WO2012036012A1 - 酸性成分除去剤の製造方法および気体中の酸性成分除去方法 - Google Patents

酸性成分除去剤の製造方法および気体中の酸性成分除去方法 Download PDF

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WO2012036012A1
WO2012036012A1 PCT/JP2011/070172 JP2011070172W WO2012036012A1 WO 2012036012 A1 WO2012036012 A1 WO 2012036012A1 JP 2011070172 W JP2011070172 W JP 2011070172W WO 2012036012 A1 WO2012036012 A1 WO 2012036012A1
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Prior art keywords
acidic component
removing agent
remover
average particle
fumed silica
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PCT/JP2011/070172
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English (en)
French (fr)
Japanese (ja)
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桜井　茂
高田　英樹
松本　知子
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旭硝子株式会社
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Priority to JP2012533947A priority Critical patent/JP5799955B2/ja
Publication of WO2012036012A1 publication Critical patent/WO2012036012A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/42—Preventing the absorption of moisture or caking
    • 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
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • 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
    • B01D2251/606—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
    • B01D2253/106—Silica or silicates
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/304—Linear dimensions, e.g. particle shape, diameter
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/306—Surface area, e.g. BET-specific surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • 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
    • B01D—SEPARATION
    • B01D2273/00—Operation of filters specially adapted for separating dispersed particles from gases or vapours
    • B01D2273/12—Influencing the filter cake during filtration using filter aids
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing an acidic component remover that removes acidic components in a gas, and a method for removing an acidic component in a gas using the acidic component remover obtained by the production method.
  • Acidic components such as hydrogen chloride and sulfur oxides are contained in the exhaust gas generated by incineration of general waste and industrial waste.
  • a removing apparatus using an acidic component remover is known.
  • FIG. 1 is a block diagram showing an example of an apparatus for removing acidic components in exhaust gas.
  • the removal device includes a silo (storage facility) 1 for storing a powdery acidic component remover M, an exhaust gas passage 2 (flue) through which exhaust gas containing acidic components flows, and an acidic component remover for silo 1.
  • a silo storage facility
  • the discharge unit 1a of the silo 1 is provided with a powder quantitative supply device 5 such as a rotary valve or a table feeder.
  • a powder quantitative supply device 5 such as a rotary valve or a table feeder.
  • the acidic component removing agent M is dropped into the opening 3 a of the supply pipe 3.
  • An incinerator (not shown) for general waste, industrial waste, etc. is installed on the upstream side of the exhaust gas passage 2.
  • exhaust gas containing acidic components such as hydrogen chloride, nitrogen oxide, and sulfur oxide from the incinerator circulates.
  • the supply pipe 3 delivers the acidic component removing agent M supplied from the opening 3a to the downstream side by a gas flow such as an air flow circulated from the upstream side.
  • the downstream end of the supply pipe 3 is disposed in the exhaust gas flow path 2.
  • an ejector 3b for ejecting the acidic component removing agent M into the exhaust gas is attached.
  • the bag filter 4 includes a housing 41, an exhaust gas inlet 42 provided in a lower portion 41 a of the housing 41, a plurality of tubular filter cloths 43 disposed in a central portion 41 b of the housing 41, and an upper portion of the housing 41. And an exhaust port 44 provided in 41c.
  • the filter cloth 43 has a lower end closed and a hollow portion 43a inside.
  • the upper part 41c and the central part 41b of the housing 41 are partitioned by a partition plate 45, and the exhaust gas always passes through the filter cloth 43 when the exhaust gas moves from the central part 41b of the housing 41 to the upper part 41c.
  • the partition plate 45 is provided with a penetrating portion 45a, and a communicating tube 46 for connecting the hollow portion 43a of the filter cloth 43 and the upper portion 41c of the housing 41 is attached to the penetrating portion 45a.
  • the powder quantitative supply device 5 is operated to supply the acidic component removing agent M in the silo 1 to the supply pipe 3.
  • the acidic component removing agent M supplied to the supply pipe 3 is carried in the gas flow, sent to the downstream end, and ejected from the ejector 3b into the exhaust gas in the exhaust gas flow path 2.
  • a part of the ejected acidic component removing agent M reacts with the acidic component in the exhaust gas to become a reaction product.
  • the reaction product and the unreacted acidic component removing agent M are sent to the bag filter 4 together with the exhaust gas.
  • the reaction product and the unreacted acidic component removing agent M are deposited on the surface of the filter cloth 43 to form a filtration layer, and the acidic component in the exhaust gas is further removed by the filtration layer.
  • the exhaust gas from which the acidic component has been removed passes through the filter cloth 43 and is discharged from the discharge port 44 through the communication pipe 46.
  • An acidic component remover used in an apparatus for removing acidic components in exhaust gas slaked lime has been used in the past, but in recent years, for example, the following has been proposed.
  • An acidic component remover containing sodium hydrogen carbonate as a main component and having an average particle size of 50 ⁇ m or less, preferably 10 to 30 ⁇ m Patent Document 1.
  • the acidic component remover In order to efficiently remove the acidic component in the exhaust gas, it is necessary to make the average particle size of the acidic component remover as small as possible.
  • the acidic component remover having an average particle size of 30 ⁇ m or less has poor fluidity, or the adhesion between particles becomes large and tends to solidify, which may cause difficulty in stable handling. As a result, there is a possibility that the removal efficiency of the acidic component is deteriorated.
  • the acidic component remover when the fluidity of the acidic component remover deteriorates and the adhesion between particles increases, the acidic component remover itself easily aggregates. For example, as shown in FIG. Or a bridge phenomenon occurs in the silo 1 as shown in FIG. As a result, the supply of the acidic component removing agent stagnate, and there is a risk that the acidic component removal efficiency in the removal device will be significantly reduced.
  • the acidic component remover particles easily enter the gaps between the fibers constituting the filter cloth of the bag filter, which may cause the following problems.
  • the pressure loss in the filter cloth increases, the pressure difference of the exhaust gas between the inlet and the outlet of the bag filter (hereinafter referred to as differential pressure) increases, and the circulation amount of the exhaust gas decreases significantly.
  • differential pressure the pressure difference of the exhaust gas between the inlet and the outlet of the bag filter
  • the circulation amount of the exhaust gas decreases significantly.
  • the compressed air is flowed in the reverse direction of the flow of the exhaust gas, and the acid component remover particles are removed from the surface of the filter cloth and the fiber gap of the filter cloth ( Even if backwashing is performed, the pressure differential does not increase and does not recover.
  • Particles of the acidic component removing agent pass through the filter cloth and are observed as dust in the exhaust gas.
  • the filtration layer deposited on the surface of the filter cloth is easily peeled off from the filter cloth.
  • any of the problems (i) to (iv) may lead to a reduction in the removal efficiency of acidic components in the removal apparatus. Therefore, the following is proposed as an acidic component remover that suppresses the increase in pressure loss in the filter cloth of the bag filter, leakage of the acidic component remover from the filter cloth, and dropping of the filter layer deposited on the surface of the filter cloth.
  • It contains sodium hydrogen carbonate, alkaline earth metal carbonate and fumed silica, the alkaline earth metal carbonate ratio is 1 to 5% by mass, and the fumed silica ratio is 0.00.
  • An acidic component remover having an average particle diameter of 5 to 2.0% by mass and an average particle size of 3 to 20 ⁇ m Patent Document 4).
  • the tensile breaking force which is an index of the ease of dropping off the filtration layer and the ease of discharging from the silo, is much smaller in magnesium carbonate than in calcium carbonate (patent Table 3 in Literature 4. Further, hydrophilic fumed silica tends to be smaller than hydrophobic fumed silica (paragraph [0022] and Table 3 of Patent Document 4). Therefore, in an actual site, magnesium carbonate is suitably used as the alkaline earth metal carbonate, and hydrophilic fumed silica is suitably used as the fumed silica.
  • the present invention suppresses an increase in pressure loss in the filter cloth of the bag filter and leakage of the acidic component remover from the filter cloth, and is less likely to cause a discharge trouble from the silo, has excellent handleability, and Provided is a method for producing an acidic component remover that can sufficiently suppress the filtration layer deposited on the surface, and a method for removing an acidic component in a gas using the acidic component remover obtained by the production method.
  • a new acidic component remover that is compatible with both problems related to the influence on the filter cloth and problems related to the stability of supply to the exhaust gas from the silo, the adhesion force of the powder layer, the wall friction force, the hopper inclination angle, Provided paying attention to each element of outlet diameter, breaking stress, residual pressure loss, and leakage concentration.
  • the method for producing an acidic component remover of the present invention comprises a sodium bicarbonate (A) powder having an average particle diameter of 50 ⁇ m or more, a hydrophobic fumed silica (B) powder, and an average particle diameter of primary particles.
  • A sodium bicarbonate
  • B hydrophobic fumed silica
  • the resulting acidic component remover has an average particle size of 3 to 20 ⁇ m, acidic
  • the content ratio of the hydrophobic fumed silica (B) in the component remover is 0.2 to 0.5% by mass, and the content ratio of the colloidal calcium carbonate (C) in the acidic component remover is 1.5. It is characterized by being -2.5 mass%.
  • the average particle size of the sodium hydrogencarbonate (A) before pulverization is preferably 50 to 300 ⁇ m.
  • the average particle diameter of the primary particles of the hydrophobic fumed silica (B) is preferably 5 to 50 nm.
  • the BET specific surface area of the colloidal calcium carbonate (C) is preferably 30 m 2 / g or more, and the boiled linseed oil absorption amount of the colloidal calcium carbonate (C) is preferably 50 mL / 100 g or more. .
  • an acidic component remover having the average particle diameter by pulverizing with a pulverizing means equipped with a classifying means and classifying the pulverized product. More preferably, the powder exceeding the diameter is returned to the pulverizing means.
  • the pulverization is preferably performed by a pulverizing means selected from an impact pulverizer and a jet mill.
  • the present invention is also a method for removing an acidic component in a gas, wherein the acidic component removing agent obtained by the production method of the present invention is temporarily stored in a storage facility and then supplied into a gas containing an acidic component.
  • the acidic component removing agent is discharged from the storage facility and supported on the gas flow, and the gas flow carrying the acidic component removing agent is supplied into the gas containing the acidic component.
  • the acidic component removing agent obtained by the production method of the present invention and the acidic component removing method in gas using the same, an increase in pressure loss in the filter cloth of the bag filter and leakage of the acidic component removing agent from the filter cloth
  • it is difficult to cause a trouble of discharging from the silo the handleability is excellent, and the filtration layer deposited on the surface of the filter cloth can be sufficiently prevented from falling off.
  • FIG. 1 It is a block diagram which shows an example of the removal apparatus of the acidic component in waste gas. It is a figure explaining the rat hole phenomenon in the silo of the removal apparatus of FIG. It is a figure explaining the bridge phenomenon in the silo of the removal apparatus of FIG. It is a figure explaining a hopper inclination angle.
  • the method for producing an acidic component remover of the present invention comprises mixing sodium hydrogen carbonate (A) powder, hydrophobic fumed silica (B) powder, and colloidal calcium carbonate (C) powder, Manufacture by grinding. It is necessary that these three kinds of powders coexist for most of the period during which the pulverization is performed. Therefore, it is preferable to mix these three kinds of powders and supply the mixture to the pulverizer, or to supply these three kinds of powders to the pulverizer almost simultaneously to perform pulverization. In addition, in this specification, each powder before mixing is called raw material powder.
  • the method for producing the acidic component removing agent of the present invention is obtained by mixing raw material powders and supplying the mixture to a pulverizer or supplying each raw material powder to the pulverizer almost simultaneously for the following reason.
  • a method of pulverizing the acidic component removing agent so that the average particle size is 3 to 20 ⁇ m is preferable.
  • Hydrophobic fumed silica (B) which tends to agglomerate secondary by applying a strong shear stress to the powder during pulverization of the mixture, and colloidal carbonate having an average primary particle size of 50 nm or less Colloidal calcium carbonate in which the average particle size of hydrophobic fumed silica (B) and primary particles is 50 nm or less on the surface of particles of sodium hydrogen carbonate (A) which is efficiently crushed calcium (C) (C) can be uniformly applied in the state of primary and secondary particles.
  • the acidic component removing agent obtained by the method of the present invention has fine particles of hydrophobic fumed silica (B) on the surface of sodium hydrogencarbonate (A) particles pulverized to have an average particle size of about 3 to 20 ⁇ m. It is considered to be composed of particles having a structure in which particles and fine particles of colloidal calcium carbonate (C) are attached.
  • sodium bicarbonate (A) is pulverized, hydrophobic fumed silica (B) secondary particles are pulverized into primary particles and fine secondary particles, colloidal calcium carbonate (C) primary particles and fine particles Crushing into fine secondary particles, and fine particles (hydrophobic fumed silica (B) and colloidal calcium carbonate (C) primary particles and fine secondary particles on the surface of the pulverized sodium hydrogen carbonate (A) particles.
  • particles of the acidic component removing agent are generated by the adhesion of the secondary particles).
  • the acidic component removing agent in the present invention is a powder and is considered to be composed of an aggregate of such particles.
  • an impact pulverizer (a pulverizer using high-speed rotating blades), a jet mill (a pulverizer using a collision airflow), a ball mill, or the like is preferable.
  • a pulverizer equipped with a wind classifier the particles discharged from the pulverizer are classified, and the coarse particles are returned to the pulverizer again, while pulverizing the mixture of raw material powders.
  • An acidic component removing agent having a target average particle diameter can be obtained.
  • Jet mills are expensive in terms of power, but are suitable for pulverization as a pulverizing means, and can remove acidic particles with the desired average particle size in high yield without removing coarse particles by sieving. Can do.
  • Sodium bicarbonate (A) Sodium hydrogen carbonate (A) as a raw material powder is a powder composed of particles having an average particle diameter of 50 ⁇ m or more, and is usually preferably a powder composed of particles having an average particle diameter of 90 to 300 ⁇ m.
  • Sodium hydrogen carbonate powder is usually produced industrially by a crystallization method. It is difficult to industrially efficiently obtain a raw material powder having an average particle size of less than 50 ⁇ m by crystallization, and such a raw material powder having a small average particle size has poor flowability and is difficult to handle. In addition, a raw material powder having an excessively large average particle size requires large energy for pulverization.
  • the average particle size of sodium bicarbonate (A), which is the raw material powder here, is measured with a measuring device using a standard sieve (manufactured by Seishin Enterprise Co., Ltd., automatic dry sieving measuring instrument robot shifter RPS-105). It is a thing.
  • Hydrophobic fumed silica (B) used as a raw material powder is obtained by hydrophobizing the surface of fumed silica (hydrophilic fumed silica).
  • Fumed silica is a synthetic amorphous silica produced by a dry process. Specific examples include those produced by a combustion method, a self-combustion method, or a heating method.
  • Hydrophobing treatment includes silane treatment with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, etc., silane coupling agent treatment with vinyltrimethoxysilane, dimethylpolysiloxane treatment, methylhydrogenpolysiloxane treatment, fatty acid treatment, etc. Can be mentioned.
  • the hydrophobicity of the hydrophobic fumed silica (B) is preferably 0.8% or more and 5% or less. If the degree of hydrophobicity is less than 0.8%, the fluidization effect cannot be sufficiently obtained. When the degree of hydrophobicity exceeds 5%, the cohesiveness of the hydrophobic fumed silica (B) becomes strong on the contrary, and similarly, a sufficient effect cannot be obtained. Further, the hydrophobic fumed silica (B) can be arbitrarily selected from commercially available ones.
  • the degree of hydrophobicity of the hydrophobic fumed silica (B) is an index indicating the degree of adhesion of the hydrophobizing agent such as dimethylsilane adhering to the surface of the fumed silica.
  • the carbon content of B is measured by a combustion type carbon amount measuring device (such as SUMIGRAPH NC-80 (Sumitomo Chemical Analysis Center Co., Ltd.) or EMIA-110 (Horiba Seisakusho Co., Ltd.)). .
  • the acidic component remover it is preferable that most of the hydrophobic fumed silica (B) is uniformly dispersed on the surface of the sodium hydrogen carbonate particles in the form of primary particles. Since most of the hydrophobic fumed silica (B) is dispersed in the form of primary particles, the acidic component removing agent can be used as compared with the case where the hydrophobic fumed silica (B) is present in the form of secondary particles. The fluidity can be further moderated, and agglomeration due to aggregation can be suppressed. Therefore, the average particle diameter of the primary particles of hydrophobic fumed silica (B) used as the raw material powder is preferably 5 to 50 nm.
  • grains of hydrophobic fumed silica (B) mean the minimum unit of the structure particle judged by visual observation of a SEM (scanning electron microscope) observation image.
  • the average particle size of the primary particles of the hydrophobic fumed silica (B) is actually measured by SEM (scanning electron microscope). Specifically, the particle size of 100 primary particles is measured. , The arithmetic average of the measured values.
  • Colloidal calcium carbonate (C) generally refers to precipitated calcium carbonate (synthetic calcium carbonate) called primary colloidal calcium carbonate or colloidal calcium carbonate having a primary particle size of 0.2 ⁇ m or less. In the present invention, this colloidal calcium carbonate (C) is used as a raw material powder.
  • the average particle diameter of primary particles of colloidal calcium carbonate (C) used as the raw material powder is 50 nm or less, and more preferably 30 nm or less.
  • the primary particle of colloidal calcium carbonate (C) here refers to the minimum unit of constituent particles determined by visual observation of an SEM (scanning electron microscope) observation image.
  • the average particle diameter of primary particles of colloidal calcium carbonate (C) is actually measured by SEM (scanning electron microscope). Specifically, the particle diameter of 100 primary particles is measured and measured. The value is an arithmetic average.
  • the BET specific surface area of the colloidal calcium carbonate (C) measured by the nitrogen adsorption method is preferably 30 m 2 / g or more, and more preferably 40 m 2 / g or more.
  • the BET specific surface area is preferably 85 m 2 / g or less.
  • the amount of boiled linseed oil absorbed by the colloidal calcium carbonate (C) is preferably 50 mL / 100 g or more.
  • the amount of boiled linseed oil absorbed is preferably 100 mL / 100 g or less.
  • the boiled linseed oil absorption amount of the colloidal calcium carbonate (C) here is measured according to JIS K 5101-13.
  • the ratio (content ratio) of each component in the acidic component remover is substantially equal to the mixing ratio of each raw material powder used in the production.
  • the mixing ratio of each raw material powder and the content ratio of each component in the acidic component remover may be different.
  • sodium hydrogen carbonate (A) that is not pulverized to a predetermined size and is not taken into the acidic component remover may be generated.
  • the content ratio of each component in the acidic component remover can be calculated from the mixing ratio of each raw material powder by excluding the amount of the component that has not been incorporated into the acidic component remover.
  • the content rate of each component in an acidic component removal agent can also be determined by measuring the quantity of each component in the obtained acidic component removal agent.
  • the content of each component in the acidic component removing agent (100% by mass) is 0.2 to 0.5% by mass for hydrophobic fumed silica (B) and 1.5 to 2% for colloidal calcium carbonate (C). 5% by mass.
  • the remainder is sodium bicarbonate (A), except where there is a small amount of additive.
  • the content ratio of the hydrophobic fumed silica (B) is 0.2% by mass or more, the discharge from the silo is sufficiently improved, and if it is 0.5% by mass or less. No problems such as clogging of filter cloth occur.
  • the content ratio of the colloidal calcium carbonate (C) is less than 1.5% by mass, the rupture stress of the powder layer becomes large and a sufficient effect cannot be obtained. The effect obtained is not changed.
  • the average particle size of the acidic component remover is 3 to 20 ⁇ m, preferably 5 to 10 ⁇ m. If the average particle size of the acidic component remover is 3 ⁇ m or more, sufficient fluidity can be obtained by using hydrophobic fumed silica (B) and colloidal calcium carbonate (C) in combination. Moreover, the problem that the particle diameter is too small to pass through the filter cloth can be avoided. If the average particle diameter of the acidic component remover is 20 ⁇ m or less, the acidic component in the exhaust gas can be efficiently removed.
  • the average particle diameter of the acidic component remover is an average particle diameter on a volume basis measured using a laser diffraction / scattering particle size distribution measuring apparatus (for example, Microtrack FRA9220 manufactured by Nikkiso Co., Ltd.).
  • a laser diffraction / scattering particle size distribution measuring apparatus for example, Microtrack FRA9220 manufactured by Nikkiso Co., Ltd.
  • the average particle diameter is simply referred to, it means a value measured by this method using ethanol as a medium.
  • the breaking stress of the powder layer of the acidic component remover is preferably 300 mN or less, and more preferably 250 mN or less.
  • the breaking stress of the powder layer of the acidic component removing agent is an indicator of the consolidation strength of the powder layer inside the facility for temporarily storing a powder such as a silo and the ease of collapse. That is, if the breaking stress of the powder layer is 300 mN or less, the filtration layer deposited on the surface of the filter cloth is unlikely to fall off, and the filtration layer is subjected to backwashing (backwashing) on the filter cloth.
  • the breaking stress of the powder layer is small, but if it is too small, it is difficult to form a filtration layer on the surface of the filter cloth, and the function of removing acidic components in the exhaust gas is reduced or the chemical is wasted. Preferably it is.
  • the breaking stress of the powder layer of the acidic component removing agent can be obtained by measurement by a two-part cell method using a suspended powder layer adhesion measuring device (manufactured by Hosokawa Micron Corp., Kochi Tester CT-2 type).
  • the numerical value obtained by the filter cloth residual pressure loss test method described later is preferably 150 Pa or less, more preferably 125 Pa or less, and 100 Pa or less. More preferably, If the residual pressure loss in the filter cloth is 150 Pa or less, the degree of penetration of the acid component remover particles into the gaps between the fibers constituting the filter cloth of the bag filter is small, and the bag filter can be stably operated for a long time. However, if the residual pressure loss is too small, it is difficult to form a filtration layer on the surface of the filter cloth, and the function of removing acidic components in the exhaust gas is reduced or the chemical is wasted.
  • Leakage concentration of the acidic component removal agent from the filter cloth is preferably from 15 mg / Nm 3 or less, 5 mg / Nm 3 or less is more preferable. Most preferably, there is no leakage of the acidic component remover from the filter cloth, but if the leakage concentration is 15 mg / Nm 3 or less, the burden on the living environment due to discharged dust can be suppressed to a low level.
  • Residual pressure drop in filter cloth and leakage concentration of acid component remover from filter cloth were established in 2007 in accordance with DIN (German Federal Standard established by German Standards Association) Dust Collection Performance Tester (Filter MediaTester) Further, it can be obtained by measurement with an apparatus conforming to JIS Z8909-1 (test method for dust collecting filter cloth).
  • Gas containing an acidic component that can be treated with the acidic component remover obtained by the production method of the present invention includes hydrogen chloride from incinerators such as general waste (city waste), industrial waste, and medical waste, Exhaust gas containing hydrogen fluoride, sulfur oxide (sulfur dioxide), etc .; Exhaust gas containing sulfur oxide (sulfur dioxide, sulfur trioxide, sulfuric acid), nitrogen oxides, etc. from boilers; As impurities in the manufacturing process of various products Examples thereof include a gas in which an acidic substance is mixed as a component.
  • the temperature of the gas containing the acidic component is preferably higher than the dew point of the acid (the acid dew point is a temperature at which the acidic component is liquefied in combination with moisture in the exhaust gas).
  • the acid dew point is a temperature at which the acidic component is liquefied in combination with moisture in the exhaust gas.
  • a low temperature is preferable from the viewpoint of suppressing the production of dioxins, specifically 100 to 200 ° C. is preferable.
  • 150 to 250 ° C. is preferable from the viewpoint of the efficiency of removing acidic components and the viewpoint of heat recovery efficiency for effectively using the heat of the combustion exhaust gas.
  • the acidic component remover obtained by the production method of the present invention is contained in a gas containing an acidic component.
  • a method of collecting and reacting with a bag filter or the like after supplying and dispersing in a flue gas from a silo or the like once stored, or placing an acidic component remover on the flue gas flow to form a filter cloth on the bag filter A method of reacting when exhaust gas passes through the filtered layer, or a combination thereof, is preferable. In general, an efficient combination method is generally employed.
  • a commonly used rotary valve or table feeder can be used without any problem.
  • an acidic component removing device in the exhaust gas as shown in FIG. 1 may be used.
  • the filtration layer of the acidic component removing agent is formed on the surface of the filter cloth of the bag filter, the acidic component can be efficiently removed.
  • the acidic component remover obtained by the production method of the present invention described above contains hydrophobic fumed silica (B) and colloidal calcium carbonate (C), so that the fluidity of the acidic component remover is moderate. And agglomeration due to aggregation can be suppressed. Moreover, since it contains colloidal calcium carbonate (C), solidification of particles constituting the acidic component remover can be prevented. Thus, since it has moderate fluidity
  • Patent Document 4 it was considered that magnesium carbonate was superior to calcium carbonate and hydrophilic fumed silica was superior to hydrophobic fumed silica.
  • hydrophobic fumed silica (B) It turned out that the combination with the colloidal calcium carbonate (C) whose average particle diameter of a primary particle is 50 nm or less is the most excellent. This is because the oil absorption amount of colloidal calcium carbonate (C) having an average primary particle size of 50 nm or less during mixing and pulverization operations is large, that is, the void ratio in the secondary particles is high, so that the primary particles are more This is thought to be due to being easily crushed.
  • fumed silica is spherical and slippery, and is particularly effective as a fluidizing agent for hydrophobic fumed silica (B), but sometimes it tends to be “too effective”, such as clogging the eyes of a bag filter.
  • primary particles of colloidal calcium carbonate (C) having an average primary particle diameter of 50 nm or less are irregular shapes such as cubes and spindles, and the same phenomenon is unlikely to occur. I think.
  • the degree of hydrophobicity of the hydrophobic fumed silica was measured with a combustion type carbon content measuring device (CN analyzer (SUMIGRAPH NC-80)). Specifically, helium and oxygen are passed through the combustion furnace in this order, the temperature in the combustion furnace is raised to 800 ° C., and 20 to 30 mg of a measurement sample is weighed into a quartz cell and placed in the combustion furnace. After burning in the furnace for 1 minute, the generated gas was measured with a CN analyzer to determine the carbon content in the sample, and this was used as the degree of hydrophobicity.
  • CN analyzer SUMIGRAPH NC-80
  • the vertical load (W) and shear load (W1 to W3) used in the test were determined as shown in Table 1 according to the bulk specific gravity of the test powder. Pre-consolidation was performed by applying a vertical load to the upper lid of the lower fixed type shear cell packed with the acidic component removing agent, and the mixture was sheared to a steady value while the same vertical load was applied, followed by consolidation. Thereafter, according to Table 1, the shear stress was measured while applying a shear load, plotted to obtain a fracture envelope, and the adhesive force of the acidic component remover was determined from the intercept of the fracture envelope.
  • the vertical load (W) and shear load (W1 to W4) used in the test were determined as shown in Table 2 according to the bulk specific gravity of the test powder. Pre-consolidation by applying a vertical load to the top of a shearing cell made of stainless steel SUS316 and packed with an acidic component remover, and then measuring the shear stress while applying the shear load according to Table 2, and plotting The wall destruction envelope was obtained. The wall friction angle with the stainless steel SUS316 was obtained from the inclination of the wall fracture envelope.
  • a breaking stress test was conducted using a suspended powder layer adhesion measuring device (manufactured by Hosokawa Micron Corporation, Kohitsta CT-2 type), and the breaking stress of the acidic component removing agent was determined as follows.
  • Residual pressure loss and leakage concentration were determined in the following manner using a dust collection performance test apparatus based on JIS Z8909-1 (test method for dust collection filter cloth).
  • leak concentration Furthermore, the leak concentration from the filter cloth was calculated from the amount of powder captured by an absolute filter installed at the subsequent stage of the test filter and the amount of passing gas.
  • (Raw material powder) (A1): highly reactive slaked lime (average particle diameter by laser diffraction / scattering particle size distribution analyzer: 9 ⁇ m, BET specific surface area: 45 m 2 / g).
  • C1 Basic magnesium carbonate (average particle diameter by a laser diffraction / scattering particle size distribution analyzer: 7 ⁇ m).
  • C2 Colloidal calcium carbonate (average particle diameter of primary particles: 20 nm, BET specific surface area: 49 m 2 / g, boiled linseed oil absorption: 85 mL / 100 g).
  • C3 Colloidal calcium carbonate (average particle diameter of primary particles: 80 nm, BET specific surface area: 18 m 2 / g, boiled linseed oil absorption: 25 mL / 100 g).
  • the average particle diameter of an acidic component removal agent is an average particle diameter in the volume reference
  • Adhesive force is an index of mutual adhesive force between powders of the acidic component remover, and is preferably smaller.
  • the wall friction angle is an index of the mutual adhesive force between the acidic component removing agent and the container, and is preferably smaller.
  • the hopper inclination angle is an angle ⁇ of the silo bottom face inclination required for stable discharge of the powder from the silo described in FIG. 4, and a larger one is easier to handle.
  • the outlet diameter is the diameter of the silo outlet required for stable discharge of the acidic component remover from the silo, and is preferably smaller.
  • the breaking stress reflects the ease of collapse of the powder layer during compaction, and is an indicator of the ease with which the filter layer deposited on the surface of the filter cloth can be removed and the ease of discharge from storage facilities such as silos. The smaller one is preferable. It can be seen that the acidic component removers of Examples 3 to 8 show excellent results in all evaluation items.
  • the comparative example 12 is the same composition as Example 13 in patent document 4, the value of a residual pressure loss differs. This is because, in Patent Document 4, the apparatus conforms to German standards, whereas in this specification, measurement is performed using an apparatus conforming to JIS standards.
  • the acidic component remover obtained in Example 4 was temporarily stored in a silo provided with an aeration nozzle (M-Technique, Fluidizer) as a powder fluidization measure, and discharged with a table feeder.
  • aeration nozzle M-Technique, Fluidizer
  • the acidic component removing agent was stably discharged from the silo, and hydrogen chloride was stably removed.
  • stable operation was obtained without any problems with the bug filter.
  • Acidic component remover obtained by the production method of the present invention includes hydrogen chloride, sulfur dioxide, etc. in exhaust gas from refuse incinerators, sulfur dioxide, sulfur trioxide, sulfuric acid, etc. in exhaust gas from boilers, etc .; It is useful for removing acidic components in various gases.
  • the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2010-208383 filed on September 16, 2010 are cited herein as disclosure of the specification of the present invention. Incorporated.

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JP2016150274A (ja) * 2015-02-16 2016-08-22 公立大学法人大阪府立大学 排ガス処理方法及び排ガス処理装置
EP3027292A4 (en) * 2013-10-04 2016-10-12 Marsulex Environmental Tech CIRCULATING DRY SCRUBBER SYSTEM AND METHOD
JP2017094266A (ja) * 2015-11-24 2017-06-01 栗田工業株式会社 酸性ガス処理剤および酸性ガス処理方法
WO2018012434A1 (ja) * 2016-07-12 2018-01-18 旭硝子株式会社 酸性成分除去剤、その製造方法および酸性成分除去方法
CN111001291A (zh) * 2019-12-19 2020-04-14 哈尔滨蔚蓝环保设备制造有限公司 一种炉外钠基干法脱硫装置及方法
CN111888925A (zh) * 2020-08-03 2020-11-06 北京予知环保科技有限公司 干法脱硫组件、脱硫除尘单元、一体化设备、系统
CN112495156A (zh) * 2020-09-30 2021-03-16 山东大学 一种降低三氧化硫及氯化氢排放的工艺及系统
CN114452791A (zh) * 2021-12-29 2022-05-10 深圳华明环保科技有限公司 一种含二氧化硫的气体的脱酸方法
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Publication number Priority date Publication date Assignee Title
EP3027292A4 (en) * 2013-10-04 2016-10-12 Marsulex Environmental Tech CIRCULATING DRY SCRUBBER SYSTEM AND METHOD
JP2016150274A (ja) * 2015-02-16 2016-08-22 公立大学法人大阪府立大学 排ガス処理方法及び排ガス処理装置
JP2017094266A (ja) * 2015-11-24 2017-06-01 栗田工業株式会社 酸性ガス処理剤および酸性ガス処理方法
WO2018012434A1 (ja) * 2016-07-12 2018-01-18 旭硝子株式会社 酸性成分除去剤、その製造方法および酸性成分除去方法
CN111001291A (zh) * 2019-12-19 2020-04-14 哈尔滨蔚蓝环保设备制造有限公司 一种炉外钠基干法脱硫装置及方法
CN111888925A (zh) * 2020-08-03 2020-11-06 北京予知环保科技有限公司 干法脱硫组件、脱硫除尘单元、一体化设备、系统
CN112495156A (zh) * 2020-09-30 2021-03-16 山东大学 一种降低三氧化硫及氯化氢排放的工艺及系统
CN114452791A (zh) * 2021-12-29 2022-05-10 深圳华明环保科技有限公司 一种含二氧化硫的气体的脱酸方法
CN115445686A (zh) * 2022-09-01 2022-12-09 青岛康禾园绿色食品有限公司 一种肉类营养成分检测设备

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