CN110997129A - Adsorbent composition for electrostatic precipitator - Google Patents

Adsorbent composition for electrostatic precipitator Download PDF

Info

Publication number
CN110997129A
CN110997129A CN201880049441.7A CN201880049441A CN110997129A CN 110997129 A CN110997129 A CN 110997129A CN 201880049441 A CN201880049441 A CN 201880049441A CN 110997129 A CN110997129 A CN 110997129A
Authority
CN
China
Prior art keywords
calcium
sorbent composition
powdered
metal ion
flue gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201880049441.7A
Other languages
Chinese (zh)
Inventor
罗德尼·傅
格雷戈里·马丁·菲利佩利
约翰·海斯沃尔夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lhoist Recherche et Developpement SA
Original Assignee
Lhoist Recherche et Developpement SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US15/657,294 external-priority patent/US10898876B2/en
Application filed by Lhoist Recherche et Developpement SA filed Critical Lhoist Recherche et Developpement SA
Publication of CN110997129A publication Critical patent/CN110997129A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/83—Solid phase processes with moving reactants
    • 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
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • 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
    • B01J20/0203—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
    • B01J20/0274—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 characterised by the type of anion
    • B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/01—Pretreatment of the gases prior to electrostatic precipitation
    • B03C3/013—Conditioning by chemical additives, e.g. with SO3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/11—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1122—Metals
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Abstract

Disclosed is a powdery calcium-magnesium compound; a calcium magnesium based sorbent composition for flue gas treatment and compatible with electrostatic precipitators; and a method for reducing the resistivity of a powdered sorbent composition in a flue gas treatment device comprising an electrostatic precipitator.

Description

Adsorbent composition for electrostatic precipitator
Technical Field
The present invention relates to a calcium-magnesium compound and a sorbent composition for use in a flue gas plant equipped with an electrostatic precipitator, a method for obtaining such a sorbent composition and a method of treating flue gas using an electrostatic precipitator, the method of treating flue gas comprising the step of injecting such a sorbent composition. In another aspect, the invention relates to a flue gas treatment plant using the sorbent composition according to the invention.
Background
Combustion of fuel in industrial processes or energy production produces fly ash and acid gases, and the release of these into the atmosphere must be minimized. Fly ash can be removed from flue gas streams by electrostatic precipitators (ESP). Some examples of electrostatic precipitators are disclosed in U.S. Pat. No. 4,502,872, U.S. Pat. No. 8,328,902 or U.S. Pat. No. 6,797,035. Electrostatic precipitators typically include a housing having a flue gas inlet and a flue gas outlet, the housing containing a plurality of collecting and discharge electrodes spaced apart from one another and a plurality of hoppers located below a collecting plate. A voltage is applied between the discharge electrode and the collecting electrode to generate an electrostatic field that charges the particulate material in the flue gas, thereby obtaining a charged particulate material. The charged particulate material is collected by the dust collecting electrode. The electrostatic precipitator further comprises a rapper which provides mechanical impact or vibration to the collecting electrode to dislodge collected particles from the collecting electrode. The collected particles fall into a hopper provided at the bottom of the housing, and the hopper is periodically or continuously emptied. The collecting electrodes may be planar or may be in the form of a tubular or honeycomb structure, while the discharge electrodes are typically in the form of wires or rods.
Typically, flue gas treatment plants comprising an electrostatic precipitator are provided with an air preheater, wherein the air preheater is sometimes included in the boiler and/or provided as an additional element of the flue gas plant. The air preheater includes a heat exchanger for using heat from a flue gas stream produced by the boiler to heat the boiler combustion air, thereby increasing the thermal efficiency of the boiler. In some embodiments, the flue gas treatment comprises a plurality of electrostatic precipitators. The cold-side electrostatic precipitator is located downstream of the air preheater and therefore operates at a lower temperature, typically below 200 c (392F). The hot side electrostatic precipitator is located upstream of the air preheater and operates at a higher temperature, typically above 250 ℃ (482 ° F).
With existing facilities, electrostatic precipitator units have sometimes been operated at the limits of their design capabilities due to the introduction of stricter particulate matter emission limits and/or changes in the operating conditions of the facility (e.g., refueling) over the years.
The doi-Anderson (Deutsch-Anderson) equation summarizes approximately the collection efficiency of an electrostatic precipitator:
Figure BDA0002378141220000021
wherein η is the dust collecting efficiency in fractional representation, AcIs the area of the dust collecting electrode, VpmIs the particle movement velocity and Q is the volumetric flow rate of the gas. The properties of the particles that affect the dust collection efficiency are mainly the particle size distribution and its resistivity. The resistivity of the particles affects the velocity of particle movement as described in the Deutsch-Anderson equation.
Various attempts have been made to reduce the resistivity of the particles. Such as known from us patent 4,439,351That is, for the electrostatic precipitator to operate effectively, the resistivity of fly ash must be 1E7 (1X 10)7) Ohm cm to 2E10 (2X 10)10) In ohm cm. Another document, "Mastropietro, R.A. impact of Hydrated LimeInjecton electric Perform in ASTM Symposium on LimeUtilization"; 2012; pp 2-10 "states that fly ash resistivity should be 1E8(1 × 10)8) Ohm cm to 1E11 (1X 10)11) In ohm cm. However, fly ash is generally higher in resistivity and chemical additives, such as SO, are used3、HCl、NH3、Na2CO3、Na2SO4And NH (CH)2CH2OH) to reduce the resistivity of the fly ash. However, those additives are prone to release undesirable compounds. The same document discloses the use of polymers to reduce the resistivity of fly ash. However, polymer additives typically degrade at high temperatures and therefore must be injected into the flue gas stream at low temperatures.
Document us patent 6,126,910 discloses the use of an electrostatic precipitator for removing acid gases from flue gases by spraying a solution of sodium bisulfite, calcium bisulfite, magnesium bisulfite, potassium bisulfite or ammonium bisulfite, or a combination thereof, into the gas stream upstream of the electrostatic precipitator unit. The bisulfite selectively removes acid gases such as HCl, HF, and SO3But not sulfur dioxide. Reagents such as hydrated lime must then be used to remove sulfur dioxide from the flue gas. Document US6,803,025 discloses a similar process wherein acidic gases such as HCl, HF, SO in flue gas are removed using a reaction compound selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonium hydroxide, potassium carbonate and potassium bicarbonate3And part of SO2. However, the remaining SO2It must still be removed by using another reagent, such as hydrated lime. For the treatment of flue gases released by power plants, the amount of chloride released by burning fuel or coal is typically relative to SO2Is very low and, therefore, the flue gas treatment process can be simplifiedTo use hydrated lime only as the sorbent.
Document WO2015/119880 relates to the disadvantage that for flue gas treatment with an electrostatic precipitator unit, natural ore (trona) or hydrated lime is used as sorbent. Sodium-based sorbents are known to reduce the resistivity of particulate matter, however, the main disadvantage of using sodium sorbents is the increase in heavy metals leached from the fly ash, leading to potential environmental pollution. Calcium hydroxide-based sorbents do not present the problem of leaching of heavy metals from fly ash, but they are known to increase the resistivity of particulate matter (fly ash) entrained in the flue gas stream, such that when calcium-based sorbents are used, the efficiency of the electrostatic precipitator unit may be reduced. This same document discloses a composition for reducing the resistivity of particles in flue gases and capturing acid gases, wherein the composition comprises a composition having the formula (Li)1-α-βNaαKβ)w(Mg1-δCaδ)x(OH)y(CO3)z·nH2O, more specifically of the formula NawCax(OH)y(CO3)z·nH2Alkali/alkaline earth metal particles of O, wherein the ratio of W to x is from about 1/3 to about 3/1. Thus, the composition still presents a large amount of sodium, which not only may leach the sodium itself, but sodium is also known to increase leaching of heavy metals contained in the fly ash.
US6,797,035 discloses a method of reducing the resistivity of fly ash by spraying an aqueous solution of potassium nitrate or potassium nitrite into the flue gas stream, or by injecting a powder of potassium nitrate or potassium nitrite into a duct through which the flue gas flows. The disadvantage of using these nitrate or nitrite powders is that they react with other substances than fly ash and cause less reactive chemicals to reach the electrostatic precipitator dust collection plates. It is therefore suggested to inject these nitrates as a finely sieved powder to reduce the exposed reaction surface area and inhibit reaction with nitrogen oxides and sulfur oxides.
US7,744,678B 2 discloses a process wherein the addition of 0.2 wt% to 3.5 wt% of an alkali metal species (including sodium) to a calcium hydroxide sorbent provides a counter-currentSO2Improved reactivity of capture. The addition of alkali metal species is maintained up to 30 < SSA < 40 (m) with BET Specific Surface Area (SSA) obtained by nitrogen adsorption2In g) is carried out.
Combinations of sodium salts and hydrated lime in concentrations beyond those mentioned in US7,744,678B 2 are undesirable because there are three adverse effects: (1) an increase in sodium content will result in an increase in leaching of heavy metals from fly ash residue, (2) such a reaction occurs in hydrated lime mixtures of sodium salts: this reaction takes place in the presence of water to form sodium hydroxide, thus raising the pH of the mixture above pH 12.5, causing safety problems, (3) the addition of sodium to hydrated lime in hydrated form reduces the BET specific surface area of hydrated lime, thereby reducing reactivity to acid gases.
Foo et al, 2016, 16/19, at Power plant contaminant control and carbon management, "MEGA" symposium for Baltimore, MD, and proposed the use of enhanced hydrated lime sorbents for SO removal in cold-side electrostatic precipitators2Successful industrial application of the method. With CaSO4Laboratory resistivity measurements were made on fly ash and hydrated lime and enhanced hydrated lime mixtures with CaSO added4To simulate typical fly ash residues. The enhanced hydrated lime of this document has a height of more than 40m2Surface area per gram, greater than 0.2cm3Pore volume per gram, and median particle diameter d between 6 and 12 microns50And an acceptable maximum resistivity of 1E11 (1X 10) has been found to exist11) Ohm cm.
However, there is still a need to provide calcium magnesium compounds: which can be advantageously used in flue gas treatment plants that are highly compatible with electrostatic precipitators.
It is an object of the present invention to provide calcium-magnesium compounds and sorbent compositions comprising said calcium-magnesium compounds which eliminate the disadvantages inherent in the use of these sorbents in electrostatic precipitator units.
Disclosure of Invention
According to a first aspect, the invention relates to a calcium-magnesium compound in powder form,the powdery calcium-magnesium compound contains at least: a calcium magnesium carbonate in an amount greater than or equal to 80% by weight, or a calcium magnesium hydroxide in an amount greater than or equal to 80% by weight, relative to the total weight of the powdered calcium magnesium compound; and further, has a molecular weight of less than 1E11 (1X 10) at 300 ℃ (372 DEG F)11) Ohm cm and higher than 1E7 (1X 10)7) Ohm cm, advantageously lower than 1E10 (1X 10)10) Ohm cm and higher than 5E7 (5X 10)7) Ohm cm, preferably below 5E9 (5X 10)9) Ohm cm, more preferably below 1E9 (l.times.10)9) Ohm cm, even more preferably below 5E8 (5X 10)8) Resistivity R in ohm cm300。
Indeed, it was surprisingly observed that the resistivity at 300 ℃ (372 ° F) was still below 1E11(1 × 10)11) Ohm cm, preferably below 1E10 (l.times.10)10) Ohm cm, powdered calcium magnesium compounds can be successfully used in flue gas treatment using electrostatic precipitators, which means that powdered calcium magnesium compounds are robust and do not decompose at relatively high temperatures. Thus, the powdery calcium-magnesium compound can favorably change the resistivity of fly ash without adversely affecting the operation of the electrostatic precipitator.
In fact, if the powdered calcium-magnesium is a calcium-magnesium compound containing at least calcium-magnesium carbonate in a content greater than or equal to 80% by weight, preferably greater than or equal to 82% by weight, more preferably greater than or equal to 85% by weight, advantageously greater than or equal to 88% by weight, with respect to the total weight of the powdered calcium-magnesium compound, the powdered calcium-magnesium compound is preferably injected at a location close to the boiler or even in the boiler, i.e. where it is intended to inject the powdered calcium-magnesium compound into the flue gas stream, at a temperature that favours a suitable capture of polluting compounds of the flue gas by a high carbonate content. In this case, since the product does not decompose, its resistivity at a temperature of 300 ℃ (372 ° F) is still low enough to change the resistivity of the mixture of fly ash and injected calcium magnesium compounds present in the flue gas.
Within the meaning of the present invention, the term "calcium-magnesium compound having a calcium-magnesium carbonate content greater than or equal to 80% by weight, preferably greater than or equal to 82% by weight, more preferably greater than or equal to 85% by weight, advantageously greater than or equal to 88% by weight, relative to the total weight of the powdered calcium-magnesium compound" means a natural calcium and/or magnesium carbonate, such as dolomite, limestone, or even precipitated calcium and/or magnesium carbonate.
The molar ratio of calcium to magnesium in dolomite may vary between 0.8 and 1.2. The calcium to magnesium ratio in the calcium magnesium compound may also be higher or lower, up to 0.01 to 10 or even 100. In fact, natural limestone contains magnesium carbonate in a content that can vary between 1% and 10% by weight with respect to the total weight of the powdery calcium-magnesium compound. If the compound in question is magnesium carbonate, its content in calcium carbonate may also vary between 1 and 10 wt.%.
The calcium magnesium compound may also contain impurities. The impurities include in particular all the impurities present in natural limestone and dolomite, such as clays of the aluminosilicate type, silica, impurities based on iron or manganese.
In fact, if the powdered calcium-magnesium compound is a calcium-magnesium compound having a calcium-magnesium hydroxide content at least greater than or equal to 80% by weight, preferably greater than or equal to 82% by weight, more preferably greater than or equal to 85% by weight, advantageously greater than or equal to 88% by weight, with respect to the total weight of the powdered calcium-magnesium compound, it is preferable to inject the calcium-magnesium compound close to the upstream of the preheater, since in the position of the flue gas stream where the calcium-magnesium compound is to be injected inside it, the temperature favours a suitable capture of the polluting compounds of the flue gas by a high hydroxide content. In this case, since the product does not decompose, its resistivity at a temperature of 300 ℃ (372 ° F) is still low enough to change the resistivity of the mixture of fly ash and injected calcium magnesium compounds present in the flue gas.
The term "calcium-magnesium compound having a calcium-magnesium hydroxide content greater than or equal to 80% by weight, preferably greater than or equal to 82% by weight, more preferably greater than or equal to 85% by weight, advantageously greater than or equal to 88% by weight, relative to the total weight of the powdered calcium-magnesium compound" is within the meaning of the present invention. Thus, the at least one calcium-magnesium compound according to the invention is formed at least by (calcareous) slaked lime, dolomitic lime (or dolomite), magnesium slaked lime.
The molar ratio of calcium to magnesium in dolomite (also known as muscovite mica) may vary between 0.8 and 1.2. The calcium to magnesium ratio in the calcium magnesium compound may also be higher or lower, up to 0.01 to 10 or even 100. In fact, natural limestone contains magnesium carbonate in a content that can vary between 1% and 10% by weight with respect to the total weight of the powdery calcium-magnesium compound. In practice, the natural limestone is roasted to form quicklime, which is then further slaked to provide hydrated lime comprising magnesium carbonate in an amount which may vary between 1 and 10 wt%. If the compound in question is baked to form magnesium oxide and the magnesium oxide is to be further ripened to provide magnesium carbonate of magnesium hydroxide, its content in the calcium carbonate may also vary between 1 wt% and 10 wt%. It must be noted that a part of the magnesium oxide may not yet be aged.
The calcium magnesium compound may also contain impurities. The impurities include in particular all the impurities present in natural limestone and dolomite, such as clays of the aluminosilicate type, silica, impurities based on iron or manganese.
CaCO in calcium-magnesium compounds3、MgCO3、Ca(OH)2And Mg (OH)2The content can be easily determined using a conventional method. For example, they can be analyzed by X-fluorescence in combination with loss-on-ignition measurements and CO according to EN 459-2:2010E standard2Volume measurements, wherein the procedure of the X-fluorescence analysis is described in standard EN 15309.
Preferably, the calcium-magnesium compound according to the invention has a structure of less than 5E11 (5X 10)11) Ohm cm, preferably below 1E11 (1X 10)11) Ohm cm and more preferably below 5E10 (5X 10)10) Maximum resistivity R in ohm cmmax。
Advantageously, the calcium-magnesium compound is doped with at least one metal ion M selected from the group of metal ions having an atomic number less than or equal to 74 and belonging to the transition metal ions or post-transition metal ions, in an amount greater than or equal to 0.05% by weight and less than or equal to 5% by weight, relative to the total weight of the powdered calcium-magnesium compound.
In a particular embodiment, the calcium-magnesium compound according to the invention is further doped with at least one counterion X selected from the group consisting of nitrate, nitrite and mixtures thereof, in an amount greater than or equal to 0.05% and less than or equal to 5% by weight relative to the total weight of the powdered calcium-magnesium compound.
In a preferred embodiment of the calcium-magnesium compound according to the invention, the total weight of the metal ion and the counter ion is greater than or equal to 0.1% by weight and less than or equal to 5% by weight, preferably between 0.3% and 3% by weight, relative to the total weight of the powdered calcium-magnesium compound.
In yet another preferred embodiment, the calcium-magnesium compound of the invention further comprises sodium in an amount of up to 3.5 wt% expressed as sodium equivalent relative to the total weight of the powdered calcium-magnesium compound. Preferably, sodium is in a minimum amount of 0.2 wt% relative to the total weight of the powdered calcium-magnesium compound and expressed as sodium equivalents.
As set forth in the aforementioned Foo et al (2016) document, it is known that this amount of sodium in the sodium additive form has a slight effect on the decrease in the resistivity of the adsorbent. Applicants have found that such an amount of sodium additive in combination with the presence of at least one metal ion and/or counter ion as described below further has an additional effect on reducing the resistivity of the sorbent composition. The use of a sodium additive in combination with the presence of at least one metal ion and/or counterion described below reduces the resistivity of the sorbent composition more than when the presence of at least one metal ion and/or counterion described below is used alone in the calcium magnesium compound and when sodium is used alone in the calcium magnesium compound.
In an advantageous embodiment of the calcium-magnesium compound, the metal ion M is Cu2+、Fe2+、Fe3+、Mn2+、Co2+、Mo2 +、Ni2+、Zn2+An ion of (1).
Preferably, the metal ion M is Cu2+、Fe2+、Fe3+An ion of (1).
Preferably, the counterion X is nitrate.
It has been found that the presence of metal ions as disclosed above and/or counter ions as described hereinbefore in the calcium magnesium compound reduces the resistivity of the calcium magnesium compound.
In a preferred embodiment, the powdered calcium magnesium comprises d50Particles between 5 μm and 25 μm, preferably between 5 μm and 20 μm, more preferably between 5 μm and 16 μm.
Symbol dxRepresents the diameter, expressed in μm, measured by laser granulometry, optionally after sonication in methanol, relative to which X% by mass of the particles are smaller than or equal to this diameter.
Preferably, the calcium-magnesium compound according to the invention has a calcium-magnesium content of at least 20m, in particular if the powdered calcium-magnesium compound is a calcium-magnesium compound comprising at least a calcium-magnesium hydroxide content of greater than or equal to 80 wt. -%2A/g, preferably of at least 25m2A/g, preferably at least 30m2Per g, more preferably at least 35m2BET specific surface area in g. BET surface areas were determined by nitrogen adsorption manometry after degassing in vacuo at 190 ℃ (374 ° F) for at least 2 hours as described in ISO 9277/2010E standard and calculated according to the multipoint BET method.
Preferably, the sorbent composition according to the invention has at least 0.1cm, in particular if the powdered calcium-magnesium compound is a calcium-magnesium compound comprising at least a calcium-magnesium hydroxide content greater than or equal to 80% by weight3In g, preferably at least 0.15cm3In g, preferably at least 0.17cm3In g, more preferably at least 0.2cm3BJH pore volume per g. BJH pore volume was determined by nitrogen desorption pressure measurement after degassing in vacuo at 190 ℃ (374 ° F) for at least 2 hours as described in ISO 9277/2010E standard and calculated according to BJH method.
Further embodiments of the calcium-magnesium compound according to the invention are mentioned in the appended claims.
According to a second aspect, the invention also relates to a sorbent composition for a flue gas treatment plant comprising an electrostatic precipitator, the sorbent composition comprising said calcium-magnesium compound according to the invention.
Preferably, the sorbent composition according to the invention further comprises activated carbon; lignite coke; halloysite; sepiolite; clays, such as bentonite, kaolin; vermiculite; or any other sorbent such as fireclay, aerated cement dust, perlite, expanded clay, lime sandstone dust, volcanic ash, sub-riellite dust, volcanic lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulfide, organosulfides, calcium sulfate, open hearth coke, lignite dust, fly ash, or water glass.
In a preferred embodiment, the sorbent composition according to the invention comprises a sodium-containing sodium additive added in an amount of at most 3.5 wt.%, expressed as sodium equivalents, relative to the total weight of the powdered calcium-magnesium compound. In particular, the amount of sodium in the composition will be higher than 0.2 wt% relative to the total weight of the powdered sorbent composition.
In a preferred embodiment, the sorbent composition according to the invention comprises: the metal ion M and/or the counter ion X are present in an amount greater than or equal to 0.05% and less than or equal to 5% by weight relative to the total weight of the powdered calcium-magnesium compound, and wherein preferably the total weight of the metal ion and the counter ion is greater than or equal to 0.1% and less than or equal to 5% by weight, preferably between 0.3% and 3% by weight relative to the total weight of the dry sorbent composition.
In a particular embodiment according to the invention, the sorbent composition comprises water in an amount such that the sorbent composition is in the form of a suspension. An exemplary amount may be 40 wt% to 90 wt% water, wherein the amount of adsorbent is 10 wt% to 60 wt% relative to the total weight of the adsorbent composition in suspension form.
The sorbent composition in the form of a suspension may be used, for example, in a spray dry absorber (spray dry absorber), which may be followed by an electrostatic precipitator.
In a particularly preferred embodiment, the calcium magnesium compound is hydrated lime. In this case, if the sorbent composition is in the form of a suspension, the calcium-magnesium compound will be in the form of milk of lime, wherein the solids content will be between 10% and 50% by weight relative to the total weight of the milk of lime.
Further embodiments of the sorbent composition according to the invention are mentioned in the appended claims.
According to a third aspect, the present invention relates to a method of preparing a sorbent composition for use in a flue gas treatment plant comprising an electrostatic precipitator, the method comprising the steps of:
a) providing a calcium magnesium compound to a reactor;
b) to an additive or mixture of additives comprising at least one metal ion M and/or counterion X in a calculated amount to give 0.1 to 5 wt%, preferably 0.3 to 3 wt%, of said metal ion M and/or counterion X relative to the total weight of the sorbent composition; wherein M is a metal ion having an atomic number of 74 or less and belonging to the transition metal ion or late transition metal ion, and X is nitrate, nitrite, oxygen ion (O)2-) Hydroxyl (OH)-) And mixtures thereof.
Alternatively, the present invention relates to a method of preparing a sorbent composition for use in a flue gas treatment plant comprising an electrostatic precipitator, the method comprising the steps of:
a) providing a calcium magnesium compound to a reactor;
b) to an additive or mixture of additives comprising at least one metal ion M and/or counterion X in a calculated amount to give said metal ion M and/or counterion X in an amount of 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the weight of the calcium-magnesium compound; wherein M is a metal ion having an atomic number of 74 or less and belonging to the transition metal ion or late transition metal ion, and X is nitrate, nitrite, oxygen ion (O)2-) Hydroxyl (OH)-) To do so byAnd mixtures thereof.
In a preferred embodiment, the sorbent composition comprises d50Particles between 5 μm and 25 μm, preferably between 5 μm and 20 μm, more preferably between 5 μm and 16 μm.
In a preferred embodiment of the process according to the invention, the calcium-magnesium compound comprises at least a calcium-magnesium carbonate in a content greater than or equal to 80% by weight, relative to the total weight of the dry calcium-magnesium compound.
In another preferred embodiment of the process according to the invention, the calcium-magnesium compound comprises a calcium-magnesium hydroxide in a content greater than or equal to 80% by weight, relative to the total weight of the dry calcium-magnesium compound.
Preferably, in the method of preparing the adsorbent composition, the metal ion M is Cu2+、Fe2+、Fe3+、Mn2 +、Co2+、Mo2+、Ni2+、Zn2+An ion of (1). More preferably, in the method for preparing the adsorbent composition, the metal ion M is Cu2+、Fe2+、Fe3+An ion of (1).
Preferably, in the method of making the sorbent composition, the counterion X is nitrate.
Preferably, the process for preparing the sorbent composition comprises the step of adding an additional additive comprising sodium in sodium equivalent amounts calculated to give up to 3.5% sodium by weight of the dry sorbent composition.
In an embodiment of the production method according to the present invention, the step of supplying the calcium-magnesium compound to the reactor comprises the steps of: providing quicklime to the reactor; slaking the quicklime with a predetermined amount of water to obtain the calcium-magnesium compound having at least a calcium hydroxide content of 80 wt% or more with respect to the total weight of the dried calcium-magnesium compound having a predetermined amount of moisture.
More advantageously, said slaking step is carried out under conditions such as to obtain hydrated limeThe hydrated lime has a BET specific surface area of at least 20m as measured by nitrogen adsorption2A/g, preferably of at least 25m2A/g, preferably at least 30m2Per g, more preferably at least 35m2/g。
In another preferred embodiment, said slaking step is carried out under conditions such as to obtain hydrated lime having a diameter less than or equal to that of
Figure BDA0002378141220000111
The BJH pore volume measured by nitrogen desorption method is at least 0.1cm3/g、0.15cm3In g, preferably at least 0.17cm3In g, more preferably at least 0.2cm3/g。
Preferably, the maturation step is carried out under the same conditions as described in applicant's U.S. patent 6,322,769, which is incorporated by reference.
In an alternative embodiment of the preparation process according to the invention, the maturing step is carried out under the same conditions as described in the applicant's us patent 7,744,678, which is incorporated herein by reference.
In an embodiment of the method for preparing a sorbent according to the invention, the step of adding an additive or a mixture of additives comprising at least one metal ion M and/or counter ion X is carried out before the step of slaking the quicklime.
In another embodiment of the process for preparing the sorbent composition, the step of adding an additive or a mixture of additives comprising at least one metal ion M and/or counterion X is carried out during the step of slaking the quicklime.
Alternatively, in the process for preparing the sorbent composition, the step of adding an additive or a mixture of additives comprising at least one metal ion M and/or counterion X is carried out after the step of slaking quick lime.
The applicant has found that the addition of an additive or a mixture of additives comprising at least one metal ion M and/or a counter ion X is carried out during or after said maturing stepDoes not substantially change the surface area of, for example, a calcium magnesium compound as an adsorbent, and does not substantially change its pore volume. In particular, the specific surface area and pore volume of the sorbent compositions according to the invention are substantially the same as those of calcium hydroxide sorbents prepared by methods such as those described in U.S. Pat. nos. 6,322,769 and 7,744,678, which are incorporated herein by reference. Thus, ensuring SO is preserved2Adsorbent properties to remove efficiency.
Preferably, the preparation method is characterized in that the method further comprises: preferably, the step of adding activated carbon, lignite coke, halloysite, sepiolite, clay, bentonite, kaolin, vermiculite, fire clay, aerated cement dust, perlite, expanded clay, lime sandstone dust, volcanic ash, halite dust, pozzolanic lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulfide, organosulfides, calcium sulfate, hearth coke, lignite powder, fly ash or water glass after the aging step.
Further embodiments of the method for preparing the sorbent composition according to the invention are mentioned in the appended claims.
In a fourth aspect, the present invention relates to a flue gas treatment process using an apparatus comprising an injection zone arranged upstream of an electrostatic precipitator, characterized in that the flue gas treatment process comprises the step of injecting a sorbent composition according to the invention in said injection zone.
More specifically, the flue gas treatment process with an apparatus is characterized in that it comprises a step of injecting in the injection zone a sorbent composition comprising a calcium-magnesium sorbent, at least one metal ion M, and optionally at least one counter ion X, wherein the apparatus comprises an electrostatic precipitator and an injection zone arranged upstream of the electrostatic precipitator and through which the flue gas flows towards the electrostatic precipitator, the at least one metal ion M having an atomic number less than or equal to 74 and being a transition metal ion or a post-transition metal ion, the at least one counter ion X being selected from nitrate, nitrite, and mixtures thereof, the total amount of the at least one metal ion M and the optional at least one counter ion X being between 0.1 and 5 wt% of the weight of the dry composition, preferably between 0.3 wt% and 3.5 wt%.
According to the invention, the sorbent composition has a lower electrical resistivity than prior art calcium-magnesium sorbents, particularly at temperatures of 300 ℃ (372 ° F). The sorbent composition of the invention injected in the injection zone to mix with the flue gas is effective in removing SO2And other gaseous acids, and the lower resistivity of such sorbent compositions improves the collection of particulate matter on the collecting electrodes of electrostatic precipitators.
In a preferred embodiment of the method according to the invention, the sorbent composition comprises at least calcium magnesium carbonate as calcium magnesium compound and the sorbent composition is injected into the injection zone, wherein the temperature of the flue gas is greater than or equal to 850 ℃ (1562 ° F).
In another preferred embodiment of the method according to the invention, the sorbent composition comprises at least calcium magnesium hydroxide as calcium magnesium compound and is injected into the injection zone, wherein the temperature of the flue gas is greater than or equal to 180 ℃ (356 ° F), preferably greater than 200 ℃ (392 ° F), more preferably between 300 ℃ (372 ° F) and 425 ℃ (797 ° F).
Preferably, in the flue gas treatment method according to the invention, the calcium-magnesium compound in the sorbent composition is mixed with an additive or a mixture of additives comprising at least one metal ion M and/or a counter ion X prior to the injecting step.
Alternatively, in the flue gas treatment method according to the invention, a calcium-magnesium compound and an additive or a mixture of additives comprising at least one metal ion M and/or a counter ion X are separately injected into the injection zone and mixed with the flue gas.
When the sorbent composition comprises primarily a carbonate sorbent (typically at temperatures above 850 ℃ (1562 ° F), the sorbent composition can be used in flue gas treatment processes according to the present invention over a wide temperature range, for example, between 100 ℃ (212 ° F) to 425 ℃ (797 ° F) or even higher.
Advantageously, the additive of the sorbent composition according to the invention does not decompose at temperatures above 180 ℃ (356 ° F), so that the sorbent composition can be injected into the injection zone where the temperature is greater than or equal to 180 ℃ (356 ° F), preferably greater than or equal to 300 ℃ (372 ° F). Since the injection zone is located upstream of the air preheater, the temperature of the injection zone ranges from 300 ℃ (372 ° F) to 425 ℃ (797 ° F), preferably from 350 ℃ (662 ° F) to 380 ℃ (716 ° F).
Preferably, in the flue gas treatment method according to the invention, the injection zone is located upstream of an air preheater which itself is located upstream of the electrostatic precipitator.
Preferably, in the flue gas treatment method according to the present invention, the ion M is Cu2+、Fe2+、Fe3+、Mn2+、Co2+、Mo2+、Ni2+、Zn2+An ion of (1).
More preferably, in the flue gas treatment method of the present invention, the ion M is Cu2+、Fe2+、Fe3+An ion of (1).
Preferably, in the flue gas treatment method of the present invention, the counter ion X is nitrate.
Preferably, in the flue gas treatment process of the present invention, the sorbent composition comprises an additional additive comprising sodium in an amount of at most 3.5 wt%, expressed as sodium equivalents, relative to the weight of the dry composition.
Preferably, in the flue gas treatment method of the present invention, the sorbent composition has at least 20m2BET specific surface area in g.
Preferably, in the flue gas treatment method of the present invention, the adsorbent composition has a value of at least 0 obtained by nitrogen desorption.1cm3BJH pore volume per g.
Preferably, in the flue gas treatment process of the present invention, the sorbent composition has a desorption of nitrogen gas of at least 0.15cm3In g, preferably at least 0.17cm3In g, more preferably at least 0.2cm3BJH pore volume per g.
Preferably, in the flue gas treatment method of the present invention, the sorbent composition further comprises activated carbon, lignite coke, halloysite, sepiolite, clay, bentonite, kaolin, vermiculite, fireclay, aerated cement dust, perlite, expanded clay, lime sandstone dust, volcanic ash, sub-ryite dust, volcanic ash lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulfide, organosulfides, calcium sulfate, furnace coke, lignite dust, fly ash, or water glass.
Further embodiments of the flue gas treatment method according to the invention are mentioned in the appended claims.
In a fifth aspect, the present invention relates to a flue gas treatment plant comprising an electrostatic precipitator located downstream of an air preheater, said air preheater being connected to said electrostatic precipitator by a duct, characterized in that the flue gas treatment plant further comprises an injection zone arranged upstream of said air preheater for injecting a sorbent composition according to the invention.
Other embodiments of the flue gas treatment plant according to the invention are mentioned in the appended claims.
Preferably, the flue gas treatment plant or apparatus is used in a plant, in particular a coal or fuel plant, which utilises sulphur or other acid gas precursorsElectric powerFlue gas of a plant.
Preferably, the flue gas treatment apparatus further comprises a reservoir containing the sorbent composition to provide the sorbent composition to the injection zone through a sorbent inlet.
The invention may also be described as a method of reducing the electrical resistivity of a powdered sorbent composition for use in a flue gas treatment plant comprising an electrostatic precipitator to below 1E11 ohm-cm and above 1E07 ohm-cm at 300 ℃, wherein the electrical resistivity of the powdered sorbent composition is measured in an electrical resistivity cell of an oven under an air flow having a humidity of 10%, the powdered sorbent composition comprising a powdered calcium magnesium compound comprising at least calcium magnesium carbonate in an amount of greater than or equal to 80 wt% or calcium magnesium hydroxide in an amount of greater than or equal to 80 wt%, relative to the total weight of the powdered calcium magnesium content, the method comprising the steps of:
a) providing the powdered sorbent composition in a reactor; and
b) adding to said powdered sorbent composition an additive or a mixture of additives comprising at least one metal ion M and/or counterion X in a calculated amount to give 0.1 to 5 wt%, preferably 0.3 to 3 wt% of said metal ion M and/or counterion X relative to the total weight of the dry sorbent composition; wherein M is a metal ion having an atomic number of 74 or less and being a transition metal ion or a late transition metal ion, or Mg2+Or Na+Or Li+X is selected from nitrate radical, nitrite radical, oxygen ion (O)2-) And Hydroxyl (OH)-) And mixtures thereof.
Preferably, the metal ion M is selected from Cu2+、Fe2+、Fe3+、Mn2+、Co2+、Mo2+、Ni2+And Zn2+Group (d) of (a).
Preferably, the counterion X is nitrate.
Preferably, the powdery calcium-magnesium compound has at least 20m as determined by nitrogen adsorption2A/g, preferably of at least 25m2A/g, preferably at least 30m2Per g, more preferably at least 35m2BET specific surface area in g.
Preferably, the powdery calcium-magnesium compound has a particle size of less than or equal to the diameterIn that
Figure BDA0002378141220000151
At least 0.1cm as determined by nitrogen desorption3/g、0.15cm3In g, preferably at least 0.17cm3In g, more preferably at least 0.2cm3BJH pore volume per g.
Preferably, the powdered sorbent composition further comprises activated carbon, lignite coke, halloysite, sepiolite, clay, bentonite, kaolin, vermiculite, fireclay, aerated cement dust, perlite, expanded clay, lime sandstone dust, volcanic ash, crinite dust, pozzolanic lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulfide, organosulfides, calcium sulfate, furnace coke, lignite dust, fly ash, or water glass.
Preferably, the method of reducing the resistivity of the powdered sorbent composition further comprises: a step of adding to the powdered sorbent composition a sodium-containing additive in an amount of at most 3.5 wt.%, expressed as sodium equivalents, relative to the total weight of the powdered sorbent composition.
Preferably, the powdered calcium magnesium compound is hydrated lime.
The invention also relates to the use of a powdered sorbent composition as described herein in a flue gas treatment process using an apparatus comprising an electrostatic precipitator.
Drawings
Fig. 1 shows a schematic embodiment of a flue gas treatment plant for carrying out a flue gas treatment method with a sorbent composition according to the invention.
Detailed Description
According to a first aspect, the present invention relates to a sorbent composition for flue gas treatment equipment comprising an electrostatic precipitator, said sorbent composition comprising a calcium magnesium compound, characterized in that said sorbent composition further comprises an additive or a mixture of additives in an amount of between 0.1% and 5% by weight, preferably between 0.3% and 3% by weight of the dry composition, said additive or mixture of additives comprising at least one metal ion M having an atomic number less than or equal to 74 and being a transition metal ion or a post-transition metal ion, and at least one counterion X selected from nitrate, nitrite, and mixtures thereof.
In a preferred embodiment, the calcium magnesium compound is based on hydrated lime.
The calcium hydroxide adsorbent is produced by reacting (or slaking) calcium oxide, CaO or quicklime with water in a so-called hydrator (also referred to as a slaking unit). Alternatively, the calcium magnesium hydroxide sorbent is made by reacting dolomitic lime (also known as dolomitic lime) or magnesian lime with water in a hydrator. Alternatively, quicklime and dolomitic lime may be mixed together and slaked with water in a hydrator to provide a mixture of calcium hydroxide and calcium magnesium hydroxide. Hereinafter, the method of preparing the sorbent composition will refer to quicklime, but the preparation method is not limited to using quicklime as a starting material, and dolomitic lime or a combination of dolomitic lime and/or magnesitic lime and quicklime may also be used as a starting material.
The method for preparing said sorbent composition according to the invention comprises a step of slaking quick lime with a predetermined amount of water to obtain hydrated lime having a predetermined amount of moisture, characterized in that it comprises a step of adding an amount of additive or mixture of additives such as to obtain 0.1% to 5%, preferably 0.3% to 3.5%, by weight of the dry sorbent composition, of the additive or mixture of additives comprising at least one metal ion M having an atomic number less than or equal to 74 and being a transition metal ion or a post-transition metal ion, and at least one counter ion X selected from nitrate, nitrite, O, and a transition metal ion2-And OH-And mixtures thereof.
In an embodiment of the method of preparing the sorbent composition, the predetermined amount of water is a weight ratio of water to lime of 2:1 or higher in the slaking step.
In an embodiment of the method for preparing the sorbent composition, the amount of water in the slaking step may be adjusted to obtain hydrated lime having a moisture content of less than or equal to 10 wt%, preferably less than or equal to 5 wt%, preferably less than or equal to 2 wt%, more preferably less than or equal to 1 wt%, relative to the total weight of the sorbent composition in the powder state.
In another embodiment, the amount of water in the slaking step may be adjusted to obtain hydrated lime having a moisture content of 5 to 20 wt.%. The amount of water in the slaking step may also be higher in order to obtain hydrated lime having a moisture content higher than 20 wt%, all% expressed with respect to the total weight of the sorbent composition in powder state.
In an embodiment, the slaked lime obtained after the slaking step is dried in a further step.
In an embodiment of the method for preparing a sorbent composition according to the invention, the additive comprising at least one metal ion M and at least one counter ion X is added in the form of an aqueous solution or suspension or powder before or during said step of slaking calcium oxide or calcium magnesium oxide or a combination thereof.
In another embodiment of the process for preparing a sorbent composition according to the invention, the additive or mixture of additives comprising at least one metal ion M and at least one counter ion X is added in the form of an aqueous solution or suspension or powder after the ripening step. The additive or mixture of additives comprising at least one metal ion M and at least one counter ion X is preferably added to the calcium hydroxide or calcium magnesium hydroxide prior to injection into the injection zone of the flue gas treatment plant. Alternatively, the additive or mixture of additives comprising at least one metal ion M and at least one counter ion X is added upstream of the electrostatic precipitator independently of the calcium hydroxide or calcium magnesium hydroxide during injection into the injection zone of the flue gas treatment plant.
Method for preparing adsorbent compositionIn such a way that the hydrated lime obtained has a BET specific surface area, measured by nitrogen adsorption, of at least 20m2Per g and a BJH pore volume obtained by nitrogen desorption of at least 0.1m3A step of slaking quicklime under the condition of/g. One skilled in the art can employ various methods to obtain hydrated lime of this nature, such as disclosed in applicant's U.S. patent 6,322,769 and U.S. patent 7,744,678 and incorporated herein by reference.
In the process for producing the sorbent composition according to the invention, quicklime particles having a particle size distribution of less than 5mm, in particular quicklime particles having a particle size distribution of from 0mm to 2mm, are advantageously used.
Other methods for obtaining hydrated lime with high specific surface area and/or high pore volume can be found, for example, in us patent 5,492,685, in which a certain amount of alcohol (such as methanol or ethanol) is added before and/or during the step of slaking quicklime and removed after drying; in patent DE3620024, sugars are added in the maturation step to increase the specific surface area and glycols or amines are added therein to increase the flowability; in us 5,277,837 and us 5,705,141, additives such as ethylene glycol, diethylene glycol, triethylene glycol, monoethanolamine, diethanolamine, triethanolamine, or combinations thereof are added during the slaking step to increase the surface area of the hydrated lime.
In the process for preparing the adsorbent composition, the additive or mixture of additives comprising at least one metal ion M and at least one counter ion X may be added before, during or after the aging step without substantially changing the BET specific surface area of the adsorbent composition and without changing the BET specific surface area of the adsorbent composition for diameters less than or equal to that of the adsorbent composition
Figure BDA0002378141220000181
BJH pore volume of the pores of (a). Further, the BET specific surface area and BJH pore volume of the sorbent compositions according to the invention are related to U.S. patent 6, incorporated herein by reference for exampleThe BET specific surface area and BJH pore volume of the calcium hydroxide adsorbents produced by the known methods disclosed in 322,769 and 7,744,678 are substantially the same. Thus, ensuring SO is preserved2Adsorbent properties to remove efficiency.
In the method of preparing a sorbent composition according to the invention, if the hydrated lime composition is prepared according to the method described in us patent 7,744,678, the method comprises the step of adding an amount of alkali metal, preferably sodium, to the quicklime or to the slaked water or to the hydrated lime sufficient to obtain an alkali metal content in the hydrated lime of equal to or greater than 0.2 wt% and equal to or less than 3.5 wt%, based on the total weight of the dry sorbent composition. According to this embodiment, an additive or a mixture of additives containing at least one metal ion M and at least one counter ion X is added to quick lime or to slaked water or to hydrated lime in such an amount that the content of the additive or mixture of additives containing at least one metal ion M and at least one counter ion X is between 0.1% and 5%, preferably between 0.3% and 3%, by weight of the dry sorbent composition.
Various sorbent compositions have been prepared according to the method of the present invention and the resistivity of the dry powder of the sorbent compositions was measured according to the protocol set forth by IEEE (Esctcourt, 1984). In general, a resistivity cell having a defined volume is filled with a dry powder of the sorbent composition, which is then compacted by a weight to obtain a flat surface. The electrodes with the protective layer were placed on the powder surface and the resistivity of the powder was measured at various temperatures between 150 ℃ (302 ° F) and 300 ℃ (372 ° F) in an air stream with a humidity of 10% in an oven. The resistivity of the comparative example was measured under the same conditions. For each measurement, the maximum resistivity R is determinedmaxAnd resistivity at 300 ℃ (372 ° F). The resistivity measurements are shown below:
group A examples
Example 1 is a comparative sample, a calcium hydroxide adsorbent designed to remove acid gas contaminants, prepared according to US6,322,769B 1. Neither sodium nor an additive of formula MX was added.
Example 2 is a comparative sample, a calcium hydroxide adsorbent designed to remove acid gas contaminants, prepared according to US7,744,678B 2. The sample contained Na2CO31 wt% sodium in form. No other sodium or additive of formula MX was added.
Example 3 is a calcium hydroxide sorbent prepared according to the present invention using ferric nitrate as the dopant.
Table 1 shows the measured resistivity parameters RmaxAnd R300。
Table 1: resistivity parameters of calcium hydroxide adsorbents doped with sodium and iron salts.
Figure BDA0002378141220000191
As is clear from Table 1, R of example 1maxValue and R300The values are all high and above the preferred range of resistivity values between 10E7 ohm-cm and 2E10 ohm-cm.
1 wt% sodium added in example 2maxAnd R300The value is reduced by more than one order of magnitude. Surprisingly, R of R300 was obtained by adding a small amount of 0.5 wt% ferric nitratemaxThe value is reduced by nearly one order of magnitude and R is reduced300A reduction of nearly two orders of magnitude. Surprisingly, the addition of ferric nitrate is more effective than the addition of sodium.
Group B examples
A set of adsorbents was prepared by using an adsorbent prepared according to US7,744,678B 2 and adding iron and copper salts to the adsorbent according to the method of the present invention.
Example 4 is a sample of a calcium hydroxide adsorbent designed to remove acid gas contaminants prepared according to US7,744,678B 2, to which an amount of ferric nitrate has been added. According to the preparation method described in US7,744,678, a certain amount of sodium has been added.
Example 5 is a sample of a calcium hydroxide adsorbent designed to remove acid gas contaminants prepared according to US7,744,678B 2, to which an amount of copper nitrate has been added. According to the preparation method described in US7,744,678, a certain amount of sodium has been added.
Table 2: resistivity parameters of calcium hydroxide adsorbents doped with sodium, iron and copper salts.
Figure BDA0002378141220000201
Table 2 shows that for these adsorbents, the addition of ferric nitrate results in a resistivity value RmaxResistivity value R of comparative example 1maxA reduction of nearly two orders of magnitude. The addition of copper nitrate will result in a resistivity RmaxBy nearly three orders of magnitude, to reduce the resistivity R300The drop is over three orders of magnitude.
CGroup ofExamples
A set of adsorbents was prepared by using an adsorbent according to US7,744,678, and the effect of counter ions on the resistivity of the adsorbent was measured by adding various iron salts.
Example 4 is a sample of a calcium hydroxide adsorbent designed to remove acid gas contaminants prepared according to US7,744,678B 2, to which a quantity of ferric nitrate has been added. According to the preparation method described in US7,744,678, a certain amount of sodium has been added.
Example 6 is a comparative sample in which an amount of ferric sulphate has been added to a calcium hydroxide sorbent prepared according to US7,744,678B 2 designed to remove acid gas contaminants. According to the preparation method described in US7,744,678, a certain amount of sodium has been added.
Example 7 is a comparative sample, a calcium hydroxide adsorbent designed to remove acid gas contaminants, prepared according to US7,744,678B 2, to which an amount of iron acetate has been added. According to the preparation method described in US7,744,678, a certain amount of sodium has been added.
Table 3: resistivity parameters of calcium hydroxide adsorbents using different iron salts.
Figure BDA0002378141220000211
Table 3 shows that the use of ferric nitrate leads to a resistivity value R compared to comparative example 2maxReduced by four times and R is reduced300By an order of magnitude. Surprisingly, the use of iron salts of different composition, such as sulphate and acetate, resulted in a different composition for R than in comparative example 2maxAnd R300The resistivity of (2) increases. It should be noted that the use of ferric sulphate results in a resistivity R300Value of R is not greater thanmaxLow.
Group D examples
A set of adsorbents was prepared by using an adsorbent according to US7,744,678, and various copper salts have been added to measure the effect of counter ions on the resistivity of the adsorbent.
Table 4: resistivity parameters of calcium hydroxide adsorbents using different copper salts
Figure BDA0002378141220000212
Figure BDA0002378141220000221
As is clear from table 4, surprisingly, all salts except copper nitrate increased the resistivity of the adsorbent of comparative example 2.
It is to be mentioned that the examples of sorbent compositions given above are not limiting to the invention and that other additives may be used in amounts between 0.1% and 5% by weight of the dry sorbent composition to reduce the resistivity of the sorbent composition intended for use in a method of treating flue gas using an electrostatic precipitator.
It is mentioned that by using the adsorbent according to the invention, an improved collection of particulate matter on the collecting electrode of an electrostatic precipitator can be observed.
According to another aspect, the invention relates to a flue gas treatment apparatus. Fig. 1 shows a schematic embodiment of a flue gas treatment plant 100, the flue gas treatment plant 100 comprising an electrostatic precipitator 101 arranged downstream of a first duct section 102, the first duct section 102 being arranged downstream of an air preheater 103, characterized in that an injection zone 104 is arranged upstream of said air preheater 103 and comprises a sorbent inlet 105. The flue gas treatment plant 100 further comprises a reservoir 106, which reservoir 106 contains the sorbent composition S for providing the sorbent composition to the injection zone through the sorbent inlet. The hot flue gas FG generated by the boiler 10 flows through an injection area in which a sorbent S according to the invention is injected, to react with the SO from the flue gas2Reacts with other acid gases and the hot flue gas then passes through an air preheater through which cool air CA flows to absorb the heat of the hot flue gas and is injected into the boiler as hot air HA. The flue gas then flows through an electrostatic precipitator 101 in which electrostatic precipitator 101 charged collecting electrodes collect particulate matter including the sorbent composition according to the invention that has reacted with the unwanted acid gases. The flue gas treatment apparatus described herein is relatively simple and well suited for use with the sorbent compositions according to the invention.
Preferably, the flue gas treatment plant is used for treating flue gas of a power plant using coal or fuel containing sulphur or other acid gas precursors.
It will be understood that the invention is not limited to the described embodiments and that many variations are possible without departing from the scope of the appended claims.
For example, in a preferred embodiment, an apparatus for flue gas treatment is described, having an electrostatic precipitator downstream of an air preheater, said air preheater being connected to said electrostatic precipitator by a duct, said duct having an injection zone for injecting a sorbent composition according to the invention, which injection zone is arranged upstream of said air preheater. An alternative within the scope of the invention may include a particulate collection device upstream of the preheater.
A further alternative of the flue gas treatment device according to the invention comprises an electrostatic precipitator, a preheater and optionally a particle collection device in that order before reaching the stack.
The particle collection means may be another electrostatic precipitator or any type of filter, such as a bag filter.
In all of these embodiments, depending on the field configuration, the sorbent composition according to the invention is injected into an injection zone located upstream of the electrostatic precipitator, wherein the electrostatic precipitator precedes or follows the preheater.

Claims (10)

1. A method for reducing the electrical resistivity of a powdered sorbent composition to less than 1E11 ohm-cm and greater than 1E07 ohm-cm at 300 ℃, for use in a flue gas treatment device comprising an electrostatic precipitator; wherein the electrical resistivity of the powdered sorbent composition is measured in an electrical resistivity cell of an oven under a flow of air having a humidity of 10%, the powdered sorbent composition comprising a powdered calcium-magnesium compound comprising at least a calcium-magnesium carbonate in an amount of greater than or equal to 80 wt% or a calcium-magnesium hydroxide in an amount of greater than or equal to 80 wt%, relative to the total weight of the powdered calcium-magnesium content, the method comprising the steps of:
a) providing the powdered sorbent composition in a reactor; and
b) adding an additive or a mixture of additives comprising at least one metal ion M and/or a counterion X to the powdered sorbent composition in a calculated amount to give 0.1 to 5 wt% of the metal ion M and/or counterion X relative to the total weight of dry sorbent composition; wherein M is a metal ion having an atomic number of 74 or less and being a transition metal ion or a post-transition metal ion, or Mg2+Or Na+Or Li+(ii) a And X is selected from nitrate, nitrite, oxygen ion O2-And hydroxyl OH-And mixtures thereof.
2. The method of claim 1, wherein the metal ion M is selected from the group consisting of Cu2+、Fe2+、Fe3+、Mn2+、Co2+、Mo2+、Ni2+And Zn2+Group (d) of (a).
3. The process of claim 1 or 2, wherein the counterion X is nitrate.
4. Method according to any one of the preceding claims, wherein the powdery calcium-magnesium compound has a size of at least 20m as determined by nitrogen adsorption2BET specific surface area in g.
5. Method according to any one of the preceding claims, wherein the powdery calcium-magnesium compound has a diameter of less than or equal to the diameter determined by nitrogen desorption
Figure FDA0002378141210000011
At least 0.1cm3/g、0.15cm3BJH pore volume per g.
6. The method of any one of the preceding claims, wherein the powdered sorbent composition further comprises activated carbon, lignite coke, halloysite, sepiolite, clay, bentonite, kaolin, vermiculite, fireclay, aerated cement dust, perlite, expanded clay, lime sandstone dust, pozzolan, sub-bearing rock dust, pozzolan lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulfide, organosulfides, calcium sulfate, furnace coke, lignite dust, fly ash, or water glass.
7. The method according to any one of the preceding claims, further comprising the step of adding a sodium-containing sodium additive to the powdered sorbent composition, the sodium additive being added in an amount of at most 3.5 wt%, expressed in sodium equivalents, relative to the total weight of the powdered sorbent composition.
8. The method according to any one of the preceding claims, wherein the powdered calcium magnesium compound is hydrated lime.
9. A powdered sorbent composition for flue gas treatment equipment comprising an electrostatic precipitator, the powdered sorbent composition comprising a powdered calcium-magnesium compound comprising at least a calcium-magnesium carbonate in an amount of greater than or equal to 80 wt% or a calcium-magnesium hydroxide in an amount of greater than or equal to 80 wt%, relative to the total weight of the powdered calcium-magnesium content, characterized in that the powdered sorbent composition has a reduced electrical resistivity of less than 1E11 ohm-cm and greater than 1E07 ohm-cm at 300 ℃; wherein the resistivity of the powdered sorbent composition is measured in a resistivity cell of an oven under a stream of air having a humidity of 10%, the reduced resistivity being achieved by a calculated amount of an additive or mixture of additives comprising at least one metal ion M and/or at least one counterion X, the calculated amount being such as to yield 0.1 to 5 wt% of the metal ion M and/or counterion X relative to the total weight of the dry sorbent composition; wherein M is a metal ion having an atomic number of 74 or less and being a transition metal ion or a late transition metal ion, or Mg2+Or Na+Or Li+And X is selected from the group consisting of nitrate, nitrite, and oxyanion O2-And hydroxyl OH-A counter ion of (1).
10. Use of the powdered sorbent composition of claim 9 or obtainable by the process of any one of claims 1 to 8 in a flue gas treatment process with an apparatus comprising an electrostatic precipitator.
CN201880049441.7A 2017-07-24 2018-07-24 Adsorbent composition for electrostatic precipitator Pending CN110997129A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EPPCT/EP2017/068625 2017-07-24
US15/657,294 2017-07-24
US15/657,294 US10898876B2 (en) 2017-07-24 2017-07-24 Sorbent composition for an electrostatic precipitator
EP2017068625 2017-07-24
PCT/EP2018/070012 WO2019020613A1 (en) 2017-07-24 2018-07-24 Sorbent composition for an electrostatic precipitator

Publications (1)

Publication Number Publication Date
CN110997129A true CN110997129A (en) 2020-04-10

Family

ID=62916705

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880049441.7A Pending CN110997129A (en) 2017-07-24 2018-07-24 Adsorbent composition for electrostatic precipitator

Country Status (11)

Country Link
EP (1) EP3658275A1 (en)
JP (1) JP2020528004A (en)
KR (1) KR20200035038A (en)
CN (1) CN110997129A (en)
BE (1) BE1025964B1 (en)
BR (1) BR112020001082A2 (en)
CA (1) CA3070255A1 (en)
CL (1) CL2020000143A1 (en)
CO (1) CO2020000463A2 (en)
SG (1) SG11202000483QA (en)
WO (1) WO2019020613A1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5234877A (en) * 1990-07-16 1993-08-10 Board Of Trustees Operating Michigan State University Composite clay materials for removal of SOx from gas streams
US5298473A (en) * 1990-07-16 1994-03-29 Board Of Trustees Operating Michigan State University Hydrated lime clay composites for the removal of SOx from flue gas streams
US5334564A (en) * 1990-07-16 1994-08-02 Board Of Trustees Operating Michigan State University Method for the preparation of highly reactive clay composites for the removal of SOx from flue gas streams
WO2005028083A1 (en) * 2003-09-18 2005-03-31 Japan Science And Technology Agency Novel desulfurizing agent for dry desulfurization process
CN101370735A (en) * 2005-06-28 2009-02-18 勒瓦研究开发股份有限公司 Pulverulent lime composition, method for the production thereof, and use of the same
US20150110698A1 (en) * 2012-03-30 2015-04-23 Fuel Tech, Inc. Process for Sulfur Dioxide, Hydrochloric Acid and Mercury Mediation
US20160151760A1 (en) * 2013-07-18 2016-06-02 Novinda Corporation Carbonate Modified Compositions for Reduction of Flue Gas Resistivity
CN106413857A (en) * 2014-06-04 2017-02-15 索尔维公司 Stabilization of at least one heavy metal contained in a sodic fly ash using a water-soluble source of silicate and a material containing calcium and/or magnesium

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4439351A (en) 1982-07-06 1984-03-27 Calgon Corporation Use of anionic or cationic polymers to lower the electrical resistivity of fly ash
US4502872A (en) 1983-03-31 1985-03-05 Combustion Engineering, Inc. Discharge electrode wire assembly for electrostatic precipitator
DE3620024A1 (en) 1986-06-13 1987-12-17 Fels Werke Peine Salzgitter Process for preparing finely divided calcium hydroxide
US5223239A (en) 1990-07-24 1993-06-29 Research Corporation Technologies, Inc. Method of preparing hydrated lime
US5173279A (en) 1990-11-21 1992-12-22 Lhoist Recherche Et Developpement S.A. Method and composition for treating flue or exhaust gases utilizing modified calcium hydroxide
US5705141A (en) 1990-11-21 1998-01-06 Lhoist Researche Et Developpement S.A. Calcium and/or magnesium hydroxide, and preparation and use thereof
BE1009692A3 (en) 1995-10-19 1997-07-01 Lhoist Rech & Dev Sa PARTICLE Ca (OH) 2.
US6126910A (en) 1997-10-14 2000-10-03 Wilhelm; James H. Method for removing acid gases from flue gas
US6797035B2 (en) * 2002-08-30 2004-09-28 Ada Environmental Solutions, Llc Oxidizing additives for control of particulate emissions
US6803025B2 (en) 2002-12-05 2004-10-12 Frank B. Meserole Process for removing SO3/H2SO4 from flue gases
DK1967276T3 (en) 2007-03-05 2019-08-12 General Electric Technology Gmbh A METHOD OF DETERMINING THE DUST LOAD OF AN ELECTROSTATIC FILTER AND A METHOD AND DEVICE TO CONTROL THE BANKING OF AN ELECTROSTATIC FILTER
WO2015119880A1 (en) 2014-02-04 2015-08-13 Novinda Corporation Flue-gas treatment aid

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5234877A (en) * 1990-07-16 1993-08-10 Board Of Trustees Operating Michigan State University Composite clay materials for removal of SOx from gas streams
US5298473A (en) * 1990-07-16 1994-03-29 Board Of Trustees Operating Michigan State University Hydrated lime clay composites for the removal of SOx from flue gas streams
US5334564A (en) * 1990-07-16 1994-08-02 Board Of Trustees Operating Michigan State University Method for the preparation of highly reactive clay composites for the removal of SOx from flue gas streams
WO2005028083A1 (en) * 2003-09-18 2005-03-31 Japan Science And Technology Agency Novel desulfurizing agent for dry desulfurization process
CN101370735A (en) * 2005-06-28 2009-02-18 勒瓦研究开发股份有限公司 Pulverulent lime composition, method for the production thereof, and use of the same
CN103626216A (en) * 2005-06-28 2014-03-12 勒瓦研究开发股份有限公司 Pulverulent lime composition, method for the production thereof, and use of the same
US20150110698A1 (en) * 2012-03-30 2015-04-23 Fuel Tech, Inc. Process for Sulfur Dioxide, Hydrochloric Acid and Mercury Mediation
US20160151760A1 (en) * 2013-07-18 2016-06-02 Novinda Corporation Carbonate Modified Compositions for Reduction of Flue Gas Resistivity
CN106413857A (en) * 2014-06-04 2017-02-15 索尔维公司 Stabilization of at least one heavy metal contained in a sodic fly ash using a water-soluble source of silicate and a material containing calcium and/or magnesium

Also Published As

Publication number Publication date
BR112020001082A2 (en) 2020-07-21
JP2020528004A (en) 2020-09-17
CO2020000463A2 (en) 2020-05-05
CA3070255A1 (en) 2019-01-31
EP3658275A1 (en) 2020-06-03
BE1025964A1 (en) 2019-08-23
SG11202000483QA (en) 2020-02-27
CL2020000143A1 (en) 2020-05-29
KR20200035038A (en) 2020-04-01
WO2019020613A1 (en) 2019-01-31
BE1025964B1 (en) 2019-08-28

Similar Documents

Publication Publication Date Title
US8609046B2 (en) Gas stream treatment process
US20170113085A1 (en) Treatment method for coal fly ash
KR101573002B1 (en) COMPOSITION FOR REMOVING SOx IN EXHAUSTED GAS AND METHOD FOR REMOVING Sox IN EXHAUSTED GAS
EP3151929A1 (en) Stabilization of at least one heavy metal contained in a sodic fly ash using a water-soluble source of silicate and a material containing calcium and/or magnesium
US20150314155A1 (en) Treatment of Sodic Fly Ash for Reducing the Leachability of Selenium Contained Herein
US20220105523A1 (en) Hydrated lime with reduced resistivity and method of manufacture
US10898876B2 (en) Sorbent composition for an electrostatic precipitator
US10024534B2 (en) Stabilization of sodic fly ash of type F using calcium-based material
CN110997129A (en) Adsorbent composition for electrostatic precipitator
WO2019020609A1 (en) Sorbent composition for an electrostatic precipitator
CN112399884B (en) Sorbent compositions for electrostatic precipitators
US10874975B2 (en) Sorbent composition for an electrostatic precipitator
US20200230570A1 (en) Sorbent composition for an electrostatic precipitator
KR101787418B1 (en) A Composite of low grade lime with CO2 emission reducing and removal of sulfur oxides in exhausted gas and improvement of high basicity efficiency in smelting process and manufacturing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200410

WD01 Invention patent application deemed withdrawn after publication