• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Mineral solid composition for the abatement of dioxins and furans as well as heavy metals, in particular mercury, present in the flue gases, the process for the preparation of such a composition and its use for the abatement of dioxins and furans as well as heavy metals, especially mercury, present in the flue gases, by contacting the flue gases with said mineral solid composition.
    公开号:BE1019420A5
    申请号:E2010/0433
    申请日:2010-07-13
    公开日:2012-07-03
    发明作者:Alain Brasseur；Jean-Paul Pirard；Alain Laudet
    申请人:Lhoist Rech & Dev Sa；Univ Liege；
    IPC主号:
    专利说明:

    "MINERAL SOLID COMPOSITION. ITS PREPARATION METHOD AND ITS USE IN ABATEMENT OF DIOXINS AND HEAVY METALS FROM SMOKE GASES "
    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.
    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. For the purposes of the invention, 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). Indeed, 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.
    The term "heavy metals" refers mainly to metals with a density greater than 5000 kg / m3, particularly 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. 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.
    For example, 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.
    In many situations, particularly in the case of waste incineration plants, 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. However, the use of these carbon compounds in the flue gases has two major drawbacks: - the increase in the total organic carbon content in the dust present in the discharge of these fumes, carbon content which is severely regulated; - the risk of flammability, all the more important as the temperature of the gases to be purified is high.
    An improvement made by those skilled in the art to solve the ignition problems of carbon compounds has been to use them mixed with non-flammable substances, such as lime. Unfortunately, this improvement did reduce the risk of ignition of carbon compounds but did not completely eliminate them. Indeed, hot spots can still appear, even at low temperature (for example 150 ° C), especially in the presence of air infiltration in areas where the carbon compounds are subject to accumulation.
    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 removal of catalytic nitrogen oxides is generally carried out at a gas temperature above 200 ° C, which is not compatible with the use of carbon compounds. For good compatibility with a process step using the carbon compounds, it is necessary to alternate cooling of the flue gas and heating thereof. This represents a significant energy loss and an additional cost. It is therefore difficult to integrate the carbon compounds in a flue gas treatment process, given the ignition problems that these compounds cause.
    The documents "ES 8704428" or "ES 2136496", and "GIL, ISABEL GUIJARRO; ECHEVERRIA, SAGRAR IO MENDIOROZ; MARTIN-LAZARO, PEDRO JUAN BERMEJO; ANDRES, VICENTA MUNOZ, Mercury removal from gaseous streams.Effects of adsorbent geometry, Revista de la Real Academia de Ciencias Exactas, Fisicas and Naturales (Espana) (1996), 90 (3), pp. 197-204 "mention that it is possible to get rid of carbon for the reduction of heavy metals, in particular mercury, by the use of sulfur as reagent. Sulfur is deposited on a mineral support, such as natural silicates. Such formulations thus overcome the aforementioned drawbacks of the carbon compounds. In this case, 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.
    Unfortunately, silicates functionalized with sulfur compounds are the subject of a dangerous, heavy and expensive manufacture which penalizes its use. For example, 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, very toxic and extremely flammable, is dangerous and the strict molar proportion required 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.
    It is noted that the substitutes for the carbon compounds described above are limited to the reduction of heavy metals.
    Other 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). However, not all phyllosilicates exhibit good sorption solids for dioxins. For example, Japanese Acid Clay montmorillonite (JAC), K10 montmorillonite, and 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. In these compositions, 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. Moreover, 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.
    DE 198 24 237 discloses mineral compounds to which additives for capturing mercury are added. The additives disclosed are generally sulfur compounds, providing in this respect a teaching similar to the Spanish references mentioned above. The use of chlorites, which are mineral phyllosilicates of the chlorite group, is also mentioned.
    As can be seen, the prior art provides for substitutes for carbon compounds for the purification of flue gases, but the proposed solutions have for their object either the reduction of dioxins or the reduction of heavy metals.
    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. However, the effectiveness of sepiolite for the abatement of IWHWWHUHWLRQVWLRQV. . .j-w ,. - "requiring a priori 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 said mineral compound is chosen from phyllosilicates of the "palygorskite-sepiolite" group according to the Dana classification, said inorganic compound being doped with a halide salt and retaining its initial crystal structure, said halide salt being present in a dry basis amount ranging from 0.5% to 20% by weight based on the weight of the composition.
    Indeed, it has been observed very unexpectedly and unpredictably that 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 not dangerous.
    The effect of this composition according to the invention on the reduction rate of dioxins and heavy metals is particularly unexpected for the following reasons. Measurements of the specific surface area BET and the porous volume BJH, carried out directly on the doped mineral compound, show a sometimes significant decrease of these 2 characteristics, at least with a high doping salt content. Moreover, it is conceivable that the crystallization of a salt on a porous support should modify the accessibility to pores for large molecules such as dioxins. Finally, covering the surface of a porous solid, even a partial one, with a compound of a different nature, is capable of modifying the ability to adsorb molecules such as dioxins. These elements suggest a risk of reducing the performance of the abatement of the doped mineral compound relative to the undoped mineral compound, since it is known that the abatement capacities of dioxins and heavy metals are directly influenced by the aforementioned elements.
    In a particular embodiment, the mineral compound is selected from the group of phyllosilicates of the sepiolite subgroup according to the Dana classification.
    high porosity, typically a pore volume of between 0.20 and 0.60 cm3 / g, in particular between 0.25 and 0.40 cm3 / g, 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. Moreover, these phyllosilicates typically have a specific surface area of 100 to 200 m 2 / g, particularly from 110 to 160 m 2 / g.
    By "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 halide salt-doped inorganic compound contains, on a dry basis, from 1% to 15%, in particular from 1.5% to 10% by weight of halide salt based on the weight of the composition according to the invention. 'invention. The halide salt may be an alkaline or alkaline earth metal halide, in particular NaCl, NaBr or NaI, KCl, KBr or Kl, CaCl 2, CaBr 2 or Cal 2, MgCl 2, MgBr 2 or Mgl 2, or also NH 4 Cl, NH 4 Br or NH 4 or one of their mixtures.
    In a particular embodiment according to the invention, 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 130 m 2 /boy Wut.
    Preferably, 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 cm3 / g, measured by the BJH method, applied to the nitrogen desorption isotherm, obtained at a liquid nitrogen temperature of about 77 K for pores between 2 and 100 nm.
    Advantageously, the inorganic compound according to the invention is in pulverulent form, namely that the size of the particles is predominantly (more than 90%) less than 1 mm and substantially greater than 1 μm, that is to say that it preferably has a dgo less than 1 mm.
    By d90 is meant the interpolated value of the particle size distribution curve, such that 90% of the particles have a dimension smaller than said value.
    Unexpectedly, it has been possible to demonstrate that these inorganic compounds thus doped with a halide salt make it possible to remove with great efficiency heavy metals, especially in the gaseous state, in particular mercury and especially mercury. metal Hg °, in the flue gases, while preserving the abatement properties of dioxins that these inorganic compounds have in the absence of doping, in particular by retaining the initial crystalline structure.
    Other embodiments of the product according to the invention are indicated in the appended claims.
    The present invention also relates to a process for preparing a mineral solid composition according to the invention. This process comprises the steps of: feeding a solid material of sorption which is a mineral compound, preferably non-functionalized, chosen from the phyllosilicates of the group "palygorskite-sepiolite" according to the classification of Dana, - feeding in a salt of halide, and contacting said mineral compound and said halide salt with formation of a halide salt-doped mineral compound.
    Advantageously, said contacting of said mineral compound and said halide salt is carried out with stirring.
    Preferably, said fed mineral compound has a humidity of between 0.1 and 100 g / kg, advantageously between 2 and 90 g / kg.
    Advantageously, said contacting is carried out at ambient temperature.
    In a preferred embodiment of the process according to the invention, said halide salt is in liquid form, in aqueous phase.
    In addition, 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.
    In a preferred alternative embodiment of the process according to the invention, 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.
    Preferably, 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. It should be noted that a low concentration of salt in the solution leads to a more difficult implementation of the mixture as well as subsequent drying more expensive. Moreover, the concentration of the solution is limited by the solubility of the salt. The halide salt and the mineral compound are brought into contact so as to promote the most homogeneous distribution possible of the halide salt on the external but also the accessible internal surface of the mineral compound.
    Advantageously, 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.) such that the doped mineral compound reaches a temperature between 60 and 200 ° C, in particular between 75 and 170 ° C, in order to reach a residual moisture preferably less than 100g / kg, preferably less than 50 g / kg.
    As mentioned above, preferably, in the process according to the invention, said halide salt is an alkaline halide, an alkaline earth halide or the like, preferably selected from the group consisting of NaCl, NaBr, NaI, KCl, KBr. , K1, CaCl2, CaBr2, Cal2, MgCl2, MgBr2, Mg12, NH4Cl, NH4Bru NH4I or mixtures thereof.
    Other embodiments of the process according to the invention are indicated in the appended claims.
    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 ° C, preferably between 110 and 300 ° C and more preferably between 120 and 250 ° C. The possibility of operating at temperatures close to or above 200 ° C. makes it possible to maintain a relatively constant temperature throughout the flue gas treatment process and to avoid or limit the consecutive cooling and heating steps for the flue gas treatment. elimination of dioxins and heavy metals, then that of nitrogen compounds by catalysis.
    Advantageously, 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 μm. 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. Such a treatment comprises a step of eliminating major acid pollutants by contacting said flue gases with basic reagents. In general, 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 / Nm3.
    When the use of the doped mineral compound according to the invention for the reduction of dioxins and heavy metals in the flue gas is integrated into a complete treatment of flue gas, said basic reagents, for example lime, and said compound doped mineral are used separately or in 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.
    Other uses according to the invention are mentioned in the appended claims.
    Other features, details and advantages of the invention will emerge from the description given below, without limitation and with reference to examples.
    The invention will now be described in more detail by way of non-limiting examples.
    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. A stream of nitrogen containing 600 μg / Nm3 of metallic mercury (Hg °), with a total flow rate of 2.8 10 6 Nm 3 / s passes through this bed. A VM-3000 detector from Mercury Instruments is used to measure the metal mercury content at the reactor outlet. Prior to arrival at the detector, the gas passes through a solution of SnCk, so as to convert the possible mercury fraction in ionic form to metallic mercury. In this way, all the mercury is measured. This device makes it possible to evaluate the abatement capacity of mercury by a solid by applying the principle of the breakthrough curve. The abatement capacity is expressed in (μg Hg) / g of solid. Table 1 summarizes the method of preparation and the mercury abatement performance for Examples 1 to 5 and the Comparative Example.
    Comparative example
    Commercially available industrial grade sepiolite is placed in the reactor described above. A breakthrough curve is made at a fixed temperature of 130 ° C. The mercury abatement capacity of this undoped sepiolite in the device previously described is 9 (μg Hg) / g of sepiolite.
    Example f
    According to the invention, 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 75 ° C in an oven, so as to reach a residual moisture of less than 50 g / kg. 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 (μg Hg) / g of doped sepiolite.
    Example 2
    According to the invention, 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. The amount of NaCl deposited on the sepiolite after drying is 6% expressed by weight relative to the weight of the composition. The mercury abatement capacity of this NaCl-doped sepiolite is equal to 48 (μg Hg) / g of doped sepiolite.
    Example 3 Example 2 is reproduced but with 27% by weight MgCl solution based on 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 (μg Hg) / g of doped sepiolite.
    EXAMPLE 4 Example 2 is reproduced but with a 27% by weight solution of CaBr 2 based on 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 (μg Hg) / g of doped sepiolite.
    EXAMPLE 5 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 mercury reduction capacity measured is equal to 1770 (μg Hg) / g of doped sepiolite.
    Table 1 - Synthesis of Laboratory Tests
    EXAMPLE 6 Influence of the Temperature of the Reactor 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 made at fixed temperatures of 130 ° C, 180 ° C; 200 ° C, 250 ° C and 300 ° C. The mercury reduction capacity measured is respectively equal to 208, 426, 582, 750 and 672 (μg Hg) / g of doped sepiolite under the conditions of the test. These results demonstrate the advantageous use of the doped compositions according to the invention, especially between 180 ° C. and 300 ° C.
    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%, 15% and 30%, respectively, in order to obtain an additive content. of 1.2%, 2.3% and 4.6%, respectively. 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 (μg Hg) Ig of sepiolite doped under the conditions of the test.
    Surprisingly, it is found that 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. On the other hand, there is a significant increase in the mercury reduction for an increasing concentration of halide salt of the doped sepiolite. The results are summarized in Table 2 below.
    Table 2 - Evolution of specific surface area, pore volume and mercury removal, as a function of doping additive content
    Example 8 - Industrial scale
    According to the invention, analogous sepiolite is doped with that of the comparative example by spraying in an industrial mixer. For this purpose, 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 cage mill (cage mill), using hot gases at about 400-450 ° C and a residence time such that the gases leave the mill / dryer at about 150 ° vs. 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 Nm3 / h of fumes to be treated. The doped sepiolite is metered by means of a screw and pneumatically injected into the gas stream at 150 ° C. at a rate of 3 kg / h, then collected in a bag filter, in particular with the combustion dusts.
    The mercury concentrations upstream of the injection point of the doped sepiolite and downstream of the atomic absorption bag filter (MERCEM of Sick-Maihak) were measured. The concentrations measured, normalized on dry gases and reported at 11% oxygen are: - 85 pg / Nm3 upstream and - 14 pg / Nm3 downstream of the bag filter. This result is significantly lower than the current regulation of 50 pg / Nm3 and shows a mercury abatement rate of 84%.
    At the same time as measuring the mercury content, 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 / Nm3 on dry gases and brought to a concentration of 11% of O2. This result fully complies with the emission regulations of 0.1 ng TEQ / Nm3 sec, reduced to 11% of 02.
    Example 9 - Industrial scale
    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 Nm3 / 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 (MERCEM of Sick-Maihak) were measured. The measured mercury concentrations, normalized on dry gases and reported at 11% oxygen, are from 0.1 μg / Nm3 to 0.8 μg / Nm3. These results are significantly lower than the current regulation of 50 pg / Nm3.
    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 / Nm3 on dry gases and brought to a concentration of 11% of 02. and fully complies with the emission regulations of 0.1 ng TEQ / Nm3 sec, reduced to 11% of 02.
    It should be understood that the present invention is in no way limited to the embodiments described above and that many modifications can be made without departing from the scope of the appended claims.
    权利要求:
    Claims (18)
    [1]
    1. Composition for reducing heavy metals and dioxins in flue gases comprising a solid sorption material which is a mineral compound, preferably non-functionalized, characterized in that said inorganic compound is chosen from phyllosilicates of the group "palygorskite" -sepiolite "according to the Dana classification, said mineral compound being doped with a halide salt and retaining its initial crystalline structure, said halide salt being present in an amount on a dry basis ranging from 0.5% to 20% by weight based on the weight of the composition.
    [2]
    The composition of claim 1, wherein said mineral compound is selected from the group of phyllosilicates of the sepiolite subgroup according to the Dana classification.
    [3]
    A composition according to claim 1 or claim 2, wherein said halide salt is an alkali halide, alkaline earth halide or the like, preferably selected from the group consisting of NaCl, NaBr, NaI, KCl, KBr, KI, CaCl2, CaBr2, Cal2, MgCl2, MgBr2, Mg12, NH4Cl, NH4Bru NH4I or mixtures thereof.
    [4]
    A composition according to any one of the preceding claims, wherein said halide salt is present in a dry basis amount of from 1% to 15% by weight and in particular from 1.5% to 10% by weight of halide salt based on the weight of the composition.
    [5]
    5. Composition according to any one of the preceding claims, in which the inorganic compound doped with said halide salt has a BET specific surface area of between 70 and 170 m 2 / g, preferably between 80 and 140 m 2 / g and more preferential between 90 and 130 m2 / g.
    [6]
    6. Composition according to any one of the preceding claims, wherein said inorganic compound doped with said halide salt has a pore volume of between 0.15 and 0.32 cm3 / g, preferably between 0.20 and 0, 30 cm3 / g and more preferably between 0.22 and 0.28 cm3 / g, measured by the BJH method, applied to the nitrogen desorption isotherm.
    [7]
    7. A process for producing a composition for reducing heavy metals and dioxins, comprising the steps of: feeding a solid sorption material which is a mineral compound, preferably non-functionalized, chosen from phyllosilicates of the group according to the Dana classification, feeding to a halide salt, and contacting said mineral compound and said halide salt with the formation of a halide salt doped mineral compound.
    [8]
    8. The method of claim 7, wherein said contacting said mineral compound and said halide salt is carried out with stirring.
    [9]
    9. The method of claim 7 or claim 8, wherein said fed mineral compound has a moisture of between 0.1 and 100 g / kg, preferably between 2 and 90 g / kg.
    [10]
    The method of any of claims 7 to 9, wherein said contacting is performed at room temperature.
    [11]
    11. The process according to any one of claims 7 to 10, wherein said halide salt is in liquid form, in aqueous phase.
    [12]
    12. The method according to any one of claims 7 to 11, wherein said step of contacting said mineral compound and said halide salt is a spraying of said halide salt on said mineral compound optionally with stirring.
    [13]
    13. The method of claim 11, wherein said step of contacting said mineral compound and said halide salt is a soaking said mineral compound in said halide salt in the liquid phase, optionally with stirring.
    [14]
    The process according to any one of claims 11 to 13, wherein said liquid phase halide salt is an aqueous solution having a halide salt content of between 1% and 30%, particularly between % and 27%, preferably between 10% and 27% by weight relative to the total weight of said solution.
    [15]
    15. Method according to one of claims 7 to 14, further comprising one or more steps of drying and / or deagglomeration of said halide salt doped mineral compound, preferably at a temperature between 60 and 200 ° C, in particular between 75 and 170 ° C.
    [16]
    The process according to any one of claims 7 to 15, wherein said halide salt is an alkaline halide, an alkaline earth halide or the like, preferably selected from the group consisting of NaCl, NaBr, NaI, KCl, KBr, KI, CaCl2, CaBr2, Cal2, MgCl2, MgBr2, Mg12, NH4Cl, NH4Br or NH4I or mixtures thereof.
    [17]
    17. Use of the composition according to any one of claims 1 to 6 for the reduction of dioxins and heavy metals, preferably in the gaseous state, in particular mercury and especially mercury Hg ° in the gases of fumes.
    [18]
    18. Use according to claim 17, in admixture with a basic reagent such as lime.
    类似技术:
    公开号 | 公开日 | 专利标题
    BE1019420A5|2012-07-03|MINERAL SOLID COMPOSITION, PROCESS FOR THE PREPARATION THEREOF AND ITS USE IN THE ABATEMENT OF DIOXINS AND HEAVY METALS FROM SMOKE GASES.
    Johari et al.2016|Adsorption enhancement of elemental mercury by various surface modified coconut husk as eco-friendly low-cost adsorbents
    CN107530620B|2021-01-29|Flue gas purification system and method using sorbent polymer composites
    CA2559567C|2012-07-31|Method for abating mercury in flue gases
    BE1019419A5|2012-07-03|MINERAL SOLID COMPOSITION, PROCESS FOR THE PREPARATION THEREOF AND USE THEREOF IN HEAVY METAL ABATEMENT OF SMOKE GASES.
    CA2748297C|2017-09-05|Preparation of a solid containing zinc oxide used for purifying a gas or a liquid
    FR2992233A1|2013-12-27|ELEMENTARY SULFUR COMPOUND CAPTURING MASS REMOVED FROM POROUS SUPPORT FOR CAPTURING HEAVY METALS
    BE1023752B1|2017-07-11|LIME BASED SORBENT COMPOSITION FOR REMOVAL OF MERCURY AND METHOD FOR MANUFACTURING THE SAME
    BE1023883B1|2017-09-05|COMPOSITION FOR THE PURIFICATION OF SMOKE GAS
    EP3079806A2|2016-10-19|Hydrated lime composition for exhaust gas treatment
    Musmarraa et al.2015|A comparison among different sorbents for mercury adsorption from flue gas
    BE1024549A1|2018-03-30|COMPOSITION FOR THE PURIFICATION OF SMOKE GAS
    JP3521730B2|2004-04-19|How to remove organic chlorine compounds
    RU2574541C2|2016-02-10|Solid mineral composition, method for obtaining and application thereof for reducing content of heavy metals in waste gas
    WO2021228791A1|2021-11-18|Material for removing gaseous nitrogen oxides from a gaseous fluid
    KR20120062703A|2012-06-14|Solid mineral composition, method for preparing same and use thereof for reducing heavy metals in flue gas
    MX2012000589A|2012-06-01|Solid mineral composition, method for preparing same and use thereof for reducing heavy metals in flue gas.
    同族专利:
    公开号 | 公开日
    EP2454007A1|2012-05-23|
    PL2454007T3|2018-01-31|
    US20120134903A1|2012-05-31|
    CA2767282A1|2011-01-20|
    EP2454007B1|2017-08-02|
    CN102497921B|2015-08-19|
    JP5722888B2|2015-05-27|
    KR20120085718A|2012-08-01|
    FR2949979A1|2011-03-18|
    NZ598097A|2013-08-30|
    AU2010272573A1|2012-02-23|
    IL217480D0|2012-02-29|
    RU2012104806A|2013-09-27|
    WO2011006898A1|2011-01-20|
    JP2012532754A|2012-12-20|
    SG177490A1|2012-02-28|
    UA108615C2|2015-05-25|
    RU2543210C2|2015-02-27|
    CN102497921A|2012-06-13|
    MX2012000590A|2012-06-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR1481646A|1966-05-31|1967-05-19|Union Carbide Corp|Siliceous adsorbent compositions and their preparation process|
    JPS59160534A|1983-03-03|1984-09-11|Takeda Chem Ind Ltd|Adsorbent for mercury vapor and treatment of mercury vapor-containing gas|
    JPH01155930A|1987-12-11|1989-06-19|Onoda Cement Co Ltd|Inorganic complex drying agent|
    DE19824237A1|1998-05-29|1999-12-02|Walhalla Kalk Entwicklungs Und|Reagents for purifying waste gases or waste water, removing inorganic and organic contaminants from e.g. incineration or smelting waste gases|
    DE10228459A1|2002-06-26|2004-01-15|Iko Minerals Gmbh|Silicate adsorbent for removing both heavy metal and organic contaminants from exhaust gases is made by mixing a modified tectosilicate and a modified layered silicate|
    BE1015949A3|2004-03-15|2005-12-06|Lhoist Rech & Dev Sa|Method for reduction of mercury and heavy metal smoke gas.|
    US20090297413A1|2004-08-30|2009-12-03|Energy & Environmental Research Center Foundation|Sorbents for the oxidation and removal of mercury|
    WO2006099291A2|2005-03-14|2006-09-21|Praxair Technology, Inc.|Adsorbents for mercury removal from flue gas|
    JPS4953591A|1972-09-29|1974-05-24|
    JPH0211300B2|1982-07-08|1990-03-13|Takeda Chemical Industries Ltd|
    ES8704428A1|1986-02-11|1987-04-16|Consejo Superior Investigacion|Mercury vapour adsorbent prodn.|
    RU2035993C1|1993-09-30|1995-05-27|Александр Ефимович Горенбейн|Method for producing sorbents for purification gases against mercury|
    JPH09208336A|1996-01-30|1997-08-12|Ootake Seramu Kk|Basic porous body and its production|
    ES2136496B1|1996-06-18|2000-10-01|Consejo Superior Investigacion|NATURAL SILICATE SULFURATION PROCEDURE TO RETAIN METAL VAPORS.|
    JP2000140627A|1998-11-10|2000-05-23|Takuma Co Ltd|Dioxin removing material, dioxin removing method and regenerating method of dioxin removing material|
    JP3242902B2|1999-07-21|2001-12-25|クリン化成株式会社|Garbage bag for dioxin measures|
    JP2001276606A|2000-03-31|2001-10-09|Hitachi Zosen Corp|Adsorbing agent for removing organic harmful substance in exhaust gas and method for removing harmful substance|
    JP3790890B2|2001-07-19|2006-06-28|日立造船株式会社|Production inhibitor and production inhibition method for chlorinated aromatic compounds|
    RU2200053C1|2001-11-27|2003-03-10|Рынейский Вадим Анатольевич|Flue gas cleaning plant|
    PL1872054T3|2005-03-17|2019-07-31|Nox Ii International, Ltd.|Reducing mercury emissions from the burning of coal|
    US8906823B2|2007-09-24|2014-12-09|Basf Corporation|Pollutant emission control sorbents and methods of manufacture and use|
    US8871006B2|2009-07-13|2014-10-28|S. A. Lhoist Recherche Et Developpement|Solid mineral composition, method for preparing same and use thereof for reducing heavy metals in flue gas|US10155227B2|2012-08-24|2018-12-18|Mississippi Lime Company|Systems and method for removal of acid gas in a circulating dry scrubber|
    CN102814180B|2012-06-07|2017-12-22|盐城工学院|For attapulgite carrier catalyst for oxidation of elemental mercury in flue gas and preparation method thereof|
    US10668480B1|2014-09-05|2020-06-02|Mississippi Lime Company|Systems and method for removal of acid gas in a circulating dry scrubber|
    CN104918886B|2012-11-13|2018-08-10|巴斯夫欧洲公司|The preparation of zeolitic material and the purposes in the method that oxygenate is converted to alkene|
    US10221094B1|2013-03-04|2019-03-05|Mississippi Lime Company|Method of manufacturing hydrated lime|
    US9963386B1|2013-03-04|2018-05-08|Mississippi Lime Company|Method of manufacturing hydrated lime|
    CN103381337B|2013-06-26|2016-01-20|广东电网公司电力科学研究院|A kind of catalytic oxidation additive for wet flue gas demercuration and preparation method thereof|
    US9751043B1|2014-09-05|2017-09-05|Mississippi Lime Company|Systems and method for removal of acid gas in a circulating dry scrubber|
    CA2995357A1|2015-08-11|2017-02-16|Calgon Carbon Corporation|Enhanced sorbent formulation for removal of mercury from flue gas|
    CN105435735A|2015-11-19|2016-03-30|兰州坤仑环保科技有限公司|Water heavy metal ion attapulgite adsorbent|
    CN105944554A|2016-06-08|2016-09-21|黄立维|Method and device for removing harmful gas|
    US11148149B2|2017-12-29|2021-10-19|Mississippi Lime Company|Hydrated lime with reduced resistivity and method of manufacture|
    CN111389219B|2020-03-27|2021-11-02|浙江浙能技术研究院有限公司|Ammonia injection control method for start-stop stage of coal-fired boiler|
    法律状态:
    2021-04-28| MM| Lapsed because of non-payment of the annual fee|Effective date: 20200731 |
    优先权:
    申请号 | 申请日 | 专利标题
    BE200900427|2009-07-13|
    BE200900427|2009-07-13|
    US33225410P| true| 2010-05-07|2010-05-07|
    US33225410|2010-05-07|
    [返回顶部]