting compound has reacted to be converted into an amorphous compound which does not retain its initial crystalline structure.
• This document also discloses the compounds obtained in composite form.
• the abatement results mentioned in the examples relate solely to liquids such as water or to gases such as oxygen or possibly butane or the like.
• Patent EP 1732668 B1 provides for the use of non-functional mineral compounds of the "palygorskite-sepiolite” group according to the Dana classification for the reduction of heavy metals, in particular mercury.
• the effectiveness of sepiolite for the abatement of mercury appears limited, in comparison with activated carbons, requiring a priori an overdose.
• the object of the invention is to overcome the drawbacks of the prior art by providing a composition as mentioned at the beginning, in which the said inorganic compound is doped with a halide salt.
• this mineral compound doped with a halide in the form of salt allows a joint and effective reduction of dioxins and heavy metals, especially in the gaseous state, present in the gases. of fumes, using a single mineral compound, whose manufacture and implementation are simple and non-hazardous.
• the mineral compound is selected from the group of phyilosilicates of the sepiolite subgroup according to the Dana classification.
• the phyilosicates covered by the invention have a high porosity, typically a pore volume of between 0.20 and 0.60 cm 3 / g, in particular between 0.25 and 0.40 cnfVg, measured by the BJH method, applied to the nitrogen desorption isotherm, obtained at the temperature of liquid nitrogen (77 K). This porous volume range is for pores between 2 and 100 nanometers in size.
• these phyilosicates typically have a specific surface area of 100 to 200 m 2 / g, particularly from 110 to 160 ng / g.
• halide salt-doped mineral compound is meant a mineral compound mentioned above whose surface accessible to the flue gas is partially or completely covered by a halide salt.
• the gas accessible surface comprises not only the outer surface of the particles constituting the mineral compound but also some or all of the inner surface of these particles, partially porous.
• the inorganic compound doped with a halide salt contains, on a dry basis, from 0.5% to 20%, preferably from 1% to 15%, in particular from 1.5% to 10% by weight of sodium salt. halide based on the weight of the composition according to the invention.
• the halide salt may be an alkaline or alkaline earth halide, in particular NaCl, NaBr or NaI 1 KCl, KBr or Kl, CaCl 2 , CaBr 2 or CaCl 2 , MgCl 2 , MgBr 2 or MgI 2 , or else NH 4 CI, NH 4 Br or NH 4 I or a mixture thereof.
• the mineral compound doped with said halide salt has a BET specific surface area of between 70 and 170 m 2 / g, often between 80 and 140 m 2 / g and in particular between 90 and and 130 m 2 / g.
• the inorganic compound doped with said halide salt has a pore volume of between 0.15 and 0.32 cm 3 / g, preferably between 0.20 and 0.30 cm 3 / g and more preferably between 0.22 and 0.28 cm 3 / g, measured by the BJH method, applied to the nitrogen desorption isotherm, obtained at a liquid nitrogen temperature of about 77 K for pore size between 2 and 100 nm.
• the inorganic compound according to the invention is in picvéruiente form, namely that the size of the particles is predominantly (more than 90%) less than 1 mm and substantially greater than 1 ⁇ m, that is to say that it preferably has a d 90 smaller than 1 mm.
• d 90 is meant the interpolated value of the particle size distribution curve, such that 90% of the particles have a dimension smaller than said value.
• the present invention also relates to a process for preparing a mineral solid composition according to the invention. This process comprises the steps of:
• a solid material of sorption which is a mineral compound, preferably non-functionalized, chosen from the phyllosilicates of the "palygorskite-sepiolite” group according to the Dana classification,
• contacting said ore compound and said halide salt with the formation of a halide salt-doped mineral compound is carried out with stirring.
• said fed mineral compound has a humidity of between 0.1 and 100 g / kg, advantageously between 2 and 90 g / kg.
• said contacting is carried out at ambient temperature.
• said halide salt is in liquid form, in aqueous phase.
• said step of bringing said mineral compound into contact with said halide salt is advantageously a spraying of said halide salt on said mineral compound, optionally in the presence of stirring.
• said step of bringing said mineral compound into contact with said halide salt is a dipping in one or more steps, optionally with stirring and optionally with drying steps and / or intermediate deagglomeration, said mineral compound in said liquid phase halide salt.
• said halide salt in the liquid phase is an aqueous solution having a halide salt content of between 1% and the salt saturation of the solution, in particular between 1% and 30%, in particular between 5% and 27%, preferably between 10% and 27% by weight relative to the total weight of said solution.
• a low salt concentration in the solution leads to more difficult mixing and subsequent drying.
• the concentration of the solution is limited by the solubility of the salt.
• the process according to the invention further comprises a step of drying and / or deagglomeration of said halide salt-doped mineral compound, preferably according to operating conditions (ambient temperature, residence time, etc.).
• operating conditions ambient temperature, residence time, etc.
• doped inorganic compound reaches a temperature of between 60 and 200 0 C 1 in particular between 75 and 170 0 C, in order to achieve a residual moisture content of preferably less than 100 g / kg, preferably less than 50 g / kg .
• said salt of halide is an alkaline halide, an alkaline earth halide or the like, preferably selected from the group consisting of NaCl, NaBr, NaI, KCl 1 KBr. , Ki 1 CaCl 2 , CaBr 2 , CaCl 2 , MgCl 2 , MgBr 2 , MgI 2 , NH 4 Cl, NH 4 Br or NH 4 I or mixtures thereof.
• the present invention also relates to a use of a mineral solid composition as described above, for the reduction of dioxins and heavy metals, in particular in the gaseous state, in particular mercury and especially mercury metal Hg °, present in the flue gases, by contacting the flue gases with the aforementioned mineral solid composition and using a mixture of basic reagent and said mineral solid composition for the treatment of flue gases.
• the doped mineral compound according to the invention is therefore brought into contact with the flue gas to be treated, either as such, or in combination with a basic agent commonly used for the reduction of acid gases from fumes, such as lime or the like. . Therefore, the implementation of the mineral solid composition according to the invention requires only obtaining a simple product of use, preferably dry.
• the use of the doped mineral compound according to the invention for the reduction of dioxins and heavy metals thus comprises contacting said doped mineral compound, preferably in the dry state, carried out at a temperature in the range from 70.degree. at 350 0 C, preferably between 110 and 300 0 C and more preferably between 120 and 250 0 C.
• a temperature in the range from 70.degree. at 350 0 C preferably between 110 and 300 0 C and more preferably between 120 and 250 0 C.
• the inorganic compound according to the invention is used in pulverulent form, namely that the size of the particles is predominantly (more than 90%) less than 1 mm and substantially greater than 1 ⁇ m.
• the mineral compound is then injected pneumatically into the gas vein.
• the use of the doped mineral compound according to the invention for the reduction of dioxins and heavy metals in the flue gas is often to be included in a complete flue gas treatment.
• a treatment comprises a step of eliminating major acid pollutants by contacting said flue gases with basic reagents.
• the main acid pollutants in the flue gases include hydrochloric acid, hydrofluoric acid, sulfur oxides or nitrogen oxides, their emission levels in the flue gases before treatment are order of several tens to several hundred mg / Nm 3 .
• the doped mineral compound according to the invention for the reduction of dioxins and heavy metals in gases
• said basic reagents for example lime
• said doped mineral compound are used separately or in a mixture. This last case allows a gain of investment and space since since then two stages can be realized simultaneously and at the same place.
• Examples 1 to 7 and the comparative example are laboratory scale tests, according to the following experimental procedure.
• the inorganic compound doped with a halide salt (Examples 1 to 5 according to the invention) or undoped (comparative example) are placed in the center of a cylindrical reactor 110 mm long and 10 mm inside diameter so to form a homogeneous bed on rock wool, which corresponds to about 0.1 g of mineral compound.
• Instruments measure the level of metallic mercury at the outlet of the reactor. Prior to its arrival at the detector, the gas passes through a solution of SnCl 2 , so as to convert the possible mercury fraction present in ionic form into metallic mercury.
• the soaking of a sepiolite analogous to that of the comparative example is carried out.
• This soaking is carried out by immersing the sepiolite in an aqueous solution with a content of 10% by weight of KBr relative to the weight of the aqueous solution.
• the wet sepiolite thus doped is dried and deagglomerated at a temperature of
• the amount of KBr deposited on the sepiolite after drying is 10% by weight relative to the weight of the composition obtained according to the invention.
• the mercury reduction capacity of this KBr-doped sepiolite according to the invention in the device previously described and operating under the same operating conditions as in the comparative example, is 255 ⁇ g Hg / g of doped sepiolite. .
• a spraying of a sepiolite analogous to that of the comparative example is carried out.
• Spraying is carried out from an aqueous solution with a content of 27% by weight of NaCl based on the weight of the aqueous solution.
• the solution is sprayed on the sepiolite with mechanical stirring, until a humidity of 20% is obtained.
• the wet sepiolite thus doped is dried and deagglomerated, at a temperature of 150 ° C. in an oven, so as to reach a residual moisture of less than 50 g / kg.
• NaCl deposited on the sepiolite after drying is 6% expressed by weight relative to the weight of the composition.
• the abatement capacity mercury of this sepiolite doped with NaC! is equal to 48 ( ⁇ g Hg) / g of doped sepiolite.
• Example 2 is reproduced but with a solution containing 27% by weight of MgCb relative to the weight of the aqueous solution.
• the amount of MgCb deposited on the sepiolite after drying is 5% expressed by weight relative to the weight of the composition.
• the mercury reduction capacity measured is equal to 190 ( ⁇ g Hg) / g of doped sepiolite.
• Example 2 is reproduced but with 27% by weight CaBr 2 solution relative to the weight of the aqueous solution.
• the amount of CaBr 2 deposited on the sepiolite after drying is 6%, expressed by weight relative to the weight of the composition.
• the mercury reduction capacity measured is equal to 343 ( ⁇ g Hg) / g of doped sepiolite.
• Example 2 is reproduced but with a solution containing 27% by weight of MgBr 2 relative to the weight of the aqueous solution, the amount of MgBr 2 deposited on the sepiolite after drying is 7% expressed by weight relative to the weight of the composition.
• the measured mercury abatement capacity is equal to 1770 ( ⁇ g Hg) / g of doped sepiolite.
• Example 4 is reproduced but the amount of CaBr 2 deposited on the sepiolite after drying is 2% expressed by weight relative to the weight of the composition.
• a breakthrough curve is produced at fixed temperatures of 13O 0 C, 18O 0 C; 200 0 C, 250 0 C and 300 0 C.
• the mercury reduction capacity measured is respectively equal to 208, 426, 582, 750 and 672 ( ⁇ g Hg) / g of sepiolite doped under the conditions of the test.
• Example 7 effect of the concentration of the doping solution
• Example 2 is repeated by impregnating 4 samples of sepiolite analogous to that of the comparative example by spraying with solutions of KBr with a concentration of 5%, 10%,
• the sepiolite thus doped according to the invention is placed in a reactor maintained at a fixed temperature of 130 ° C.
• the mercury abatement capacity is respectively 33, 44 and 75 ( ⁇ g Hg) / g of doped sepiolite under the conditions of the test.
• the doping according to the invention does not significantly alter the initial specific surface area and pore volume of the undoped mineral compound, in the concentration range and with the dopant in question, which makes it possible to predict the conservation of dioxin abatement performances.
• Table 2 Evolution of specific surface area, pore volume and mercury removal, as a function of doping additive content
• analogous sepiolite is doped with that of the comparative example by spraying in an industrial mixer.
• an aqueous solution with a content of 20% by weight of KBr is sprayed with respect to the weight of the aqueous solution.
• the flow of sepiolite doped, wet at 17%, is 200 kg / h.
• the latter is deagglomerated and dried in a mill / caged dryer (cage m / 7 /), using hot gases at about 400-450 0 C and a residence time such that the gases leave the mill / dryer at approximately 150 0 C.
• a sepiolite according to the invention is obtained, dried and 5% by weight of KBr relative to the weight of the composition.
• the sepiolite thus doped is used in a treatment line of 7 t / h of waste from a household waste incinerator, producing approximately 43,000 Nm 3 / h of fumes to be treated.
• the doped sepiolite is metered by means of a screw and injected pneumatically into the gas stream at 150 ° C. at a rate of 3 kg / h, and then collected in a bag filter, in particular with the combustion dusts.
• the dioxin content was measured at the stack by an approved body according to the standards EN 1948 (1997) and ISO 9096 (2003).
• the value obtained is 0.04 ng TEQ / Nm 3 on dry gases and brought to a concentration of 11% of 0 2 - This result perfectly meets the emission regulations of 0.1 ng TEQ / Nm 3 sec, reduced to 11% Cl 1 O 2 .
• the same doped sepiolite is used as in Example 10 in a treatment line of 7 t / h of waste from a household waste incinerator, producing approximately 43,000 Nm 3 / h of fumes to be treated.
• the doped sepiolite is metered by means of screws and pneumatically injected into the gas stream at 180 ° C. at a rate of 8 kg / h, and then collected in a bag filter, in particular with the combustion dusts.
• Mercury concentrations downstream of the atomic absorption bag filter were measured.
• the measured mercury concentrations, normalized on dry gases and reported at 11% oxygen, are from 0.1 ⁇ g / Nm 3 to 0.8 ⁇ g / Nm 3 . These results are significantly lower than the current regulations of 50 ⁇ g / Nm 3 .
• Dioxin content was measured at the stack by an approved body according to EN 1948 (1997) and ISO 9096 (2003). It is 0.003 ng TEQ / Nm 3 on dry gases and brought to a concentration of 11% of 0 2 . and fully complies with the emission regulations of 0.1 ng TEQ / Nm 3 sec, reduced to 11% O 2 .

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