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    • 专利摘要:
    The invention relates to a composition for the purification of flue gas containing 1 to 99% by weight of a powder of a sodium salt of carbonic acid and 1 to 99% by weight of a powder of an absorbent material wherein the powder of an absorbent material has a specific pore volume which is equal to or greater than 0.1 cm3 / g. The invention also relates to a method for the purification of dry flue gas and the use of an absorbent material for improving the fluidity and / or the storage ability and / or the absorption capacity of the HF. a sodium salt of carbonic acid.
    公开号:BE1024549B1
    申请号:E2016/5974
    申请日:2016-12-23
    公开日:2018-04-04
    发明作者:Martin Sindram；Walter Diethelm；Christopher Pust；Xavier Pettiau
    申请人:S.A. Lhoist Recherche Et Developpement；
    IPC主号:
    专利说明:

    (73) Holder (s):
    S.A. LHOIST RESEARCH AND DEVELOPMENT 1342, OTTIGNIES-LOUVAIN-LA-NEUVE Belgium (72) Inventory:
    SINDRAM Martin 58256 ENNEPETAL Germany
    DIETHELM Walter 40822 METTMANN Germany
    PUST Christopher 40625 DUSSELDORF Germany
    PETTIAU Xavier 6010 COUILLET Belgium (54) COMPOSITION FOR THE PURIFICATION OF SMOKE GAS (57) The invention relates to a composition for the purification of smoke gas containing 1 to 99% by weight of a powder of a sodium salt d carbonic acid and 1 to 99% by weight of a powder of an absorbent material, in which the powder of an absorbent material has a specific pore volume which is equal to or greater than 0.1 cm 3 / g. The invention also relates to a method for the purification of flue gases by the dry route and the use of an absorbent material to improve the fluidity and / or the storage capacity and / or the absorption capacity of HF a sodium salt of carbonic acid.
    Elimination of S0 with mixtures of Sorbacal SP with ground sodium hydrogen carbonate
    Fraclton of sodium hydrogen carbonate crushed in the mixed (% and weight)
    Figure 1
    BELGIAN INVENTION PATENT
    FPS Economy, SMEs, Middle Classes & Energy
    Publication number: 1024549 Deposit number: BE2016 / 5974
    Intellectual Property Office International Classification: B01D 53/50 B01J 20/28 B01J 20/04 B01J 20/30 B01D 53/68 Date of issue: 04/04/2018
    The Minister of the Economy,
    Having regard to the Paris Convention of March 20, 1883 for the Protection of Industrial Property;
    Considering the law of March 28, 1984 on patents for invention, article 22, for patent applications introduced before September 22, 2014;
    Given Title 1 “Patents for invention” of Book XI of the Code of Economic Law, article XI.24, for patent applications introduced from September 22, 2014;
    Having regard to the Royal Decree of 2 December 1986 relating to the request, the issue and the maintenance in force of invention patents, article 28;
    Considering the patent application received by the Intellectual Property Office on December 23, 2016.
    Whereas for patent applications falling within the scope of Title 1, Book XI of the Code of Economic Law (hereinafter CDE), in accordance with article XI. 19, §4, paragraph 2, of the CDE, if the patent application has been the subject of a search report mentioning a lack of unity of invention within the meaning of the §ler of article XI.19 cited above and in the event that the applicant does not limit or file a divisional application in accordance with the results of the search report, the granted patent will be limited to the claims for which the search report has been drawn up.
    Stopped :
    First article. - It is issued to
    S.A. LHOIST RESEARCH AND DEVELOPMENT, Rue Charles Dubois 28, 1342 OTTIGNIES-LOUVAINLA-NEUVE Belgium;
    represented by
    GEVERS PATENTS, Holidaystraat 5, 1831, DIEGEM;
    a Belgian invention patent with a duration of 20 years, subject to the payment of the annual fees referred to in article XI.48, §1 of the Code of Economic Law, for: COMPOSITION FOR THE PURIFICATION OF SMOKE GAS.
    INVENTOR (S):
    SINDRAM Martin, Heilenbecker Strasse 372, 58256, ENNEPETAL;
    DIETHELM Walter, Am Schüttenhassel 5, 40822, METTMANN;
    PUST Christopher, Akazienallee 9, 40625, DUSSELDORF;
    PETTIAU Xavier, Rue des Briqueteries 43, 6010, COUILLET;
    PRIORITY (S):
    12/30/2015 EP 15203139.9;
    DIVISION:
    divided from the basic application: filing date of the basic application:
    Article 2. - This patent is granted without prior examination of the patentability of the invention, without guarantee of the merit of the invention or of the accuracy of the description thereof and at the risk and peril of the applicant (s) ( s).
    Brussels, 04/04/2018, By special delegation:
    BE2016 / 5974
    COMPOSITION FOR THE PURIFICATION OF SMOKE GAS
    The present invention relates to a composition for the purification of flue gases by dry process, a process for manufacturing said composition, and the use of said composition for the purification of smoke gases by dry process. The invention also relates to a method for the purification of smoke gases by the dry route and the use of an absorbent material to improve the fluidity and / or the storage capacity and / or the absorption capacity of HF of a sodium salt of carbonic acid.
    Many industrial processes produce smoke gases. For example, in the smoke of fossil resources, for example in power plants such as coal-fired power plants, large quantities of smoke gases are produced. Also in the incineration of waste, large quantities of smoke gases are produced.
    Smoke gases often contain dangerous or even toxic pollutants, for example sulfur oxides, such as sulfur dioxide (SO2) or sulfur trioxide (SO3), and / or hydrogen halides, such as hydrogen fluoride (HF) and / or hydrogen chloride (HCl).
    Attempts have been made to reduce the levels of pollutants in the air. In particular, methods for purifying flue gases have been devised to reduce the quantities of pollutants emitted for example by waste incineration plants and by plants powered by fossil resources. These methods usually include contacting the smoke gas with an absorbent, also known as a sorbent.
    Different processes have been devised for purifying flue gases, also called flue gas purification. In wet treatment, an alkaline absorbent such as limestone or a lime-based material is contacted with the flue gas usually under the
    BE2016 / 5974 forms an aqueous slurry. The disadvantages of wet cleaning include corrosion of equipment, the need for treatment or reuse of wastewater.
    In a dry treatment, also called dry gas purification or injection of dry sorbent, the absorbent is normally brought into contact with the smoke gas in the dry state. After absorption, the dry reaction products are normally collected downstream in a dust collection unit which usually has a fabric filter or an electrostatic filter. A big advantage of dry flue gas purification is the simplicity of the equipment required to implement a dry flue gas purification.
    Lime-based materials, such as hydrated lime (Ca (OH) 2 ), or alkali metal salts of carbonic acid, such as sodium hydrogencarbonate (NaHCO 3 ) or sodium sesquicarbonate such as trôna (Na 2 CO 3 * NaHCO 3 * 2H 2 O), are often used as absorbents in the purification of smoke gases by dry process.
    It has been suggested to use both sodium hydrogencarbonate and hydrated lime for the purification of flue gases. Document JP Hll-165036 A describes a process for the purification of flue gases by simultaneous injection of sodium hydrogencarbonate and hydrated lime via two separate injection systems in the flue gas stream. However, the two separate injection systems increase the cost of the flue gas purification system.
    In addition, improved absorbents have been reported, particularly improved calcium hydroxide particles.
    For example, document EP 0 861 209 B1 describes particles of calcium hydroxide having a total pore volume of at least 0.1 cm 3 / g for the capture of acid gases. The
    BE2016 / 5974 calcium hydroxide particles are prepared by quenching quicklime particles (CaO) having a reactivity above 30 ° C / minute with sufficient water to obtain calcium hydroxide having residual moisture between 15 and 30% by weight, followed by drying and grinding. The particles are reported to be more effective than the standard calcium hydroxide particles in capturing sulfur dioxide and hydrogen chloride.
    Document WO 2007000433 A2 describes a hydrated lime powder comprising up to 3.5% by weight of an alkali metal and having a BET specific surface of 25 m 2 / g or more as well as a total pore volume BJH of 0 , 1 cm 3 / g. Hydrated lime is prepared by quenching quicklime. The alkali metal is introduced into the hydrated lime by means of an alkali metal salt which is advantageously added to the quenching water for quicklime. Hydrated lime is reported to be more effective than other absorbents based on hydrated lime in capturing sulfur dioxide and hydrogen chloride.
    Generally, in order to increase the absorbency of the adsorbents, these are ground into fine powders having a small particle size. The smaller the particle size, the larger the specific surface area of the particle, and therefore of the absorbent, which absorbent can react with the pollutants in the flue gas. As a characteristic value of the particle size of a powder, the so-called d 5 o value is often used. The d 50 value of the powder particles is normally determined by the particle size distribution of the powder. The size for which 50% of the powder will pass through a theoretical opening of a sieve, determined from the particle size distribution, is commonly called the dso value Typically, dso values less than 40 μm, or even less than 20 μm, are desirable for absorbents.
    BE2016 / 5974
    Maintaining a low d 5 o in a powder of a sodium salt of carbonic acid is difficult, in particular for the throne and for sodium hydrogen carbonate.
    Although a particular powder less than
    40 pm or even lower resulting of the powder maintained sure of long
    sodium carbonic acid, into sodium hydrogencarbonate, having a d 50 to 20 pm, the small grain size with fine grains cannot be periods of time. Normally, after a few days or even after a day, the particles of the powder of a sodium salt of carbonic acid, in particular of sodium hydrogen carbonate, begin to re-agglomerate, thus forming larger aggregates. A powder containing larger aggregates is undesirable because of the reduced surface area. For this reason, the sodium salts of carbonic acid, in particular sodium hydrogen carbonate, are normally ground on site immediately before use. This makes it necessary to have grinders for the sodium salt of carbonic acid, which increase the cost of the flue gas purification system, also because of their maintenance cost. Thus, the storage capacity of powders of sodium salts and carbonic acid, in particular of throne or sodium hydrogencarbonate, having a low d 50 , is difficult.
    In addition to their specific surface, the particles can also contain a certain porosity, normally specified by the specific pore volume of the material. If the pores forming the porosity are accessible from outside the particles, this also usually increases the specific surface area of the particles. Consequently, if the material under study has a large specific pore volume, it also normally has a high specific surface. However, the reverse is not necessarily the case. For example, fumed silica, sometimes also called pyrogenic silica, is a
    BE2016 / 5974 particulate material having a specific surface of 50 to 600 m 2 / g, the particles of which are non-porous.
    Another problem with powders of sodium salts of carbonic acid is their fluidity. When stored for example in silos, powders of sodium salts of carbonic acid tend to become denser, presumably by the action of gravity. In this process, the powder loses its fluidity, making it difficult to get the powder out of the silo. In order to make the powder accessible, it must be agitated, for example with pressurized air, so that the fluidity of the powder is restored.
    Yet another problem observed during the grinding of sodium salts and carbonic acid, in particular sodium hydrogencarbonate, is the agglutination of the ground material on the grinding equipment, for example on the walls of the mill. This agglutination effect makes regular maintenance of the crushers necessary. Attempts to overcome this agglutination effect include the addition of stearic acid, calcium stearate, trimethylolpropane, or glycols during grinding, particularly with sodium hydrogencarbonate. While this helps reduce the agglutination effect, the additional additives increase the cost of the process.
    In addition to compositions consisting mainly of a single absorbent, mixtures of absorbents are also known.
    WO 2007031552 A1 describes an SO3-containing smoke gas absorbent composition which contains an additive and an absorbent based on sodium such as sodium hydrogencarbonate or mechanically refined throne. The additive is chosen from magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, and mixtures thereof, and it is present in the mixture in an amount preferably between 0.1% and 5%, especially between 0.5 and 2% by weight of
    BE2016 / 5974 the sodium-based absorbent.
    Document DE 202 10 008 U1 describes a composition for the purification of flue gases based on quick lime (CaO). The composition may further contain calcium hydroxide and sodium hydrogencarbonate. Preference is given to compositions which mainly contain quicklime.
    Document US 4,859,438 describes a process for removing hazardous substances in flue gases, using mixtures of dry absorbents based on hydrated oxides, hydroxides or oxides. Dry absorbents can include sodium hydrogen carbonate and one or more of NH4HCO3, Al (OH) 3, silica gel, calcium hydroxide, and salts with water of crystallization such as CaCl2 or AI2O3. It is reported that the elimination of hazardous substances in the flue gases is improved with the composition.
    Document EP 1 004 345 A2 describes a treatment agent for the elimination of acid components in a gas. The treating agent contains sodium hydrogen carbonate in an amount preferably at least 70% by weight, and may contain another component such as potassium hydrogen carbonate, slaked lime, calcium carbonate, zeolite, activated carbon, or silica or diatomaceous earth. In order to prevent agglomeration, the treating agent may contain silica powder, fumed silica, white carbon, basic magnesium carbonate, calcium carbonate or diatomaceous earth. The composition of EP 1 004 345 A2 can effectively remove the acidic components in a flue gas.
    The examples of compositions of the prior art, mentioned above, remain silent about the porosity of the absorbents and / or the advantageous effects resulting therefrom.
    Despite progress made in maintaining
    BE2016 / 5974 the suitability for storage, solutions are desired which help maintain the particle size distribution, in particular the d 50 value, of a powder. In addition, absorbent compositions are desired having good absorbency of sulfur oxides and / or hydrogen halides. In addition, compositions having good fluidity are desired, particularly after a certain storage time.
    An object of the present invention therefore resides in the provision of a composition having good fluidity, good storage capacity, and / or good absorbency of pollutants such as sulfur oxides and / or halides d 'hydrogen. In particular, an object of the present invention resides in the provision of a composition having a fluidity as high as possible, in particular after a certain storage time, and having at the same time a good absorption capacity of the sulfur oxide. This combination of a capacity for absorbing sulfur oxide and as high a fluidity as possible is difficult to obtain because the compounds having a good capacity for absorbing sulfur oxides, such as for example sodium hydrogen carbonate. , are known for their limited fluidity, in particular after a certain storage time.
    Some or all of these objects can be achieved by using the present invention. In particular, some or all of these objects can be achieved by the composition of claim 1, the method of claim 10, the composition of claim 15, the method of claim 16, the use of claim 17, and the use of claim 18.
    Other embodiments are described in the dependent claims and will be discussed in the following.
    BE2016 / 5974
    The invention provides a composition for the purification of smoke gases, said composition containing, in each case relative to the total weight of the composition:
    at. 1 to 99% by weight of a powder of a sodium salt of carbonic acid; and
    b. 1 to 99% by weight of a powder of an absorbent material;
    wherein said powder of said absorbent material has a specific pore volume which is equal to or greater than 0.1 cm 3 / g.
    It has surprisingly been found that as a result of the unique combination of 1 to 99% by weight of a powder of a sodium salt of carbonic acid with 1 to 99% by weight of a powder of a material absorbent, in which said powder of said absorbent material has a specific pore volume which is equal to or greater than 0.1 cm 3 / g, a composition for the purification of smoke gases is obtained which can be well stored and / or has good fluidity and / or has good absorbency of pollutants, such as sulfur oxides and / or hydrogen halides. It has been found in particular that compositions containing a powder of a sodium salt of carbonic acid and a powder of an absorbent material having a specific pore volume equal to or greater than 0.1 cm 3 / g have much better fluidity , in particular in comparison with pure powders of alkali metal salts of carbonic acid, and good absorption power of sulfur oxides.
    Without wishing to be bound by a scientific theory, it turns out that the high specific porosity of the powder of the absorbent material facilitates the storage of the composition and / or the maintenance of good fluidity, possibly by trapping of moisture and / or liquids inside the absorbent material particles. In this way, one can maintain an unchanged surface of the particles.
    This can help prevent aggregation. This can also help maintain fluidity.
    BE2016 / 5974
    Surprisingly, it has also been found that when using the above composition in the purification of flue gases, peak concentrations of hydrogen fluoride do not result in very high consumption of the composition .
    It has also been found that the use of a sodium salt of carbonic acid is particularly effective in increasing the absorption capacity of the sulfur oxides of the resulting compositions. Compositions containing sodium salts of carbonic acid have been found to be more economical than compositions containing other alkali metal salts of carbonic acid.
    The absorbency of an absorbent (or an absorbent composition) describes in particular its capacity to retain pollutants, in particular sulfur oxides and / or hydrogen halides. The absorbency can for example be expressed in absolute terms, that is to say by the absolute quantity of pollutant absorbed by the absorbent (or the absorbent composition), or in relative terms, that is to say say by the quantity of pollutant absorbed by the absorbent (or the absorbent composition) compared to a reference absorbent (or an absorbent composition).
    The fluidity of a material without cohesion, in particular of a powder, is linked to its accessibility from a storage container. Good fluidity can normally be attributed to cohesive materials, in particular powders, which can easily flow from the storage container, for example from a silo, due to the action of gravity. In particular, for non-cohesive materials having good fluidity, no other action promoting the flow is required on the material. Materials without cohesion, in particular powders, which have a propensity to obstruct the flow out of the silo, for example by forming consolidated bridges (for example via droplets of
    BE2016 / 5974 liquid) between particles, can normally be said to have poor fluidity. The fluidity of a material without cohesion, in particular of a powder, can for example be described by means of the value FFC. Higher FFC values indicate better fluidity.
    The methods for determining the FFC value are known to those skilled in the art and are also described, for example, in the article by Dietmar Schulze Zur Fließfähigkeit von Schüttgütern - Definition und Meßverfahren, published in the journal Chemie Ingenieur Technik by Wiley VCH, 1995, Volume 67, 1st edition, pages 60-68, or in Powders and Bulk Solids - Behavior, Characterization, Storage and Flow by Dietmar Schulze, Springer-Verlag Berlin Heidelberg, 2008. The FFC value can for example be determined by a compression test uniaxial. In the uniaxial compression test, normally a hollow cylinder, ideally with walls without friction, is filled with the material without cohesion, in particular of the powder, which is the subject of the study, and an SI constraint - the consolidation constraint - is applied in the vertical direction in the first step. The SI constraint can also be called sigmai, σι. Then the consolidation constraint SI on the sample is released, and the hollow cylinder is removed. Then, an increasing vertical compressive stress is applied to the sample of material without consolidated cylindrical cohesion, in particular the consolidated powder sample, until the stress Sc at which the cylindrical sample breaks (or becomes defective). The stress Sc can be called compressive force or limit of elasticity not confined, and is sometimes also called sigma c , a c . The defect of the consolidated cylindrical sample following the application of the constraint Sc indicates the initial flow of the material without consolidated cohesion, in particular of the consolidated powder. The FFC value can then be determined by the ratio FFC = Sl / Sc.
    BE2016 / 5974
    The fluidity of a non-cohesive material, especially a powder, can also be determined using a Jenike shear tester. In this case, the test method for determining the FFC value usually requires the determination of what is called the elastic limit or the plotting of elastic locus, from which SI and Sc, and therefore the FFC value, can to be determined. The determination of the elasticity trace is described in the references of Dietmar Schulze mentioned above and normally requires a pre-shear treatment of the sample (shear of the sample up to the point of constant shear stress, however a first consolidation force is applied), followed by a measurement step (shear of the sample up to the maximum shear stress at which the particles begin to move relative to each other, however, a force of consolidation less than that in the pre-shearing treatment is applied). For each point of the elastic limit plot, a new sample is required which must be subjected to the same pre-shearing treatment. From the resulting elastic limit plot, SI and Sc and therefore the FFC value can be determined.
    In addition, it is also possible to describe and / or generally determine the fluidity using an annular shear tester, for example an annular shear tester <
    annular shear, cohesion, in particular introduced into an annular shear cell of the tester. A cover is normally placed on top of the sample and fixed with a crosspiece. Then an S is usually
    type RST-XS. In The sample of the powder) East
    material without usually applied stress normal to the sample via the shear cell cover. During the measurement, the shear cell usually
    BE2016 / 5974 turns slowly, while the cover and the crosspiece are prevented from turning by two tie rods connected from opposite sides of the crosspiece. The bottom of the shear cell and the bottom side of the cover are normally rough so that the rotation of the shear cell induces a shear stress which can be measured by the forces acting on the two tie rods. The measurement steps are similar to the steps described above, although it is possible to determine a full elasticity locus plot with a single sample. From the resulting elastic limit plot, SI and Sc, and therefore the FFC value, can then be determined.
    According to one embodiment, the composition has a fluidity value, in particular an FFC value, in particular determined by means of an annular shear tester RST-XS, of 0.2 or more, in particular of 0.3 or more, or 0.4 or more, or 0.5 or more, or 0.6 or more, or 0.7 or more, or 0.8 or more, or 0.9 or more , or 1.0 or more, or 1.1 or more, or 1.2 or more, or 1.3 or more.
    According to one embodiment of the invention, the composition contains 1 to 70% by weight, preferably 1 to 50% by weight or 1 to 30% by weight or 5 to 30% by weight or 10 to 30% by weight or 13 to 30% by weight or 13 to 20% by weight or 13 to% by weight or 5 to 99% by weight or 10 to 99% by weight or 15 to 99% by weight or 15 to 90% by weight or 15 80% by weight or 75% by weight or 15 to 70% by weight or 15 to 65% by weight or 15 to 60% by weight or 15 to 50% by weight or 15 to 45% by weight or 15 to 40 % by weight or 15 to 30% by weight or 15 to 25% by weight or 15 to 20% by weight or 15 to 18% by weight of the powder of sodium salt of carbonic acid, relative to It has been discovered that of the sodium salt of acid total weight of the composition, compositions with these carbonic quantities have a particularly good fluidity, in
    BE2016 / 5974 particular after a certain time of storage time. It has also been found that, within these ranges, the absorbency of sulfur dioxide is improved. Furthermore, it has been found that a composition having a particularly well balanced property profile can be obtained if the sodium salt of carbonic acid is present in an amount of about 10 to 25% by weight, in particular 15 at 25% by weight, relative to the total weight of the composition.
    According to another embodiment of the invention, the composition contains 30 to 99% by weight, preferably 50 to 99% by weight or 70 to 99% by weight or 70 to 95% by weight or 70 to 90% by weight. weight or 70 to 87% by weight or 80 to% by weight or 82 to 87% by weight or 1 to 95% by weight or 1 to 90% by weight or 1 to 85% by weight or 10 to 85% by weight or 85% by weight or 25 to 85% by weight or 30 to 85% by weight or 35 to 85% by weight or 40 to 85% by weight or 50 to 85% by weight or 55 to 85% by weight or 60 to 85% by weight or 70 to 85% by weight or 75 to 85% by weight or 80 to 85% by weight or 82 to 85% by weight of the powder of the absorbent material, relative to the total weight of the composition. It has been found that compositions with these amounts of the absorbent material have particularly good fluidity. It has been found that a composition having a particularly well balanced property profile can be obtained if the absorbent material is present in an amount of about 70 to 90% by weight, in particular 64 to 85% by weight, relative to the total weight of the composition.
    The particles of the powder of the sodium salt of carbonic acid can have various sizes, advantageous that the particles are in accordance with another embodiment of the invention, the powder of sodium salt of carbonic acid has a smaller particle size dso at 50 pm, in particular less than 45 pm or less than 40 pm or less than 35 pm or less than 30 pm
    It is however small. So,
    BE2016 / 5974 or less than 25 μιη or less than 20 pm or less than 15 pm or less than 12 pm. It is particularly preferred that the powder of a sodium salt of carbonic acid has a particle size d 5 o less than 20 pm, more preferably less than 15 pm or less than 12 pm. Preferably, the powder of the sodium salt of carbonic acid has a particle size d 97 of less than 180 µm, in particular less than 170 µm or less than 160 µm or less than 150 µm or less than 140 µm or less than 125 µm. It has been found that powders of sodium salts of carbonic acid having particle sizes as mentioned above absorb the pollutants more effectively.
    In order to obtain an effective composition for the purification of flue gases, various sodium salts of carbonic acid can be used. Preferably, the sodium salt of carbonic acid is chosen from the group consisting of sodium hydrogencarbonate, sodium carbonate, sodium sesquicarbonate, and mixtures thereof. More preferably, the sodium salt of carbonic acid is sodium hydrogencarbonate and / or sodium sesquicarbonate. It has been found that with the above-mentioned carbonic acid sodium salts, the absorbency, in particular the absorbency of sulfur dioxide, is very good.
    Sodium sesquicarbonate can for example be
    used under the form of enthroned who can be directly extract of a deposit. The enthroned extract from a deposit can so be used with or without subsequent refining.
    Sodium hydrogencarbonate can for example be used in the form of nahcolite extracted from a deposit and / or as a product of a chemical process. The nahcolite extracted from a deposit can thus be used with or without subsequent refining.
    The throne extracted from a deposit may contain impurities such as shortite, dolomitic shale,
    BE2016 / 5974 quartz, illite, calcite, feldspar, and / or sodium fluoride. The throne extracted from a deposit may contain the invention may be containing calcium, up to 20% by weight, preferably up to 15% by weight, better still up to 10% by weight, better still up to at 5% by weight, better still up to 3% by weight of the abovementioned impurities, relative to the total weight of the throne.
    The composition according to the invention can contain different materials serving as absorbent material. Preferably, the absorbent material is an absorbent of sulfur oxides, in particular sulfur dioxide, and / or a material absorbing hydrogen halides, in particular hydrogen chloride and / or hydrogen fluoride.
    The materials contained as an absorbent material in the composition advantageously according to material materials containing calcium and magnesium, and / or materials containing magnesium. Examples of calcium-containing materials include limestone, quicklime, and hydrated lime. Examples of materials containing calcium and magnesium include raw dolomite (dolomite), quicklime dolomitic, and hydrated lime dolomitic. Examples of magnesium-containing materials include magnesium carbonate, magnesium oxide, and magnesium hydroxide.
    Preferably, the absorbent material contained as a powder in the composition according to the invention is chosen from the group consisting of limestone, quicklime, hydrated lime, raw dolomite (dolomite), quicklime dolomitic, dolomitic hydrated lime, magnesium carbonate, magnesium oxide, magnesium hydroxide, and mixtures thereof. Better still, the absorbent material contained in the form of a powder in the composition according to the invention is chosen from the group consisting of quicklime, hydrated lime, dolomitic quicklime, lime
    BE2016 / 5974 dolomitic hydrate, magnesium oxide, magnesium hydroxide, and mixtures thereof. Most preferably, the absorbent material contained as a powder in the composition according to the invention is hydrated lime.
    The use of the abovementioned materials, alone or in the form of a combination, proves to be advantageous in particular for the fluidity of the resulting composition and / or for the absorbency of the composition, in particular for the absorbency HF. These advantageous effects are particularly pronounced for hydrated lime as an absorbent material.
    The hydrated lime used according to the invention is also called slaked lime, and it mainly contains Ca (OH) 2- Preferably, the hydrated lime of the invention contains more than 90% by weight, better still more than 93% by weight. weight, better still more than 95% by weight, better still more than 97% by weight, better still more than 99% by weight of Ca (OH) 2 relative to the weight of hydrated lime in the composition. In addition to Ca (OH) 2 , hydrated lime can contain impurities, in particular impurities derived from SiO 2 , AI2O, AI2O3, iron oxides such as Fe 2 C> 3, MgO, MnO,
    P2O5, K2O, CaSOo and / or SO3. Preferably, the hydrated lime according to the invention contains less than 10% by weight, better still less than 7% by weight, better still less than 5% by weight, better still less than 3% by weight, better still less than 1 % by weight of the impurities listed above, relative to the weight of hydrated lime in the composition.
    Similarly, materials containing calcium, in particular limestone and quicklime, materials containing calcium and magnesium, especially raw dolomite (dolomite), quicklime dolomitic, and hydrated lime dolomitic, and materials containing magnesium, in particular magnesium carbonate, magnesium oxide, and magnesium hydroxide, may contain
    BE2016 / 5974 the impurities mentioned above in the quantities mentioned above.
    In addition to the impurities of the hydrated lime mentioned above, the hydrated lime according to the invention can also contain impurities containing calcium, in particular CaO and / or CaCCG. Calcium oxide-type impurities in hydrated lime may come from insufficient hydration of quicklime as the starting material. The calcium carbonate type impurities in the hydrated lime can come either from the initial limestone from which the hydrated lime according to the invention is derived, or from a partial carbonation reaction of the hydrated lime with air. The calcium oxide content of the hydrated lime according to the invention is preferably less than 5% by weight, better still less than 3% by weight, better still less than 2% by weight, better still less than 1% by weight relative to the weight of hydrated lime in the composition. The calcium carbonate content of the hydrated lime according to the invention is preferably less than 15% by weight, better still less than 10% by weight, better still less than 6% by weight, better still less than 4% by weight relative to the weight of hydrated lime in the composition.
    The size of the particles of absorbent material in the composition, in particular the dso value of the absorbent material, should be small. Preferably, the absorbent material has a particle size d 50 of less than 50 μm, better still less than 40 μm, or less than 30 μm, or less than 20 μm, or less than 10 μm. Optimal results are obtained when hydrated lime having a particle size dso of less than 50 μm, preferably less than 40 μm, or less than 30 μm, or less than 20 μm, is used as absorbent material in the composition. or less than 10 pm. As an absorbent material in the composition, particularly preferred is hydrated lime
    BE2016 / 5974 having a value of 5 o less than 10 pm. Advantageously, the absorbent material, in particular hydrated lime, has a particle size d 97 less than 150 μm, in particular less than 140 μm, or less than 130 μm, or less than 120 μm, or less than 110 μm, or less than 100 pm, or less than 90 pm.
    The dso value of the particles of the powder can for example be determined by determining the particle size distribution of the powder. The size for which 50% of the powder will pass through a theoretical opening of a sieve, determined from the particle size distribution, is commonly called the dso value. Therefore, the size for which 97% of the powder will pass through a theoretical opening of a sieve, determined from the particle size distribution, is commonly called the value d 97 . Those skilled in the art know different methods for determining the particle size distribution. For example, the particle size distribution can be determined by sieving experiments. For example, the particle size distribution can also be determined by laser diffraction, in particular in accordance with ISO 13320: 2009. In determining the particle size distribution of a powder by laser diffraction, the powder under study can be suspended in a liquid medium, for example in ethanol, and the suspension can be subjected to an ultrasound treatment, for example for 120 seconds, followed by a pause for example of 120 seconds. The suspension can also be stirred, for example at 70 rpm. The particle size distribution can then be determined by plotting the measurement results, in particular the cumulative sum of the percentage by mass of the measured particle sizes as a function of the measured particle sizes. The dso value and / or the d 97 value can then be determined from the particle size distribution. For the determination of the
    BE2016 / 5974 distribution of particle size and / or dso value and / or d 97 value of a powder by laser diffraction, it is possible for example to use a Helos particle size analyzer available from the company Sympatec, which uses the additional Sucell dispersing equipment.
    It has also been found that it is advantageous for the absorbent material to have a large specific surface. A composition containing an absorbent material having a specific surface of 20 m 2 / g or more, preferably 30 m 2 / g or more, or 40 m 2 / g or more, 45 m 2 or more / g, proves to be particularly effective for the purification of smoke gases. Optimal results are obtained in particular in the purification of flue gases when hydrated lime having a specific surface area equal to or greater than 20 m 2 / g, preferably equal or greater, is used as absorbent material in the composition. at 30 m 2 / g, or equal to or greater than 40 m 2 / g, or equal or greater than 45 m 2 / g.
    The specific surface of the materials described here, in particular absorbent materials, refers in particular to the specific surface, more particularly to the BET specific surface (Brunauer, Emmet, Teller). Methods for determining the specific surface of a material are known to those skilled in the art. For example, the specific surface can be determined by nitrogen adsorption measurements of a sample, preferably dried and put under vacuum at 77 K, in accordance with the BET multipoint process. For this purpose, for example, a device of the Micromeritics ASAP 2010 type can be used. In particular, the BET specific surface can be determined in accordance with DIN ISO 9277, in particular in accordance with DIN ISO 9277: 2014-01, in particular using the static volumetric determination method and in particular the multipoint analysis method.
    Also the specific pore volume of the material
    BE2016 / 5974 absorbent is preferably important. This is particularly useful for obtaining compositions having good fluidity. In addition, this is advantageous for the absorbency of the composition. Consequently, the composition preferably contains an absorbent material having a specific pore volume equal to or greater than 0.11 cm 3 / g or equal or greater than 0.12 cm 3 / g or equal or greater than 0.13 cm 3 / g or equal or greater than 0.14 cm 3 / g or equal or greater than 0.15 cm 3 / g or equal or greater than 0.16 cm 3 / g or equal or greater than 0.17 cm 3 / g or equal to or greater than 0.18 cm 3 / g or equal to or greater than 0.19 cm 3 / g or equal to or greater than 0.2 cm 3 / g. Optimal results are obtained by using, as absorbent material in the composition, hydrated lime having a specific pore volume equal to or greater than 0.11 cm 3 / g or equal or greater than 0.12 cm 3 / g or 0.13 cm 3 / g or greater or 0.14 cm 3 / g or greater or 0.15 cm 3 / g or greater or 0.16 cm 3 / g or greater or equal or greater than 0.17 cm 3 / g or equal to or greater than 0.18 cm 3 / g or equal or greater than 0.19 cm 3 / g or equal or greater than 0.2 cm 3 / g. It has been found that compositions containing an absorbent material having a large pore volume, in particular a pore volume as indicated above, have improved properties in particular with regard to their flow values, more particularly with regard to their FFC values.
    The specific pore volume described here refers in particular to the total specific pore volume, preferably of pores having a diameter less than 100 nm, determined by BJH (Barrett, Joyner, Halenda), that is to say supporting a geometry of cylindrical pore. Advantageously, the specific pore volume of the absorbent material, in particular the specific pore volume determined in accordance with BJH, can represent more than 50% by volume, preferably more than 55% by volume, better still more than 60% by volume, relative at
    BE2016 / 5974 total pore volume, the partial pore volume of pores having a diameter of 10 to 40 nm, determined in accordance with B JH. Methods for determining the specific pore volume of a material are known to those skilled in the art. For example, the specific pore volume can be determined by nitrogen desorption measurements of a sample preferably dried and placed under vacuum at 77 K. The data obtained in this way can preferably be analyzed according to the BJH method, c that is, assuming a cylindrical pore geometry. For this purpose, for example, a device of the Micromeritics ASAP 2010 type can be used. In particular, the specific pore volume determined in accordance with BJH can be determined in accordance with standard DIN 66134, in particular in accordance with standard DIN 66134: 1998- 02, in particular using the volumetric determination method.
    Methods for the manufacture of hydrated lime usable in the present invention are known to those skilled in the art. For example, document WO 97/14650 A1 describes methods for the manufacture of hydrated lime usable in the present invention.
    According to another embodiment of the invention, the composition contains clay and / or activated carbon and / or zeolites in an amount of up to 30% by weight relative to the total weight of the composition. This helps in particular to obtain a composition effective in the purification of smoke gases, in particular smoke gases also containing heavy metals and / or organic pollutants such as dioxins.
    In addition to the composition, the invention also provides methods for the manufacture of the composition intended for the purification of flue gases.
    The processes for the manufacture of the composition intended for the purification of smoke gases according to the invention
    BE2016 / 5974 basically includes the following steps:
    at. have a composition containing, in each case relative to the total weight of the composition:
    99% by weight of a powder of a sodium salt of carbonic acid, and 99% by weight of a powder of an absorbent material; and
    b. applying mechanical and / or thermal energy to the composition;
    wherein said powder of said absorbent material has a specific pore volume which is equal to or greater than 0.1 cm 3 / g.
    The steps can be performed in any desired order. Preferably, the steps are carried out in the order indicated above.
    In accordance with one embodiment of the manufacturing method of the invention, the composition in step a. contains 1 to 70% by weight, preferably 1 to 50% by weight or 1 to 30% by weight or 5 to 30% by weight or 10 to 30% by weight or 13 to 30% by weight or 13 to 20% by weight or 13 to 18% by weight or 5 to 99% by weight or 10 to 99% by weight or 15 to 99% by weight or 15 to 90% by weight or 15 to 80% by weight or 15 to 75% by weight or 15 to 70% by weight or 15 to 65% by weight or 15 to 60% by weight or 15 to 50% by weight or 15 to 45% by weight or 15 to 40% by weight or 15 to 30% by weight or 15 to 25% by weight or 15 to 20% by weight or 15 to 18% by weight of the powder of the sodium salt of carbonic acid, relative to the total weight of the composition.
    According to another embodiment of the manufacturing method of the invention, the composition in step a. contains 30 to 99% by weight, preferably 50 to 99% by weight or 70 to 99% by weight or 70 to 95% by weight or 70 to 90% by weight or 70 to 87% by weight or 80 to 87% by weight or 82 to 87% by weight or 1 to 95% by weight or 1 to 90% by weight or 1 to 85% by weight or 10 to 85% by weight or 20 to 85% by weight or 25 to
    BE2016 / 5974% by weight or 30 to 85% by weight or 35 to 85% by weight or 40 to 85% by weight or 50 to 85% by weight or 55 to 85% by weight or 60 to 85% by weight or 70 at 85% by weight or 75 to 85% by weight or 80 to 85% by weight or 82 to 85% by weight of the powder of the absorbent material, relative to the total weight of the composition.
    As regards the sodium salt of carbonic acid and / or the absorbent material of the manufacturing process according to the invention, the above provisions concerning the sodium salt of carbonic acid and / or concerning the absorbent material, respectively , will apply. In particular, the provisions concerning the granulometry and / or the type of material used for the sodium salt of carbonic acid and / or the provisions concerning the type of material used for the absorbent material, the granulometry, the specific surface and / or the pore volume of the absorbent material as described above, will apply. In addition, the provisions concerning in particular the FFC values, fluidity values, and of the composition as described above will apply.
    According to one embodiment of the manufacturing method according to the invention, thermal and / or mechanical energy is applied to the powder of a sodium salt of carbonic acid and / or to said powder of an absorbent material. This gives more flexibility in the preparation of the composition according to the invention.
    The thermal energy can for example be applied by heating the powders and / or compositions for example by heating for example in an oven, or by irradiation with an appropriate irradiation source such as a radiant radiator.
    Mechanical energy can be applied to powders and / or compositions in different forms. For example, mechanical energy can be applied by fragmentation, grinding and / or
    BE2016 / 5974 grinding. To this end, it is advantageous to use suitable devices such as ball mills, jet mills, wheel mills, pin mills, or roller mills. However, mechanical energy can also be applied to the powders and / or compositions by mixing the powders and / or compositions using a mixer. Suitable mixers can include plow mixers, rotor mixers, paddle mixers, ribbon mixers, jet mixers, and / or screw mixers. The application of mechanical energy can also comprise several stages, for example a first stage of fragmentation, grinding and / or grinding, and a second stage of mixing.
    According to another embodiment of the manufacturing method according to the invention, step b. includes a mixing and / or grinding step. In this way, the agglutination of the sodium salt of carbonic acid on the grinding equipment can be minimized. It is also possible to obtain a very homogeneous composition.
    Optimal results are obtained in the manufacturing process according to the invention when step b. comprises a grinding step in which the composition is ground to a particle size dso equal to or less than 50 μm, in particular less than 45 μm or less than 40 μm or less than 35 μm or less than 30 μm or less than 25 μm or less at 20 pm or less than 15 pm or less than 12 pm. Advantageously, the composition is ground to a particle size d 97 of less than 180 μm, in particular less than 170 μm or less than 160 μm or less than 150 μm or less than 140 μm or less than 125 μm. This can directly give a usable composition which can also be stored. This can also help reduce clumping of the grinding load on the grinding equipment.
    In addition, the invention also provides a method
    BE2016 / 5974 for the purification of smoke gases. In the process for the purification of smoke gases according to the invention, the smoke gas is brought into contact with the composition according to
    The invention.
    The composition according to the invention can be used for different purposes. Ideally, the composition according to the invention is used for the purification of smoke gases, preferably for the purification of smoke gases containing HF.
    In addition, the invention provides the use of a powder of an absorbent material having a specific pore volume which is equal to or greater than 0.1 cm 3 / g, to improve the fluidity, in particular after a certain storage time, and / or the storage capacity and / or the absorption capacity of HF of a powder of a sodium salt of carbonic acid having a particle size dso of less than 50 μm, in particular less than 45 pm or less than 40 pm. Preferably, the sodium salt of carbonic acid is sodium hydrogencarbonate and / or sodium sesquicarbonate.
    According to one embodiment of the use of the powder of an absorbent material according to the invention, the powder of the absorbent material is used in an amount of 1 to 99% by weight, in particular from 30 to 99% by weight or from 50 to 99% by weight or from 70 to 99% by weight or from 70 to 95% by weight or from 70 to 90% by weight or from 70 to 87% by weight or from 80 to 87% by weight or 82 to 87% by weight or from 1 to 95% by weight or from 1 to 90% by weight or from 1 to 85% by weight or from 10 to 85% by weight or from 20 to 85% by weight or from 25 to 85% by weight or from 30 to 85% by weight or from 35 to 85% by weight or from 40 to 85% by weight or from 50 to 85% by weight or from 55 to 85% by weight or from 60 to 85% by weight or from 70 to 85% by weight or from 75 to 85% by weight or from 80 to 85% by weight or from 82 to 85% by weight, relative to the total weight of the composition.
    6 BE2016 / 5974
    With regard to the absorbent material for using the powder of an absorbent material according to the invention, the provisions concerning the absorbent material will apply. In particular, the provisions concerning the type of material used for the absorbent material, the particle size, the specific surface and / or the pore volume of the absorbent material as described above will apply.
    Figure 1 shows the relative SO 2 absorption (called decrease in SO 2 ) in% as a function of the fraction of ground sodium hydrogencarbonate for different absorbent compositions having different contents of sodium hydrogencarbonate and hydrated lime.
    Figure 2 shows the dependence of the value of fresh samples of absorbent compositions from 18 hour old samples of absorbent compositions for different fractions of sodium hydrogencarbonate and hydrated lime, respectively.
    In the following, the invention will be further explained by examples which are illustrative only and should not be considered to be limiting in any way.
    in
    FFC and
    Used materials
    Sodium hydrogencarbonate, NaHCCL (Bicar, Solvay); hydrated lime Ca (OH) 2 , (Sorbacal® SP, Lhoist). Sorbacal® SP has a BET specific surface of approximately 40 m 2 / g, a specific pore volume BJH of approximately 0.2 cm 3 / g, and a particle size d 50 of approximately 6 μm.
    Example 1
    Preparation of compositions for the purification of smoke gases
    The sodium hydrogencarbonate was ground using
    B E2016 / 5974 a pin mill until a powder with a d 50 value of 28.9 μm is obtained, as determined by scattering of laser light in an ethanolic suspension using a Helos particle analyzer from Sympatec. The particle size analyzer has Sucell equipment, and the sample was subjected to ultrasonic treatment for 120 seconds with a pause of 120 seconds, and the suspension was stirred at 70 rpm. The ground sodium hydrogencarbonate was then mixed homogeneously with hydrated lime in the proportions indicated in Table 1 to obtain compositions for the purification of smoke gases. The mixing of the powders was carried out using a rotor mixer.
    Table 1
    Proportions of compositions for the purification of smoke gases
    Composition Amount of NaHCCb Amount of Ca (OH) 2 number [% in weight] [% in weight] 1 5 95 2 10 90 3 25 75 4 50 50 5 75 25
    Example 2
    Determination of the absorption capacity of SO 2
    The SO 2 absorption powers of compositions 3, 4 and were determined in a pilot flue gas treatment installation which is mainly described in document WO 2007/000433 A2, on pages 10 to 12 in FIG. 2 of this document. The compositions were injected in co-current flow to purify a model smoke gas under the following gas conditions:
    Temperature 220 ° C,
    B E2016 / 5974
    SO2 concentration at entry 1500 mg / Nm 3
    H 2 0 content 10%,
    Concentration of C0 2 9%,
    Average stoichiometric ratio of the absorbent composition to SO 2 (expressed relative to the entry) of 2.5.
    The results of the SO 2 absorption tests are compiled in Table 2 and presented in Figure 1 together with the results for pure hydrated lime serving as a comparative example.
    Table 2
    Composition NaHCO 3 content [% by weight] Absolute absorbency of SO 2 [% abs.] Absorbency of SO 2 relative to 100% Ca (OH) 2 [% rel. ] 100% Ca (OH) 2 (comparative) 0 23 100 3 25 32 139 4 50 46 200 5 75 59 257
    During the test, no abnormal blockage or blockage of the dosing equipment was observed. Thus, the dosing device was not affected ground sodium.
    by the presence
    This may indicate hydrated over hydrogen carbonate of the beneficial effect of lime ground sodium hydrogencarbonate.
    In addition, the absorption capacity of SO 2 in compositions 3, 4 and 5 is significantly higher than that of pure hydrated lime.
    Example 3
    Fluidity of the compositions
    B E2016 / 5974 and lime
    The fluidity of compositions 1 to 5 hydrated pure, serving as a comparative example, was studied by determining their FFC values using an annular shear tester RST-XS. The results are presented in FIG. 2 and using diamonds for the FFC values of samples of the freshly prepared composition and squares for the FFC values of samples measured 18 hours after the preparation of the compositions.
    From Figure 2, one can see the advantageous effect of the mixture of hydrated lime with sodium hydrogencarbonate powder on the fluidity after a certain storage time. For freshly prepared compositions, the FFC value of compositions having a small amount of hydrated lime is higher than that of compositions having a large amount of hydrated lime. However, after 18 hours, the FFC value of compositions having a small amount of hydrated lime is lower than that of a composition having a large amount of hydrated lime. In particular, an FFC value greater than 1 is maintained even after 18 hours for compositions containing more than 70% by weight of hydrated lime. In addition, the decrease in the FFC value is more and 5, containing by weight lime important for the compositions L. 50% by weight and 25% respectively ! hydrated, as for compositions 1 to 3 containing respectively 95% by weight, 90% by weight and 75% by weight of hydrated lime. This indicates that the decrease in fluidity over time depends on the ratio between hydrated lime and sodium hydrogencarbonate. A particularly well-balanced property profile is obtained with FFC values of about 1 or more and better absorption capacity of sulfur dioxide if the sodium hydrogen carbonate is present in an amount of about 10 to 25% by weight. , in particular in an amount of about 15 to 25% by weight. As already mentioned, higher FFC values indicate
    B E2016 / 5974 better fluidity.
    It is important to note that it is also observed that compositions containing more than 25% by weight of hydrated lime can be stored at least temporarily without exhibiting the disadvantageous handling properties of pure ground sodium hydrogen carbonate.
    BE2016 / 5974
    权利要求:
    Claims (5)
    [1]
    1 to 99% by weight of a powder of an absorbent material; and
    b. applying mechanical and / or thermal energy to the composition;
    wherein said powder of said absorbent material has a specific pore volume which is equal to or greater than 0.1 cm 3 / g.
    12. The method of claim 11, wherein the composition in step a. contains 1 to 70% by weight, in particular 1 to 50% by weight or 1 to 30% by weight or 5 to 30%
    in weight or 10 to 30 % in weight or 13 to 30 % by weight or 13 at 20 % in weight or 13 to 18% by weight or 5 at 99% by weight or 10 at 99% by weight or 15 99% in weight or 15 90% by weight or 15 at 80 % by weight or 15 to 75% in weight or 15 to 70% by weight or 15 to 65% in weight or 15 to 60% in weight or 15 to 50% in weight or 15 to 45 % in weight or 15 to 40% in weight or 15 to 30 O,O in weight or 15 to 25% in weight or 15 to 20 % by weight or 15 at
    18% by weight of said powder of said sodium salt of carbonic acid, relative to the total weight of the composition,
    35 BE2016 / 5974 and / or in which the composition in step a. contains 30 to 99% by weight, in particular 50 to 99% by weight or 70 to 99% by weight or 70 to 95% by weight or 70 to 90% by weight or 70 to 87% by weight or 80 to 87% by weight or 82 to 87% by weight or 1 to 95% by weight or 1 to 90% by weight or 1 to 85% by weight or 10 to 85% by weight or 20 to 85% by weight or 25 to 85% by weight or 30 to 85% by weight or 35 to 85% by weight or 40 to 85% by weight or 50 to 85% by weight or 55 to 85% by weight or 60 to 85% by weight or 70 to 85% by weight or 75 to 85% by weight or 80 to 85% by weight or 82 to 85% by weight of said powder of said absorbent material, relative to the total weight of the composition.
    13. A method according to any one of claims 11 and 12, wherein said sodium salt of carbonic acid is as defined in any one of claims 3 to 5 and / or said powder of said absorbent material is as defined in any one of claims 6 to 8.
    14. Method according to any one of claims 11 to 13, in which thermal and / or mechanical energy is applied to said powder of a sodium salt of carbonic acid and / or to said powder of an absorbent material.
    15. Method according to any one of claims 11 to 14, in which step b. comprises a mixing and / or grinding step, and optionally in which, in the grinding step, the composition is milled to a particle size d 50 equal to or less than 50 μm, in particular less than 45 μm or less than 40 μm or less than 35 pm or less than 30 pm or less than 25 pm or less than 20 pm or less than
    15 pm or less than 12 pm; and / or in which the composition is ground to a particle size d 97 of less than 180 μm, in particular less than 170 μm or less than 160 μm or
    1 to 99% by weight of a powder of a sodium salt of carbonic acid, and
    1. Composition for the purification of smoke gases, said composition containing, in each case relative to the total weight of the composition:
    at. 1 to 99% by weight of a powder of a sodium salt of carbonic acid; and
    b. 1 to 99% by weight of a powder of an absorbent material;
    wherein said powder of said absorbent material has a specific pore volume which is equal to or greater than 0.1 cm 3 / g.
    [2]
    2. Composition according to claim 1, which composition contains 1 to 70% by weight, in particular 1 to
    50% by weight or 1 to 30% by weight or 5 to 30% by weight or 10 to 30% by weight or 13 to 30% by weight or 13 to 20% by weight or
    13 to 18% by weight or 5 to 99% by weight or 10 to 99% by weight or 15 to 99% by weight or 15 to 90% by weight or 15 to 80% by weight or 15 to 75% by weight or 15 at 70% by weight or 15 to 65% by weight or 15 to 60% by weight or 15 to 50% by weight or 15 to
    45% by weight or 15 to 40% by weight or 15 to 30% by weight or
    15 to 25% by weight or 15 to 20% by weight or 15 to 18% by weight of said powder of said sodium salt of carbonic acid, relative to the total weight of the composition, and / or which composition contains 30 to 99 % by weight, in particular 50 to 99% by weight or 70 to 99% by weight or 70 to 95% by weight or 70 to 90% by weight or 70 to 87% by weight or 80 to 87% by weight or 82 to 87% by weight or 1 to 95% by weight or 1 to 90% by weight or 1 to 85% by weight or 10 to 85% by weight or 20 to 85% by weight or 25 to 85% by weight or 30 to 85 % by weight or 35 to 85% by weight or 40 to 85% by weight or 50 to 85% by weight or 55 to 85% by weight or 60 to 85% by weight or 70 to 85% by weight or 75 to 85% by weight or 80 to 85% by weight or 82 to 85% by weight of said powder of said absorbent material, relative to the total weight of the composition.
    BE2016 / 5974
    [3]
    3 6 B E2016 / 5974 less than 150 pm or less than 140 pm or less than 125 pm.
    16. Composition for the purification of a smoke gas obtainable by the method according to any one of claims 11 to 15.
    17. Process for the purification of smoke gases, in which the smoke gases are brought into contact with a composition according to any one of claims 1 to 10 and 16.
    18. Use of a composition according to any one of claims 1 to 10 and 16 for the purification of smoke gases, in particular smoke gases containing HF.
    19. Use of a powder of an absorbent material having a specific pore volume equal to or greater than 0.1 cm 3 / g to improve the fluidity, in particular after a certain storage time, and / or the ability to storage and / or the absorption capacity of HF of a powder of a sodium salt of carbonic acid having a particle size d 50 of less than 50 μm, in particular less than 45 μm or less than 40 μm.
    20. Use according to claim 19, wherein said powder of said absorbent material is used in an amount of from 1 to 99% by weight, in particular from 30 to 99% by weight or from 50 to 99% by weight or from 70 to 99 % by weight or from 70 to 95% by weight or from 70 to 90% by weight or from 70 to 87% by weight or from 80 to 87% by weight or from 82 to 87% by weight or from 1 to 95% by by weight or from 1 to 90% by weight or from 1 to 85% by weight or from 10 to 85% by weight or from 20 to 85% by weight or from 25 to 85% by weight or from 30 to 85% by weight or from 35 to 85% by weight or from 40 to 85% by weight or from 50 to 85% by weight or from 55 to 85% by weight or from 60 to 85% by weight or from 70 to 85% by
    BE2016 / 5974 weight or from 75 to 85% by weight or from 80 to 85% by weight or from 82 to 85% by weight, relative to the total weight of the composition; and / or wherein said powder of said absorbent material is as defined in any one of
    3. Composition according to claim 1 or claim 2, wherein said powder of said sodium salt of carbonic acid has a particle size d 50 of less than 50 µm, in particular less than 45 µm or less than 40 µm or less than 35 µm or less than 30 pm or less than 25 pm or less than 20 pm or less than 15 pm or less than 12 pm; and / or wherein said powder of said sodium salt of carbonic acid has a particle size d 97 less than 180 pm, in particular less than 170 pm or less than 160 pm or less than 150 pm or less than 140 pm or less than 125 pm.
    [4]
    4. Composition according to any one of the preceding claims, in which said sodium salt of carbonic acid is chosen from the group consisting of sodium hydrogencarbonate, sodium carbonate, sodium sesquicarbonate, and mixtures thereof.
    5. Composition according to any one of the preceding claims, in which said sodium salt of carbonic acid is sodium hydrogencarbonate and / or sodium sesquicarbonate.
    6. Composition according to any one of the preceding claims, in which said absorbent material is chosen from the group consisting of limestone, quicklime, hydrated lime, raw dolomite (dolomite), quicklime dolomitic, lime dolomitic hydrate, magnesium carbonate, magnesium oxide, magnesium hydroxide, and mixtures thereof.
    7. Composition according to any one of the preceding claims, in which said material
    BE2016 / 5974 absorbent is hydrated lime.
    8. Composition according to any one of the preceding claims, in which said absorbent material, in particular said hydrated lime, has a particle size d 5 o of less than 50 μm, in particular less than 40 μm, or less than 30 μm, or less at 20 pm, or less than 10 pm; and / or in which said absorbent material, in particular said hydrated lime, has a particle size d 97 less than 150 μm, in particular less than 140 μm, or less than 130 μm, or less than 120 μm, or less than 110 μm, or less than 100 pm, or less than 90 pm; and / or in which said absorbent material, in particular said hydrated lime, has a specific surface equal to or greater than 20 m 2 / g, in particular equal to or greater than 30 m 2 / g, or equal to or greater than 40 m 2 / g, or equal to or greater than 45 m 2 / g; and / or in which said absorbent material, in particular said hydrated lime, has a specific pore volume equal to or greater than 0.11 cm 3 / g or equal or greater than 0.12 cm 3 / g or equal or greater than 0, 13 cm 3 / g or equal to or greater than 0.14 cm 3 / g or equal or greater than 0.15 cm 3 / g or equal or greater than 0.16 cm 3 / g or equal or greater than 0.17 cm 3 / g or equal or greater than 0.18 cm 3 / g or equal or greater than 0.19 cm 3 / g or equal or greater than 0.2 cm 3 / g.
    9. Composition according to any one ofprevious claims which composition containsclay and / or activated carbon and / or zeolites in onequantity up to 30% by weight relative to the weighttotal of the composition. 10. Composition according to 1 'a any of
    previous claims, which composition has a flow value, in particular an FFC value, in particular
    34 B E2016 / 5974 determined by using an annular shear tester RST-XS, 0.2 or more, in particular 0.3 or more, or 0.4 or more, or 0.5 or more , or 0.6 or more, or 0.7 or more, or 0.8 or more, or 0.9 or more, or 1.0 or more, or 1.1 or more, or 1.2 or more, or 1.3 or more.
    11. Process for the manufacture of a composition for the purification of flue gases according to any one of claims 1 to 10, comprising the operations consisting in:
    at. have a composition containing, in each case relative to the total weight of the composition:
    [5]
    5 claims 6 to 8; and / or wherein said sodium salt of carbonic acid is sodium hydrogencarbonate and / or sodium sesquicarbonate.
    BE2016 / 5974
    Removal of SO 2 by mixtures of Sorbacal SP with ground sodium hydrogen carbonate, if measured in a flue gas treatment plant (220 ° C., 1500 g; rtro : i of SOj. Stoichiometric ratio of 2.5, 10% H 2 0.9% COJ
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4668489A|1984-01-30|1987-05-26|Efb Inc.|Method for treating gas streams|
    EP0190416A3|1984-11-30|1988-07-27|Waagner-Biro Aktiengesellschaft|Process for separating pollutants from combustion gases|
    BE1009692A3|1995-10-19|1997-07-01|Lhoist Rech & Dev Sa|PARTICLE Ca 2.|
    JP3948075B2|1997-10-01|2007-07-25|旭硝子株式会社|Acid component removal agent and acid component removal method|
    JPH11165036A|1997-12-04|1999-06-22|Abb Kk|Dual alkali treatment of exhaust gas from incinerator|
    US6352653B1|1998-11-26|2002-03-05|Asahi Glass Company Ltd.|Acid component-removing agent, method for producing it and method for removing acid components|
    JP3828008B2|2001-12-20|2006-09-27|上田石灰製造株式会社|Acid gas absorbent|
    DE20210008U1|2002-04-16|2002-10-24|Walhalla Kalk Gmbh & Co Kg|Exhaust gas cleaning reagents|
    JP4581682B2|2004-12-27|2010-11-17|旭硝子株式会社|Reduction method of dioxins in fly ash of garbage incineration equipment|
    WO2006113301A1|2005-04-19|2006-10-26|Carmeuse North America Services, Inc.|Method for producing activated lime for removal of acid gases from a combustion gas|
    BE1016661A3|2005-06-28|2007-04-03|Lhoist Rech & Dev Sa|PULVERULENT LIME COMPOSITION, METHOD FOR MANUFACTURING THE SAME, AND USE THEREOF|
    JP2009507632A|2005-09-15|2009-02-26|ソルベイ・ケミカルズ・インコーポレーテッド|Removal of sulfur trioxide from exhaust gas stream|
    WO2007135823A1|2006-05-19|2007-11-29|Asahi Glass Company, Limited|Method of removing halogen gas and remover for halogen gas|
    CN101773768A|2010-03-16|2010-07-14|长春惠工净化工业有限公司|Dechlorinating agent used for removing HCl from gas by dry method and preparation method thereof|
    JP5691211B2|2010-03-25|2015-04-01|栗田工業株式会社|Combustion exhaust gas treatment method|
    KR20130050668A|2011-11-08|2013-05-16|주식회사 포스코|Method for removal of sulfur oxides in exhausted gas using the high activity calciumhydrooxide|
    JP5991677B2|2012-09-24|2016-09-14|三菱重工環境・化学エンジニアリング株式会社|Exhaust gas treatment equipment|
    BE1021753B1|2013-12-10|2016-01-15|New Lime Development Sprl|HYDRATED LIME COMPOSITION FOR THE TREATMENT OF SMOKE|CN109569264A|2018-11-14|2019-04-05|广州永兴环保能源有限公司|A kind of sodium bicarbonate depickling medicament depickling test method|
    法律状态:
    2018-04-09| FG| Patent granted|Effective date: 20180404 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP15203139.9A|EP3187244A1|2015-12-30|2015-12-30|Composition for the purification of flue gas|
    EP15203139.9|2015-12-30|
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