WO2016184518A1 - Composition de sorbant à base de chaux pour l'élimination du mercure et procédé de fabrication associé - Google Patents

Composition de sorbant à base de chaux pour l'élimination du mercure et procédé de fabrication associé Download PDF

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Publication number
WO2016184518A1
WO2016184518A1 PCT/EP2015/061147 EP2015061147W WO2016184518A1 WO 2016184518 A1 WO2016184518 A1 WO 2016184518A1 EP 2015061147 W EP2015061147 W EP 2015061147W WO 2016184518 A1 WO2016184518 A1 WO 2016184518A1
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calcium
lime
magnesium
anyone
magnesium compound
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PCT/EP2015/061147
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English (en)
Inventor
Johan HEISZWOLF
Olivier NYSSEN
Vincent CLERC
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S.A. Lhoist Recherche Et Developpement
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Priority to PCT/EP2015/061147 priority Critical patent/WO2016184518A1/fr
Priority to FR1654552A priority patent/FR3036293A1/fr
Priority to BE2016/5369A priority patent/BE1023752B1/fr
Priority to PCT/EP2016/061480 priority patent/WO2016185033A1/fr
Publication of WO2016184518A1 publication Critical patent/WO2016184518A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Definitions

  • the present invention relates to a sorbent composition containing particles for removing heavy metals, in particular mercury, from flue gases.
  • Sorbent composition containing solid particles are well known in the art.
  • the carbon colors the gypsum produced from wet desulfurization process black while the whiteness of this material determines its valorization value when selling it to gypsum manufacturer.
  • activated carbon is naturally retained in the fly ash waste stream.
  • activated carbon can adversely interact with the additives used in cement and concrete formulations precluding by consequence the utilization of said fly ash containing activated carbon as additive in the cement industry that must therefore rather be disposed of, at significant cost.
  • aqueous solution of a silica containing precursor such as silicic acid, colloidal silica
  • the sorbent composition is intended to be used under aqueous suspension in two different applications.
  • the aqueous suspension is designed to be used in wet flue gas desulfurizer units, where it is stable enough.
  • the aqueous suspension is injected in the dry and hot flue gas.
  • the aqueous suspension is dried in the hot flue gas causing likely in such a case a loss of efficiency due to sensitivity towards thermal decomposition and a lack of reproducibility since the drying process of the sorbent is only undergone and not controlled.
  • tests conducted in our study have proven that spray-dried colloidal silica particles have a tendency to trap active chemical compounds into the particle core during the spray-drying step, thus reducing overall efficiency.
  • an inorganic base such as calcium hydroxide, sodium sesquicarbonate, sodium (bi)carbonate, potassium carbonate and/or calcium carbonate
  • a sulfide such as ammonium sulfide, alkali metal sulfide, alkali-earth metal sulfide and/or transition metal sulfide
  • a support such as silicate, aluminate, aluminosilicate, and/or carbon carrying the admixture.
  • the present invention relates more precisely to sorbent composition containing particles for removing heavy metals, in particular mercury, from flue gases, wherein said particles are core-shell particles with the aim to solve at least a part of the aforementioned drawbacks by providing a composition for an oxidative sorbent material used in the capture of heavy metals, and more specifically mercury, in both ionic and metallic form, and its method of manufacturing.
  • the heavy metals can be removed from a fluid, preferentially a gaseous fluid, notably from flue gas, wherein the heavy metals are usually gaseous, in coal-fired plants, municipal solid waste incinerators, and/or cement kilns and/or other industries exhaust gases.
  • a lime-based sorbent composition wherein the core comprises a calcium-magnesium compound fitting the formula aCaC0 3 .bMgC0 3 .xCa0.yMg0.zCa(OH)2.t g(OH)2.ul, wherein I represents impurities, a, b, x, y, z and t each being mass fractions > 0 and ⁇ 100%, u being mass fraction ⁇ 0 and ⁇ 20 % by weight, based on the total weight of said at least one calcium-magnesium compound, characterized in that said core is coated with a shell presenting a thickness of less than 20 ⁇ and greater than 50 nm, shielding the core from the flue gases medium and comprising at least a metal salt and a sulfur-based compound.
  • the CaC0 3 , MgC03, CaO, MgO, Ca(OH) 2 and Mg ⁇ OH) 2 contents in calcium-magnesium compounds may easily be determined with conventional methods. For example, they may be determined by X fluorescence analysis, the procedure of which is described in the EN 15309 standard, coupled with a measurement of the loss on ignition and a measurement of the C0 2 volume according to the EN 459-2:2010 E standard.
  • the impurities I notably comprise all those which are encountered in natural limestones and dolomites, such as clays of the silico-aluminate type, silica, impurities based on iron or manganese,... or those coming from the manufacturing process of the calcium-magnesium compound.
  • hydrated lime means an industrial calcium-magnesium compound made essentially of calcium dihydroxide Ca(OH) 2 with impurities.
  • the negative effect of lime is reduced, thereby increasing drastically the mercury removal capacity of the composition according to the present invention.
  • the core of calcium-magnesium particles is totally shielded from the mercury compounds by the shell layer of sulfurous compound.
  • an alkaline lime core (calcium- magnesium compound) helps to improve the stability of the sulfurous compound in the shell layer in its most reactive form being S 2" while at the same time preventing H 2 S emissions resulting from acidic conditions.
  • the sulfur-based compound in the shell can react with ionic mercury present in the flue gases and form HgS.
  • said sulfur-based compound in the lime-based sorbent composition according to the present invention, is fitting the formula A a S O v wherein a, ⁇ and ⁇ each being mass fraction with ⁇ 0 and where A is chosen in the group consisting of calcium, magnesium, potassium, sodium and their mixture.
  • said sulfur-based compound is chosen in the group consisting of sulfide salts, such as calcium sulfide, dithiocarbamates, sulfate salts, such as calcium sulfate, polymer- based dithiocarbamates, polysulfide salts, such as calcium polysulfide, and their mixture.
  • the lime-based composition according to the present invention is mainly from inorganic nature, thereby helping to reduce the global carbon content in the fly ash.
  • said metal salt in the lime-based sorbent composition according to the invention, is chosen in the group consisting of salts of titanium, vanadium, manganese, iron, nickel, copper, zinc, and their mixture, preferably copper.
  • said metal salt is a copper halide, preferably a copper chloride.
  • the lime-based sorbent composition according to the invention further comprises a doping agent chosen in the group consisting of alkali metal halides, such as sodium or potassium halides, alkali earth metal halides, such as calcium or magnesium halides, ammonium halides and their mixtures.
  • a doping agent chosen in the group consisting of alkali metal halides, such as sodium or potassium halides, alkali earth metal halides, such as calcium or magnesium halides, ammonium halides and their mixtures.
  • the lime-based sorbent composition according to the invention further comprises a dispersing agent chosen in the group consisting of (poly)sulfates, such as sodium docecyl sulfate (SDS), (poly)sulfonates, (poly)phosphates, (poly)phosphonates, such as diethylenetriamine- penta(methylene phosphonic acid) (DTPMP), polyols, and their mixtures.
  • a dispersing agent chosen in the group consisting of (poly)sulfates, such as sodium docecyl sulfate (SDS), (poly)sulfonates, (poly)phosphates, (poly)phosphonates, such as diethylenetriamine- penta(methylene phosphonic acid) (DTPMP), polyols, and their mixtures.
  • most of the core particles in the lime-based sorbent composition are made from hydrated lime, also called slaked lime, meaning that some particles might have a core being entirely slaked lime particles or a mixture of slaked and quicklime in the same core or even partially slaked lime particles; to a level such that the amount of slaked lime with respect to the calcium-magnesium particles is greater than 60 w%.
  • Said at least one calcium-magnesium compound according to the present invention is therefore at least formed with slaked lime, slaked dolomitic lime, magnesium slaked lime or burnt dolime from the calcination of natural limestones or dolomites.
  • composition according to the invention may therefore also comprise calcium or magnesium carbonates such as unburnt materials from the calcination of natural limestones or dolomites or else further products from the recarbonation of calcium-magnesium compounds. Finally it may also comprise calcium or magnesium oxides from the partial hydration (slaking) of calcium-magnesium compounds.
  • the calcium-magnesium compound of the lime-based sorbent composition presents a particle size distribution wherein di 0 is comprised in the range from 0,5 to 3 ⁇ , preferably from 0,75 to 2 ⁇ ; dg 0 is comprised in the range from 7 to 50 ⁇ , preferably from 10 to 40 ⁇ , d 50 is comprised in the range from 3 to 50 ⁇ , preferably from 4 to 30 ⁇ .
  • the notation d x represents a diameter expressed in ⁇ , relatively to which X % by mass of the measured particles are smaller or equal.
  • said shell presents a thickness of less than 10 ⁇ , preferably less than 5 ⁇ , in particular less than 2 ⁇ , and greater than 100 nm, preferably greater than 200 nm, in particular greater than 300 nm.
  • the ratio between calcium-magnesium compound (core) and sulfur ranges from 15:1 w/w to 1:1 w/w and preferably is of 2,5:1 w/w in the lime-based sorbent composition.
  • the ratio between calcium-magnesium compound (core) and said metal salt ranges from 15:1 w/w to 1:1 w/w and preferably is of 5:1 w/w in the lime-based sorbent composition according to the invention.
  • the present invention also relates to a process to produce a lime-based sorbent composition comprising the steps of :
  • said metal ammonia complex is obtained by mixing a metal salt with an ammonia solution, where the ratio between said metal salt and said ammonia ranges from 1:2 w/w to 1:10 w/w and preferably is of 1:5,5 w/w.
  • said calcium-magnesium polysulfide solution is obtained by mixing a sulfur-based compound with a calcium-magnesium compound fitting the formula pCa0.qMg0.rCa(OH)2.sMg(OH) 2 .ul, wherein I represents impurities, u being mass fractions > 0 and ⁇ 20%, p, q, r and s each being mass fractions > 0 and ⁇ 100%, with p + q + r + s > 60% by weight, based on the total weight of said at least one calcium magnesium compound to form said calcium-magnesium polysulfide solution.
  • said aqueous suspension of calcium-magnesium compound also called milk of calcium-magnesium compound
  • presents a solid content between 30 and 45 w% with respect to the total weight of the suspension of calcium-magnesium compound.
  • the aqueous suspension of calcium-magnesium compound comprises particles having a particle size distribution wherein d 50 is comprised in the range from 0,5 to 20 ⁇ , preferably from 0,5 to 10 ⁇ and more preferably from 1 to 2,5 ⁇ .
  • said sulfur-based compound is fitting the formula A a SpO v wherein a, ⁇ and y each being mass fraction with ⁇ 0 and where A is chosen in the group consisting of calcium, magnesium, potassium, sodium and their mixture.
  • said sulfur-based compound is chosen in the group consisting of sulfide salts, such as calcium sulfide, dithiocarbamates, sulfate salts, such as calcium sulfate, polymer-based dithiocarbamates, polysulfide salts, such as calcium polysulfide, and their mixture.
  • said metal salt is chosen in the group consisting of salts of titanium, vanadium, manganese, iron, nickel, copper, zinc, and their mixture, preferably copper.
  • said metal salt is a copper halide, preferably a copper chloride.
  • the process further comprises a step of adding a doping agent chosen in the group consisting of alkali metal halides, such as sodium or potassium halides, alkali earth metal halides, such as calcium or magnesium halides, ammonium halides and their mixtures.
  • a doping agent chosen in the group consisting of alkali metal halides, such as sodium or potassium halides, alkali earth metal halides, such as calcium or magnesium halides, ammonium halides and their mixtures.
  • Such doping agent can be added either to the spray dried lime- based composition, meaning after the spray drying, or to the calcium- magnesium polysulfide solution, preferably to the calcium-magnesium polysulfide solution.
  • the process further comprises a step of adding a dispersing agent chosen in the group consisting of (poly)sulfates, such as sodium docecyl sulfate (SDS), (poly)sulfonates, (poly)phosphates, (poly)phosphonates, such as diethylenetriamine-pentafmethylene phosphonic acid) (DTPMP), polyols, and their mixtures.
  • a dispersing agent chosen in the group consisting of (poly)sulfates, such as sodium docecyl sulfate (SDS), (poly)sulfonates, (poly)phosphates, (poly)phosphonates, such as diethylenetriamine-pentafmethylene phosphonic acid) (DTPMP), polyols, and their mixtures.
  • Such dispersing agent is preferably added to the aqueous suspension of calcium-magnesium compound either before, after or simultaneously with the metal ammonia complex.
  • the calcium-magnesium compound fitting the formula aCaC0 3 .bMgC0 3 .xCa0.yMg0.zCa(OH)2.tMg(OH)2.ul, z + t > 60%, preferentially ⁇ 70%, preferably > 80%, more preferably > 90%, in particular > 93% by weight, based on the total weight of said at least one calcium-magnesium compound.
  • z in the calcium-magnesium compound fitting the formula aCaC0 3 .bMgC0 3 .xCa0.yMg0.zCa(OH)2.tMg(OH) 2 .uf, z > 60%, preferentially > 70%, preferably > 80%, more preferably > 90%, in particular > 93% by weight, based on the total weight of said at least one calcium-magnesium compound.
  • said shell presents a thickness of less than 10 ⁇ , preferably less than 5 ⁇ , in particular less than 2 ⁇ , and greater than 100 nm, preferably greater than 200 nm, in particular greater than 300 nm.
  • the ratio between calcium-magnesium compound and sulfur ranges from 1:1 w/w to 1:2 w/w, preferably of 1:1,5 w/w in the calcium-magnesium polysulfide composition.
  • the ratio between said calcium-magnesium compound and said metal salt ranges from 15:1 w/w to 1:1, preferably is 5:1 w/w in the suspension of calcium-magnesium particles onto which the metal is dispersed.
  • the calcium-magnesium compound presents a specific surface area measured by manometry with adsorption of nitrogen after degassing in vacuo at 190T for at least 2 hours and calculated according to the multipoint BET method as described in the ISO 9277:2010E standard comprised between 5 m 2 /g and 50 m 2 /g.
  • Figure 1 represents a SEM picture of the particles of the sample
  • product 1 obtained from example 1, showing core-shell particles of CuCI 2 /CaS x supported on lime.
  • the particles exhibit a mean diameter around 5 ⁇ , the particle size measuring typically between 1 and 10 pm.
  • Figure 2 is a schematic presentation of the device used to measure the mercury capture with the several samples according to the invention and the one of the comparative examples.
  • Figure 3 represents the results of example 1.
  • Figure 4 represents the results of example 2.
  • Figure 5 represents the results of comparative example 1.
  • Figure 6 represents the results of comparative example 2.
  • Figure 7 represents the results of comparative example 3.
  • the invention concerns a sorbent under the form of a lime- based composition for the cleaning of waste gases charged with gaseous heavy metal, especially mercury, comprising :
  • a calcium-magnesium compound being a support for instance calcium-magnesium compound at least formed with slaked lime, slaked dolomitic lime, magnesium slaked lime, but which may also comprise calcium or magnesium carbonates or oxides
  • a support for instance calcium-magnesium compound at least formed with slaked lime, slaked dolomitic lime, magnesium slaked lime, but which may also comprise calcium or magnesium carbonates or oxides
  • a metal salt such as salts of titanium, vanadium, manganese, iron, nickel, copper, zinc, and their mixture and preferably copper chloride
  • a sulfur-containing compound such as sulfide salts, dithiocarbamates, sulfate salts, polymer-based dithiocarbamate, po!ysulfide salts and their mixture; preferably calcium sulfide, calcium polysulfide, calcium sulfate and their mixture and more preferably calcium polysulfide).
  • a doping agent such as alkali metal halides, alkali earth metal halides, ammonium halides and their mixtures, preferably sodium, potassium, calcium or magnesium halides
  • a doping agent can be added either to the spray dried lime-based composition or to the calcium-magnesium polysulfide solution, preferably to the calcium-magnesium polysulfide solution.
  • a dispersant can be mixed with the suspension of calcium-magnesium compound fitting the formula aCaC0 3 .bMgC0 3 .xCa0.yMg0.zCa(OH)2.tMg(OH)2.ul (such as (poly)sulfates, (poly)sulfonates, (poly)phosphates, (poly)phosphonates, polyols, and their mixtures, preferably diethylenetriamine-penta(methylene phosphonic acid) (DTPMP)or sodium docecyl sulfate).
  • DTPMP diethylenetriamine-penta(methylene phosphonic acid)
  • the sorbent is a powder in particular synthetized through spray drying and is notably composed of spherical particles exhibiting a core-shell structure wherein the calcium-magnesium compound making the support is the core and wherein the metal salt and sulfur-compound compose the shell.
  • the particle size distribution of this sorbent shown in Figure 1 is preferably as follows: ⁇ , with d 5 o equal to 5 m.
  • a calcium polysulfide solution is prepared separately.
  • This chemical compound has been well known for a number of years. Its production requires a basic mix of lime and elemental sulfur, both being dissolved in boiling water (80 e C-100°C), stirred at 300 rpm for 2 hours. The ratios between lime and sulfur can vary (from 1:1 w/w to 1:2). Additional chemicals can be used as well (polyphosphonate for example). For this step process, any hydrated lime or quicklime can be used (standard hydrated lime or with high surface area and/or high pore volume).
  • Copper chloride is dissolved in water with ammonia (1:3 to 1:6 w/w) to form copper ammonia complex, stable at high pH.
  • This solution is then mixed with a milk of lime (aqueous suspension of hydrated lime in water) for several hours to ensure complete dispersion of copper on the lime particles.
  • fine milk of lime meaning with a particle size distribution with a di 0 between 0,5 and 1,5 ⁇ ; a dso between 2 and 4 ⁇ and a d 90 between 5 and 10 ⁇
  • Calcium polysulfide solution was synthetized using the aforementioned process proposed with a lime/sulfur ratio of 1:1,5 w/w until the water was completely saturated with polysulfide.
  • the sulfur powder (99%) has been bought from VWR Chemicals. The solution was then filtered.
  • the spray drier was the Atomizer Model MOBILE MINOR, from the Brand GEA.
  • the tank has about a 500 dm 3 capacity, the air pressure can vary between from approximately 0 to 5,5 bar.
  • the injection rate depends on the peristaltic pump used.
  • the spray drier parameters were as follows:
  • Carbon-sulfur analysis of this product (performed on an Eltra CS 2000 using the prescription of the manufacturer with a high temperature furnace at 1450°C, using 100 mg of product 1 + 100 mg of iron phosphate to enhance the combustion) showed a total sulfur content of 11%, which was close to our expectation (11-14%).
  • Figure 2 gives a schematic representation of the mercury bench used to evaluate sorbents performances.
  • the mercury bench 1 used and illustrated in Figure 2 is composed of a few devices connected together. An exhaustive list is given below:
  • -Mercury and flue gas generator (illustrated under number 2) is the bench's central equipment designed to regulate the flow of gases 3, 4, 5, 6 (respectively N 2 , 0 2 , HCI and S0 2 ). It also controls the mercury solution 7 (aqueous solution of diluted HgCI 2 in HCI) flow to the evaporator 8 with a peristaltic pump.
  • -Evaporator 8 is an essential device and the start of the circuit, designed to turn the liquid mercury solution 7 into vapor in the gas flow composed at this point of N 2 (illustrated under number 3) and 0 2 (illustrated under number 4).
  • -Mercury reducing unit 9, 9' is a piece of equipment similar to the evaporator 8, filled with catalyst material to reduce ionic mercury into metallic mercury.
  • the oven (not illustrated) is the reactor 10 heating unit.
  • the temperature inside the reactor 10 is set around 180°C.
  • -Reactor 10 is a metallic cylinder of low width. It is plugged to a T connection allowing access to the gas flow and a thermocouple for a precise recording of the temperature inside the reactor 10. It is completed by a 2 ⁇ metallic filter located at the exit of the reactor 10.
  • -Bypass 11 is located between the central valves. It helps stabilizing the metallic and ionic mercury levels before the test begins.
  • Coolers are dedicated to the elimination of water in the gas flow which is a mandatory operation due to the analyzers 13 sensibility to water. Their temperature is set to 1°C.
  • -Flow meters 14 are devices used to measure and control the gas flow. Their function is to make sure that the flow is equally divided between the 2 lines.
  • -Mercury Analyzers are the analyzers (one on each line) for detecting metallic mercury only in the gas flow after the flow meters.
  • the first one (main line, equipped with Mercury reducing unit 9') shows the concentration of total mercury (as ionic mercury has been reduced just before).
  • the second one shows the concentration of metallic mercury only, which leads to the concentration of ionic mercury by simple subtraction.
  • the mercury bench was used to measure the mercury removal according to the following experimental procedure:
  • the tested sorbent is first mixed with purified sand (washed with HCI, triple rincing with deionized water, size between 125 ⁇ and 250 ⁇ ) and poured into a fixed bed cylindrical reactor. Then a flue gas having the following composition is injected at a total flow rate of 5.8x 10 s Nm 3 /s so as to cross this bed:
  • the test starts with a 10-minutes stabilization period, then the gas is redirected through the reactor and the test begins. It ends when the total mercury level ("Hg tot" in figures 3 to 7) is back to its baseline.
  • Calcium polysulfide solution was synthetized using the aforementioned process proposed with a lime/sulfur ratio of 1:1,5 w/w until the water was completely saturated with polysulfide.
  • the sulfur powder (99%) has been bought from VWR Chemicals. The solution was then filtered.
  • the mercury uptake value was found to be 8000 Mg/g. About 95% of total mercury was removed during 70 minutes, after a 1-hour period of stabilization.
  • Comparative example 3 About 625 g of Ludox HS-40 (colloidal silica available from Ludox HS-40 (colloidal silica available from Ludox HS-40 (colloidal silica available from Ludox HS-40).
  • Calcium polysulfide solution was synthetized using the process proposed with a lime/sulfur ratio of 1:1,5 w/w until the water was completely saturated with polysulfide. The solution was then filtered.
  • the mercury uptake value was found to be 500 ⁇ xg/g. About 93

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne une composition de sorbant contenant des particules à noyau et enveloppe pour l'élimination de métaux lourds, en particulier, le mercure à partir de gaz, le noyau comprenant un composé à base de magnésium et de calcium de formule aCaC03.bMgC03.xCa0.yMg0.zCa(OH)2.tMg(OH)2.ul, dans laquelle I représente des impuretés, a, b, x, y, z et t étant chacun des fractions de masse ≥ 0 et ≤ 100 %, u étant une fraction de masse ≥ 0 et ≤ 20 % en poids, et étant revêtu d'une enveloppe présentant une épaisseur comprise dans la plage allant de 50 nm à 20 µm, et comprenant au moins un sel métallique et un composé à base de soufre, ainsi que son procédé de fabrication.
PCT/EP2015/061147 2015-05-20 2015-05-20 Composition de sorbant à base de chaux pour l'élimination du mercure et procédé de fabrication associé WO2016184518A1 (fr)

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PCT/EP2015/061147 WO2016184518A1 (fr) 2015-05-20 2015-05-20 Composition de sorbant à base de chaux pour l'élimination du mercure et procédé de fabrication associé
FR1654552A FR3036293A1 (fr) 2015-05-20 2016-05-20
BE2016/5369A BE1023752B1 (fr) 2015-05-20 2016-05-20 Composition de sorbant à base de chaux pour l'élimination de mercure et son procédé de fabrication
PCT/EP2016/061480 WO2016185033A1 (fr) 2015-05-20 2016-05-20 Composition de sorbant à base de chaux pour l'élimination du mercure et son procédé de fabrication

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CN107265546A (zh) * 2017-06-28 2017-10-20 北京锐安科技有限公司 含重金属离子废水的处理方法
AU2020256256A1 (en) 2019-04-03 2021-11-11 Calgon Carbon Corporation Perfluoroalkyl and polyfluoroalkyl sorbent materials and methods of use
CN110975797A (zh) * 2019-12-17 2020-04-10 广州秦安农业科技有限公司 一种基于铁基泥质灰岩的汞深度处理材料及其制备方法与应用
CA3189498A1 (fr) 2020-08-31 2022-03-03 Jason P. Mazzoccoli Sorbant traite au cuivre et a l'azote et procede pour le fabriquer

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BE1023752A1 (fr) 2017-07-11
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FR3036293A1 (fr) 2016-11-25

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