JP2018122248A - Acidic gas treatment agent - Google Patents

Acidic gas treatment agent Download PDF

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JP2018122248A
JP2018122248A JP2017016548A JP2017016548A JP2018122248A JP 2018122248 A JP2018122248 A JP 2018122248A JP 2017016548 A JP2017016548 A JP 2017016548A JP 2017016548 A JP2017016548 A JP 2017016548A JP 2018122248 A JP2018122248 A JP 2018122248A
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acid gas
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JP6350690B1 (en
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恵一 水品
Keiichi Mizushina
恵一 水品
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Kurita Water Industries Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • 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
    • 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
    • B01D53/68—Halogens or halogen compounds
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size

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Abstract

PROBLEM TO BE SOLVED: To provide an acidic gas treatment agent that can treat an acidic gas efficiently by small-quantity application of it; can significantly improve solidification properties and prevent a difference pressure rise in a bag filter; and also is excellent in terms of cost.SOLUTION: An acidic gas treatment agent contains sodium bicarbonate. The sodium bicarbonate has a median size (D) of 11 μm or more and 25 μm or less, with the ratio of a modal diameter (D) to the median size (D/D) being 2.0 or less. The difference between the median size (D) and an integrated weight 30% diameter (D) is 15 μm or less, preferably, and the difference between the integrated weight 70% diameter (D) and the median size (D) is 15 μm or less, preferably.SELECTED DRAWING: Figure 1

Description

本発明は、酸性ガス処理剤に関する。より詳しくは、本発明は、一般廃棄物や産業廃棄物を焼却、焼成あるいは溶融する施設や、バイオマス発電ボイラ等から排出される燃焼排ガスに含まれる塩化水素や硫黄酸化物等の酸性ガスを中和処理する酸性ガス処理剤に関する。   The present invention relates to an acid gas treating agent. More specifically, the present invention provides an acidic gas such as hydrogen chloride and sulfur oxide contained in combustion exhaust gas discharged from facilities for incineration, firing or melting of general waste and industrial waste, biomass power generation boilers, and the like. The present invention relates to an acid gas treating agent to be summed.

廃棄物処理施設や発電ボイラなどの施設では、塩化水素や硫黄酸化物等の酸性ガスが発生し、これらの酸性ガスを中和処理するために、消石灰などのカルシウム系化合物が用いられてきた。   In facilities such as waste treatment facilities and power generation boilers, acidic gases such as hydrogen chloride and sulfur oxides are generated, and calcium-based compounds such as slaked lime have been used to neutralize these acidic gases.

しかしながら、酸性ガス処理剤として、ＪＩＳ特号消石灰や高反応消石灰を用いた場合、酸性ガスに対して、３〜４倍当量と過剰に使用する必要があるため、発生する煤塵量が増加し、飛灰処理コストの増加や最終処分場の容量を圧迫する欠点がある。また、硫黄酸化物が特異的に高い施設や塩化水素、硫黄酸化物の基準値が１５ｐｐｍ以下と湿式レベルに厳しい施設においては、安定的に処理できない欠点もある。   However, when JIS special slaked lime or highly reactive slaked lime is used as the acid gas treating agent, it is necessary to use it in excess of 3 to 4 times equivalent to the acid gas, so the amount of generated dust increases, There are disadvantages that increase the fly ash treatment cost and the capacity of the final disposal site. In addition, there is a drawback in that it cannot be stably processed in a facility where sulfur oxide is specifically high, or in a facility where the reference value of hydrogen chloride or sulfur oxide is strict at a wet level of 15 ppm or less.

そこで、炭酸水素ナトリウムなどのナトリウム系化合物もまた、酸性ガス処理剤として一般的に用いられ、普及している。炭酸水素ナトリウムは、上記消石灰と比較すると、使用量が少なくて済む。   Therefore, sodium compounds such as sodium hydrogen carbonate are also commonly used as an acid gas treating agent and are widely used. The amount of sodium bicarbonate used is less than that of the slaked lime.

例えば、特許文献１では、レーザー回折散乱法により測定した体積基準の平均粒径が１〜９μｍの炭酸水素ナトリウムを含む酸性成分除去剤が提案されている。この除去剤によると、排気ガスから効率良く塩化水素や硫黄酸化物や窒素酸化物等の酸性成分を除去でき、かつ、廃棄処理も容易で廃棄物量を削減できる。   For example, Patent Document 1 proposes an acidic component removing agent containing sodium hydrogen carbonate having a volume-based average particle diameter measured by a laser diffraction scattering method of 1 to 9 μm. According to this remover, acidic components such as hydrogen chloride, sulfur oxide, and nitrogen oxide can be efficiently removed from the exhaust gas, and the disposal process is easy and the amount of waste can be reduced.

特許文献２では、レーザー回折散乱法により測定した体積基準の平均粒径が１〜９μｍであって、粉体層の水銀圧入法による細孔分布において、細孔直径１〜１０μｍの範囲の細孔容積が０．４ｃｍ３／ｇ以上である炭酸水素ナトリウムを含む酸性成分除去剤が提案されている。この除去剤によると、少量の酸性成分除去剤で充分に塩化水素ガスを吸着除去できる。 In Patent Document 2, the volume-based average particle diameter measured by the laser diffraction scattering method is 1 to 9 μm, and the pore diameter is 1 to 10 μm in the pore distribution by the mercury intrusion method of the powder layer. An acidic component remover containing sodium hydrogen carbonate having a volume of 0.4 cm 3 / g or more has been proposed. According to this removing agent, hydrogen chloride gas can be sufficiently removed by adsorption with a small amount of acidic component removing agent.

特開２０００−２１８１２８号公報JP 2000-218128 A 特開２００６−２３９６８９号公報Japanese Patent Laid-Open No. 2006-239689

特許文献１〜２に記載の処理剤は、いずれも、炭酸水素ナトリウムの平均粒子径が１０μｍ以下であることが好ましいとしている。しかしながら、炭酸水素ナトリウムが微粒子であると、微粒子同士が凝集して固結し易いことや、微粒子にするための粉砕コストや粉砕時間を多大に要するという課題がある。   In any of the treatment agents described in Patent Documents 1 and 2, the average particle size of sodium hydrogen carbonate is preferably 10 μm or less. However, when sodium hydrogen carbonate is a fine particle, there are problems that the fine particles are easily aggregated and solidified, and that a pulverization cost and a pulverization time for making the fine particle are required.

微粒子同士の凝集を防ぐために、炭酸水素ナトリウムに固結防止剤を配合することも考えられるが、炭酸水素ナトリウムに固結防止剤を配合しても、輸送時や薬剤貯留時に酸性ガス処理剤が固結する場合がある。また、固結防止剤の配合比を高くすると、今度は、コストアップの課題が生じる。   In order to prevent agglomeration between fine particles, it is conceivable to add an anti-caking agent to sodium hydrogen carbonate, but even if an anti-caking agent is added to sodium hydrogen carbonate, the acid gas treatment agent is not used during transportation or storage of the drug. May consolidate. Moreover, when the compounding ratio of the anti-caking agent is increased, a problem of cost increase arises.

また、炭酸水素ナトリウムの平均粒子径が小さいと、排ガスを浄化するためのバグフィルタにおける差圧が上昇し、ろ布の耐久性に課題がある。   Moreover, when the average particle diameter of sodium hydrogencarbonate is small, the differential pressure | voltage in the bag filter for purifying exhaust gas will rise, and there exists a subject in durability of a filter cloth.

本発明は、このような問題に鑑みてなされたものであり、その課題は、少量であっても酸性ガスを効率的に処理できるとともに、固結性やバグフィルタにおける差圧上昇を大幅に改善でき、コスト面にも優れた酸性ガス処理剤を提供することである。   The present invention has been made in view of such problems, and the problem is that acid gas can be efficiently processed even with a small amount, and the caking property and the differential pressure increase in the bag filter are greatly improved. It is possible to provide an acid gas treating agent that is also excellent in cost.

本発明者らは、上記の課題を達成するために鋭意研究を重ねた結果、メジアン径に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）に着目し、この比の範囲を一定の範囲内にすることで、上記の課題を一挙に解決できることを見出し、本発明を完成するに至った。具体的に、本発明では、以下のようなものを提供する。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors pay attention to the ratio of the mode diameter (D m ) to the median diameter (D m / D 50 ), and the range of this ratio is kept constant. By making it within the range, it was found that the above problems could be solved at once, and the present invention was completed. Specifically, the present invention provides the following.

（１）本発明は、メジアン径（Ｄ５０）が１１μｍ以上２５μｍ以下であり、前記メジアン径に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）が２．０以下である炭酸水素ナトリウムを含有する酸性ガス処理剤である。ここで、メジアン径（Ｄ５０）は、レーザー回折散乱式粒度分布測定装置によって測定された粒度分布における質量基準における積算値が５０％となる粒子径である。また、モード径（Ｄｍ）は、レーザー回折散乱式粒度分布測定装置によって測定された粒度分布における相対粒子量が最大となる粒子径である。 (1) The present invention is a sodium hydrogen carbonate having a median diameter (D 50 ) of 11 μm or more and 25 μm or less, and a ratio of the mode diameter (D m ) to the median diameter (D m / D 50 ) of 2.0 or less. Is an acid gas treating agent containing Here, the median diameter (D 50 ) is a particle diameter at which the integrated value on the mass basis in the particle size distribution measured by the laser diffraction / scattering particle size distribution measuring device is 50%. The mode diameter (D m ) is a particle diameter at which the relative particle amount in the particle size distribution measured by the laser diffraction / scattering particle size distribution measuring device is maximized.

（２）また、本発明は、前記炭酸水素ナトリウムの前記メジアン径（Ｄ５０）と積算重量３０％径（Ｄ３０）との差が１５μｍ以下であり、前記炭酸水素ナトリウムの積算重量７０％径（Ｄ７０）と前記メジアン径（Ｄ５０）との差が１５μｍ以下である、（１）に記載の酸性ガス処理剤である。ここで、積算重量３０％径（Ｄ３０）は、レーザー回折散乱式粒度分布測定装置によって測定された粒度分布における質量基準における積算値が３０％となる粒子径である。また、積算重量７０％径（Ｄ７０）は、レーザー回折散乱式粒度分布測定装置によって測定された粒度分布における質量基準における積算値が７０％となる粒子径である。 (2) Further, in the present invention, the difference between the median diameter (D 50 ) of the sodium hydrogen carbonate and the accumulated weight 30% diameter (D 30 ) is 15 μm or less, and the accumulated weight 70% diameter of the sodium hydrogen carbonate The acid gas treating agent according to (1), wherein a difference between (D 70 ) and the median diameter (D 50 ) is 15 μm or less. Here, the cumulative weight 30% diameter (D 30 ) is a particle diameter at which the cumulative value on the mass basis in the particle size distribution measured by the laser diffraction / scattering particle size distribution measuring device is 30%. Further, the cumulative weight 70% diameter (D 70 ) is a particle diameter at which the cumulative value on the mass basis in the particle size distribution measured by the laser diffraction / scattering particle size distribution measuring device is 70%.

（３）また、本発明は、固結防止剤をさらに含有し、前記固結防止剤は、親水性物質、疎水性物質、及び粘土鉱物から選択される少なくとも１種以上を含む、（１）又は（２）に記載の酸性ガス処理剤である。   (3) The present invention further includes an anti-caking agent, and the anti-caking agent includes at least one selected from a hydrophilic substance, a hydrophobic substance, and a clay mineral, (1) Or it is an acidic gas processing agent as described in (2).

（４）また、本発明は、前記固結防止剤が、湿式シリカ、ステアリン酸カルシウム、ゼオライト、疎水性シリカ、親水性ヒュームドシリカ、ホワイトカーボン、塩基性炭酸マグネシウム、カーボンブラックのいずれか１種以上を含む、（３）に記載の酸性ガス処理剤である。   (4) Further, in the present invention, the anti-caking agent is one or more of wet silica, calcium stearate, zeolite, hydrophobic silica, hydrophilic fumed silica, white carbon, basic magnesium carbonate, and carbon black. It is an acidic gas processing agent as described in (3) containing.

（５）また、本発明は、（１）から（４）のいずれかに記載の酸性ガス処理剤を酸性ガスに添加した後、飛灰を集塵する、酸性ガス処理方法である。   (5) Moreover, this invention is an acidic gas processing method of collecting fly ash after adding the acidic gas processing agent in any one of (1) to (4) to acidic gas.

本発明によると、少量であっても酸性ガスを効率的に処理できるとともに、固結性やバグフィルタにおける差圧上昇を大幅に改善でき、コスト面にも優れた酸性ガス処理剤を提供することができる。   According to the present invention, it is possible to efficiently process acid gas even in a small amount, and to significantly improve the caking property and the differential pressure increase in the bag filter, and to provide an acid gas treating agent excellent in cost. Can do.

本実施例で使用した酸性ガス処理装置１０の概略構成を示す。The schematic structure of the acidic gas processing apparatus 10 used by the present Example is shown. 酸性ガス処理剤の固結性を評価するために使用した荷重試験装置３０の概略構成を示す。The schematic structure of the load test apparatus 30 used in order to evaluate the caking property of an acidic gas processing agent is shown.

以下、本発明の具体的な実施形態について、詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。   Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

＜酸性ガス処理剤＞
本実施形態の酸性ガス処理剤は、炭酸水素ナトリウムを含有する。炭酸水素ナトリウムは、酸性ガスの中和剤として機能する。 <Acid gas treatment agent>
The acidic gas treating agent of this embodiment contains sodium hydrogen carbonate. Sodium bicarbonate functions as a neutralizing agent for acid gas.

また、酸性ガス処理剤は、必要に応じて、固結防止剤をさらに含有することが好ましい。   Moreover, it is preferable that an acidic gas processing agent further contains an anti-caking agent as needed.

〔炭酸水素ナトリウム〕
［メジアン径（Ｄ５０）］
炭酸水素ナトリウムは、粗重曹を粉砕したものが好ましく用いられる。炭酸水素ナトリウムのメジアン径（Ｄ５０）の下限は、１１μｍ以上であり、１２．５μｍ以上であることが好ましく、１５μｍ以上であることがさらに好ましく、１７μｍ以上であることが特に好ましい。メジアン径（Ｄ５０）が小さすぎると、炭酸水素ナトリウムの微粒子どうしが凝集して固結し易いため、好ましくない。また、炭酸水素ナトリウムを微粒子にするための粉砕コストや粉砕時間が多大になるため、好ましくない。加えて、メジアン径（Ｄ５０）が小さすぎると、排ガスを浄化するためのバグフィルタにおける差圧が上昇し、ろ布の耐久性に影響を及ぼし得るため、好ましくない。 〔sodium hydrogen carbonate〕
[Median diameter (D 50)]
Sodium bicarbonate obtained by pulverizing crude sodium bicarbonate is preferably used. The lower limit of the median diameter (D 50 ) of sodium hydrogen carbonate is 11 μm or more, preferably 12.5 μm or more, more preferably 15 μm or more, and particularly preferably 17 μm or more. If the median diameter (D 50 ) is too small, the sodium hydrogen carbonate fine particles are likely to aggregate and solidify, which is not preferable. Moreover, since the grinding | pulverization cost and grinding | pulverization time for making sodium hydrogen carbonate into a fine particle become large, it is not preferable. In addition, if the median diameter (D 50 ) is too small, the differential pressure in the bag filter for purifying exhaust gas increases, which may affect the durability of the filter cloth, which is not preferable.

炭酸水素ナトリウムのメジアン径（Ｄ５０）の上限は、２５μｍ以下であり、２１μｍ以下であることが好ましく、１９．５μｍ以下であることがさらに好ましい。メジアン径（Ｄ５０）が大きすぎると、酸性ガスを処理するために必要な炭酸ナトリウムの量が、バグフィルタ入口の酸性ガスの濃度に対する好適な当量比の範囲（例えば、１．０以上５．０以下）から外れるため、好ましくない。 The upper limit of the median diameter (D 50 ) of sodium hydrogen carbonate is 25 μm or less, preferably 21 μm or less, and more preferably 19.5 μm or less. When the median diameter (D 50 ) is too large, the amount of sodium carbonate required for treating the acid gas is within a range of a suitable equivalent ratio with respect to the concentration of the acid gas at the bag filter inlet (for example, 1.0 or more and 5. 0 or less), which is not preferable.

［メジアン径（Ｄ５０）に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）］
炭酸水素ナトリウムのメジアン径（Ｄ５０）に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）は、２．０以下であり、１．５以下であることが好ましく、１．３以下であることがより好ましい。比（Ｄｍ／Ｄ５０）が大きいと、メジアン径（Ｄ５０）が適正な範囲内にあっても、酸性ガスを十分に処理することができない。 [Ratio of mode diameter (D m ) to median diameter (D 50 ) (D m / D 50 )]
The ratio of the mode diameter to the median size of the sodium hydrogen carbonate (D 50) (D m) (D m / D 50) is 2.0 or less, preferably 1.5 or less, 1.3 or less More preferably. If the ratio (D m / D 50 ) is large, the acidic gas cannot be sufficiently treated even if the median diameter (D 50 ) is within an appropriate range.

比（Ｄｍ／Ｄ５０）の下限は、特に限定されないが、モード径（Ｄｍ）の方がメジアン径（Ｄ５０）に比べて大きいため、比（Ｄｍ／Ｄ５０）の下限は、１．００以上である。 The lower limit of the ratio (D m / D 50 ) is not particularly limited, but since the mode diameter (D m ) is larger than the median diameter (D 50 ), the lower limit of the ratio (D m / D 50 ) is It is 1.00 or more.

［粒度分布のシャープさ］
炭酸水素ナトリウムのメジアン径（Ｄ５０）と積算重量３０％径（Ｄ３０）との差（Ｄ５０−Ｄ３０）の上限は、１５μｍ以下であることがが好ましく、１０μｍ以下であることがより好ましい。差（Ｄ５０−Ｄ３０）の下限は、特に限定されず、０μｍを超えていればよいが、製品歩留を高め、コスト面に優れた酸性ガス処理剤を提供するため、差（Ｄ５０−Ｄ３０）の下限は、１μｍ以上であることが好ましく、３μｍ以上であることがより好ましい。 [Sharpness of particle size distribution]
The upper limit of the difference (D 50 -D 30 ) between the median diameter (D 50 ) of sodium hydrogen carbonate and the 30% cumulative weight diameter (D 30 ) is preferably 15 μm or less, and more preferably 10 μm or less. preferable. The lower limit of the difference (D 50 -D 30 ) is not particularly limited as long as it exceeds 0 μm. However, in order to increase the product yield and provide an acid gas treating agent excellent in cost, the difference (D 50 The lower limit of −D 30 ) is preferably 1 μm or more, and more preferably 3 μm or more.

炭酸水素ナトリウムの積算重量７０％径（Ｄ７０）とメジアン径（Ｄ５０）との差（Ｄ７０−Ｄ５０）の上限は、１５μｍ以下であることが好ましく、１０μｍ以下であることがより好ましい。差（Ｄ７０−Ｄ５０）の下限は、特に限定されず、０μｍを超えていればよいが、製品歩留を高め、コスト面に優れた酸性ガス処理剤を提供するため、差（Ｄ７０−Ｄ５０）の下限は、１μｍ以上であることが好ましく、３μｍ以上であることがより好ましく、５μｍ以上であることがさらに好ましい。 The upper limit of the difference (D 70 -D 50 ) between the cumulative weight 70% diameter (D 70 ) and the median diameter (D 50 ) of sodium hydrogen carbonate is preferably 15 μm or less, and more preferably 10 μm or less. . The lower limit of the difference (D 70 -D 50 ) is not particularly limited as long as it exceeds 0 μm. However, in order to increase the product yield and provide an acid gas treating agent excellent in cost, the difference (D 70 The lower limit of −D 50 ) is preferably 1 μm or more, more preferably 3 μm or more, and further preferably 5 μm or more.

粒度分布がシャープであることによって、酸性ガスの処理性能が高まる。また、粒度分布がシャープであることによって、酸性ガス処理剤の固結を抑えることができ、結果として装置のハンドリング性能が高まる。   Due to the sharp particle size distribution, the acid gas treatment performance is enhanced. Further, since the particle size distribution is sharp, solidification of the acid gas treating agent can be suppressed, and as a result, the handling performance of the apparatus is enhanced.

〔固結防止剤〕
酸性ガス処理剤が固結し、流動性が低下するのを防ぐため、酸性ガス処理剤は、炭酸水素ナトリウムと、固結防止剤とを含有することが好ましい。 [Anti-caking agent]
In order to prevent the acidic gas treating agent from solidifying and lowering the fluidity, the acidic gas treating agent preferably contains sodium hydrogen carbonate and an anti-caking agent.

固結防止剤は、親水性物質、疎水性物質、及び粘土鉱物から選択される少なくとも１種以上を含むことが好ましい。   The anti-caking agent preferably contains at least one selected from a hydrophilic substance, a hydrophobic substance, and a clay mineral.

本実施形態において、「親水性」とは、水に非溶解性であるものの、物質表面に親水性基を有しており、物質表面が水に濡れやすい（水滴をつくらない、はじかない）性質を有する物質をいう。親水性物質として、親水性シリカ（親水性ヒュームドシリカ等）が挙げられる。   In the present embodiment, the term “hydrophilic” means a property that is insoluble in water but has a hydrophilic group on the surface of the substance, and the surface of the substance is easily wetted with water (does not form water droplets or repels). A substance having Examples of the hydrophilic substance include hydrophilic silica (hydrophilic fumed silica and the like).

本実施形態において、「疎水性」とは、水に非溶解性であり、かつ、物質表面に親水性基を有していない物質をいう。疎水性物質として、ステアリン酸カルシウム、疎水性シリカ等が挙げられる。   In the present embodiment, “hydrophobic” refers to a substance that is insoluble in water and does not have a hydrophilic group on the substance surface. Examples of the hydrophobic substance include calcium stearate and hydrophobic silica.

粘土鉱物として、ゼオライト、珪藻土、活性白土等が挙げられる。   Examples of clay minerals include zeolite, diatomaceous earth, and activated clay.

中でも、固結防止性に優れることから、固結防止剤は、ステアリン酸カルシウムを含んでいることが好ましい。   Especially, since it is excellent in anti-caking property, it is preferable that the anti-caking agent contains calcium stearate.

その他、ホワイトカーボン、塩基性炭酸マグネシウム、カーボンブラック、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、クエン酸アンモニウム、無水硫酸マグネシウム、無水リン酸ソーダ、高炉スラグ、酸化アルミニウム等、周知の固結防止剤が含まれていてもよい。   Other known anti-caking agents such as white carbon, basic magnesium carbonate, carbon black, calcium carbonate, magnesium carbonate, magnesium hydroxide, ammonium citrate, anhydrous magnesium sulfate, anhydrous sodium phosphate, blast furnace slag, aluminum oxide, etc. It may be included.

固結防止剤を含有させる場合、その含有量の下限は、酸性ガス処理剤が固結し、流動性が低下するのを防ぐことができる程度であれば、特に限定されない。例えば、固結防止剤の含有量は、炭酸水素ナトリウム１００質量部に対して０．１質量部以上であることが好ましく、０．２質量部以上であることがより好ましい。   When the anti-caking agent is contained, the lower limit of the content is not particularly limited as long as the acid gas treating agent is caking and the fluidity can be prevented from lowering. For example, the content of the anti-caking agent is preferably 0.1 parts by mass or more and more preferably 0.2 parts by mass or more with respect to 100 parts by mass of sodium bicarbonate.

含有量の上限は、脱塩残渣の処理に影響を及ぼさない程度であれば、特に限定されない。例えば、固結防止剤の含有量は、炭酸水素ナトリウム１００質量部に対して３．０質量部以下であることが好ましく、１．０質量部以下であることがより好ましく、０．８質量部以下であることがさらに好ましく、０．６質量部以下であることがよりさらに好ましい。   The upper limit of the content is not particularly limited as long as it does not affect the treatment of the desalted residue. For example, the content of the anti-caking agent is preferably 3.0 parts by mass or less, more preferably 1.0 part by mass or less, and 0.8 parts by mass with respect to 100 parts by mass of sodium bicarbonate. Or less, more preferably 0.6 parts by mass or less.

＜酸性ガス処理剤の調製方法＞
酸性ガス処理剤の調製は、以下の工程を経ることによって得ることができる。
（１）粗重曹（粒径が大きい重曹）の粉砕
（２）必要に応じて、粉砕した重曹（炭酸水素ナトリウム）と固結防止剤との混合 <Method for preparing acid gas treating agent>
The preparation of the acid gas treating agent can be obtained through the following steps.
(1) Grinding of crude baking soda (sodium bicarbonate with a large particle size) (2) Mixing of ground baking soda (sodium bicarbonate) with an anti-caking agent as required

〔（１）粗重曹の粉砕〕
まず、粗重曹を粉砕し、メジアン径（Ｄ５０）、メジアン径（Ｄ５０）に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）等を規定の範囲内に調整する。メジアン径（Ｄ５０）等の調整は、粗重曹の原料の粒径や粗重曹の原料供給量に基づき、粉砕機における粉砕ローター、分級ローターの設定値を調整することによって行われる。 [(1) Crushed sodium bicarbonate]
First, the crude baking soda is pulverized, and the median diameter (D 50 ), the ratio of the mode diameter (D m ) to the median diameter (D 50 ) (D m / D 50 ), and the like are adjusted within specified ranges. The median diameter (D 50 ) and the like are adjusted by adjusting the setting values of the grinding rotor and classification rotor in the grinder based on the particle size of the raw material of crude sodium bicarbonate and the raw material supply amount of the crude sodium bicarbonate.

〔（２）粉砕した重曹（炭酸水素ナトリウム）と固結防止剤との混合〕
また、必要に応じて、粉砕した重曹（炭酸水素ナトリウム）と固結防止剤とを混合する。混合は、リボンブレンダーやナウターミキサー等の混合機を用いて混合してもよいし、粗重曹を粉砕する際に、固結防止剤も粗重曹と一緒に添加して混合してもよい。 [(2) Mixing of ground sodium bicarbonate (sodium bicarbonate) and anti-caking agent]
If necessary, pulverized baking soda (sodium hydrogen carbonate) and an anti-caking agent are mixed. Mixing may be performed by using a mixer such as a ribbon blender or a Nauta mixer, or when the crude baking soda is pulverized, an anti-caking agent may be added together with the crude baking soda and mixed.

＜酸性ガスの処理方法＞
酸性ガスの処理は、上記酸性ガス処理剤を、酸性ガスを含む排ガスに添加して排ガス処理を行うものである。上記酸性ガス処理剤を煙道に供給し、酸性ガス処理剤と、酸性ガスを含む排ガスとを接触させることによって行われる。 <Acid gas treatment method>
In the treatment of acid gas, the acid gas treating agent is added to exhaust gas containing acid gas to perform exhaust gas treatment. The acid gas treating agent is supplied to the flue, and the acid gas treating agent is brought into contact with the exhaust gas containing the acid gas.

排ガスの種類は特に限定されるものでなく、例えば、廃棄物処理施設やバイオマスボイラ、石炭ボイラ等の燃焼施設において発生する、塩化水素や硫黄酸化物等の酸性ガスを含む排出ガスが挙げられる。   The type of the exhaust gas is not particularly limited, and examples thereof include exhaust gas containing acid gas such as hydrogen chloride and sulfur oxide generated in a waste treatment facility, a combustion facility such as a biomass boiler and a coal boiler.

酸性ガス処理剤を供給するタイミングも、集塵機において飛灰を集塵する前であれば特に限定されるものでなく、例えば、焼却炉で廃棄物等を焼却するタイミング、焼却によって生成した排ガスが煙道を通過し、排ガスの温度を減温する減温塔に至るまでの間のタイミング、排ガスを減温塔で冷却した後、冷却後の排ガスが、集塵機手前に設けられたバグフィルタに至るまでのタイミング等が挙げられる。   The timing of supplying the acid gas treating agent is not particularly limited as long as it is before dust collection by the dust collector. For example, the timing of incineration of waste in an incinerator, the exhaust gas generated by incineration is smoke The timing between passing the road and reaching the temperature reduction tower that reduces the temperature of the exhaust gas, after cooling the exhaust gas in the temperature reduction tower, until the exhaust gas after cooling reaches the bag filter provided in front of the dust collector The timing of this is mentioned.

酸性ガス処理剤の供給量は、特に限定されるものでない。過少になること、過大になることのいずれも避けるため、煙道を通過する酸性ガスの濃度をモニタリングしながら適宜調整し、対象となる燃焼施設毎の管理目標値を満足するように供給することが好ましい。   The supply amount of the acid gas treating agent is not particularly limited. To avoid both excessive and excessive, adjust the concentration of acid gas passing through the flue while monitoring it appropriately and supply it to satisfy the management target value for each target combustion facility. Is preferred.

酸性ガスを好適に処理するため、酸性ガス処理剤の供給量の下限は、０．１ｇ／ｍ３以上であることが好ましく、１ｇ／ｍ３以上であることがより好ましく、１０ｇ／ｍ３以上であることがさらに好ましい。併せて、酸性ガス処理剤の供給量の下限は、バグフィルタ入口の酸性ガスの濃度に対して、当量比で１．０以上であることが好ましく、１．２以上であることがより好ましく、１．４以上であることがさらに好ましい。 In order to treat the acidic gas suitably, the lower limit of the supply amount of the acidic gas treating agent is preferably 0.1 g / m 3 or more, more preferably 1 g / m 3 or more, and 10 g / m 3 or more. More preferably. In addition, the lower limit of the supply amount of the acidic gas treating agent is preferably 1.0 or more, more preferably 1.2 or more in terms of equivalent ratio with respect to the concentration of acidic gas at the bag filter inlet, More preferably, it is 1.4 or more.

脱塩残渣の量を抑え、飛灰処理コストをできるだけ低くするため、酸性ガス処理剤の供給量の上限は、２００ｇ／ｍ３以下の範囲内であることが好ましく、１５０ｇ／ｍ３以下の範囲内であることがより好ましい。併せて、酸性ガス処理剤の供給量の上限は、バグフィルタ入口の酸性ガスの濃度に対して、当量比で５．０以下であることが好ましく、３．０以下であることがより好ましく、２．０以下であることがさらに好ましい。 In order to suppress the amount of desalting residue and reduce the fly ash treatment cost as much as possible, the upper limit of the supply amount of the acid gas treatment agent is preferably within the range of 200 g / m 3 or less, and the range of 150 g / m 3 or less More preferably, it is within. In addition, the upper limit of the supply amount of the acidic gas treating agent is preferably 5.0 or less, more preferably 3.0 or less in terms of equivalent ratio with respect to the concentration of acidic gas at the bag filter inlet, More preferably, it is 2.0 or less.

煙道に酸性ガス処理剤を供給した後、酸性ガスと酸性ガス処理剤との反応生成物及び未反応物をそれぞれ成分とする飛灰を集塵する。飛灰の集塵は、バグフィルタ等、公知の集塵機で行えばよい。   After supplying the acid gas treating agent to the flue, fly ash containing the reaction product of the acid gas and the acid gas treating agent and the unreacted material as components is collected. The fly ash may be collected by a known dust collector such as a bag filter.

以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるもので
はない。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

＜実施例１＞ 炭酸水素ナトリウムの粒度と酸性ガス処理性能及び固結性との関係
〔酸性ガス処理性能の比較〕
［試験条件］
図１に記載の酸性ガス処理装置１０を用いて、表１に記載された６種類の炭酸ナトリウムについて、酸性ガス処理性能を比較した。なお、炭酸ナトリウムの径は、島津製作所株式会社製のＳＡＬＤ−７５００ｎａｎｏを用いて測定した。 <Example 1> Relationship between particle size of sodium hydrogen carbonate and acid gas treatment performance and solidification properties
[Test conditions]
The acid gas treatment performance of the six types of sodium carbonate listed in Table 1 was compared using the acid gas treatment apparatus 10 shown in FIG. The diameter of sodium carbonate was measured using SALD-7500 nano manufactured by Shimadzu Corporation.

図１は、本実施例で使用した酸性ガス処理装置１０の概略構成を示す。酸性ガス処理装置１０は、酸性ガスを加熱するヒーター１１と、ヒーター１１から出される酸性ガスに酸性ガス処理剤を供給する酸性ガス処理剤供給機１３と、酸性ガスと酸性ガス処理剤との反応生成物及び未反応物を集塵するバグフィルタ１５と、バグフィルタ１５で集塵された集塵物を冷却する冷却塔１７と、冷却された集塵物を中和する中和塔１８と、中和塔１８で中和された中和物を系外に排出する誘引送風機１９とを備える。   FIG. 1 shows a schematic configuration of an acid gas processing apparatus 10 used in this embodiment. The acid gas treatment device 10 includes a heater 11 that heats the acid gas, an acid gas treatment agent supplier 13 that supplies the acid gas treatment agent to the acid gas that is output from the heater 11, and a reaction between the acid gas and the acid gas treatment agent. A bag filter 15 that collects the product and unreacted material, a cooling tower 17 that cools the dust collected by the bag filter 15, a neutralization tower 18 that neutralizes the cooled dust collection, And an induction blower 19 for discharging the neutralized product neutralized by the neutralization tower 18 to the outside of the system.

ヒーター１１から酸性ガス処理剤供給機１３に向かう配管１２において、バグフィルタ１５の入口に相当する箇所に圧力計Ｐ１と、塩化水素濃度測定装置とが設けられている。圧力計Ｐ１と、塩化水素濃度測定装置とにより、バグフィルタ１５の入口圧力と、酸性ガスに含まれる塩化水素濃度とが測定可能である。   A pressure gauge P1 and a hydrogen chloride concentration measuring device are provided at a position corresponding to the inlet of the bag filter 15 in the pipe 12 from the heater 11 to the acidic gas treating agent supply machine 13. The pressure gauge P1 and the hydrogen chloride concentration measuring device can measure the inlet pressure of the bag filter 15 and the concentration of hydrogen chloride contained in the acid gas.

また、バグフィルタ１５から冷却塔１７に向かう配管１６において、バグフィルタ１５の出口に相当する箇所に圧力計Ｐ２と、塩化水素濃度測定装置とが設けられている。圧力計Ｐ２と、塩化水素濃度測定装置とにより、バグフィルタ１５の出口圧力と、バグフィルタ１５で集塵された集塵物に含まれる塩化水素濃度とが測定可能である。   Further, a pressure gauge P2 and a hydrogen chloride concentration measuring device are provided at a location corresponding to the outlet of the bag filter 15 in the pipe 16 from the bag filter 15 to the cooling tower 17. The outlet pressure of the bag filter 15 and the hydrogen chloride concentration contained in the collected dust collected by the bag filter 15 can be measured by the pressure gauge P2 and the hydrogen chloride concentration measuring device.

なお、本実施例では、塩化水素測定装置として、京都電子社製イオン電極式塩化水素計ＨＬ−２２」を使用した。   In this example, an ion electrode type hydrogen chloride meter HL-22 manufactured by Kyoto Electronics Co., Ltd. was used as the hydrogen chloride measuring device.

実施例１における試験条件は、以下のとおりである。
排ガス量：０．２８Ｎｍ３−ｄｒｙ／ｍｉｎ
バグフィルタ１５の入口における塩化水素濃度：２５０ｐｐｍ（４０７ｍｇ／Ｎｍ３）
水分量：１０％
バグフィルタ温度：１７０℃
酸性ガス処理剤の添加量：入口塩化水素濃度に対し、当量比で１．５
酸性ガス処理剤の添加時間：連続添加で９０分間 The test conditions in Example 1 are as follows.
Exhaust gas amount: 0.28 Nm 3 -dry / min
Hydrogen chloride concentration at the inlet of the bag filter 15: 250 ppm (407 mg / Nm 3 )
Moisture content: 10%
Bag filter temperature: 170 ° C
Amount of acid gas treatment agent added: 1.5 equivalent ratio to the inlet hydrogen chloride concentration
Acid gas treatment agent addition time: 90 minutes with continuous addition

［評価］
以下の式にしたがい、酸性ガス処理剤を９０分間連続添加した際の塩化水素の除去率を求めた。塩化水素の除去率が８５％以上である場合を「○」とし、８５％未満である場合を「×」とした。結果を表１に示す。
酸性ガス除去率（％）＝（入口での塩化水素濃度−出口での塩化水素濃度）／入口での塩化水素濃度×１００ [Evaluation]
According to the following formula, the removal rate of hydrogen chloride when the acidic gas treating agent was continuously added for 90 minutes was determined. The case where the removal rate of hydrogen chloride was 85% or more was indicated as “◯”, and the case where it was less than 85% was indicated as “x”. The results are shown in Table 1.
Acid gas removal rate (%) = (hydrogen chloride concentration at the inlet−hydrogen chloride concentration at the outlet) / hydrogen chloride concentration at the inlet × 100

〔酸性ガス処理剤の固結性〕
図２に示す荷重試験装置３０を用いて、以下の内容にて固結性の評価を実施した。 [Consolidation of acid gas treatment agent]
Using the load test apparatus 30 shown in FIG. 2, the caking property was evaluated as follows.

荷重試験装置３０は、１００ｍｍ×１００ｍｍの枠状升３１と、枠状升３１に収容されたサンプル（酸性ガス処理剤）に加重をかける１０ｋｇの重り３２とを備える。   The load test apparatus 30 includes a frame-shaped rod 31 of 100 mm × 100 mm and a 10 kg weight 32 that applies a load to a sample (acid gas treatment agent) accommodated in the frame-shaped rod 31.

まず、１００ｍｍ×１００ｍｍの枠状升３１に、実施例及び比較例に係る各種の酸性ガス処理剤Ｓを充填する。そして、重り３２を用いて酸性ガス処理剤Ｓに１０ｋｇの加重を１８時間かけた。   First, various acid gas treating agents S according to Examples and Comparative Examples are filled into a frame-shaped rod 31 of 100 mm × 100 mm. Then, a weight of 10 kg was applied to the acid gas treating agent S using the weight 32 for 18 hours.

その後、目開きが７１０μｍである第１の篩と、目開きが３５０μｍである第２の篩とを有する篩分装置を用い、酸性ガス処理剤Ｓを、第１の篩、第２の篩の順に振動で落下させて、第１の篩の篩上、第２の篩の篩上に残った重量を計量し、試験に供した酸性ガス処理剤Ｓ重量に対する篩残分の割合（単位：重量％）を算出した。この篩残分の割合が小さいほど、酸性ガス処理剤の固結性が小さいことを示す。この篩残分の割合を指標として、各酸性ガス処理剤の固結性を評価した。篩残分の割合が２０％以下である場合を「◎」とし、２０％を超え５０％以下である場合を「○」とし、５０％以上９０％以下を「△」とし、９０％を超える場合を「×」とした。結果を表１に示す。   Thereafter, using a sieving device having a first sieve having an opening of 710 μm and a second sieve having an opening of 350 μm, the acid gas treating agent S is mixed with the first sieve and the second sieve. Drop by vibration in order, weigh the weight remaining on the sieve of the first sieve and the sieve of the second sieve, the ratio of the sieve residue to the weight of the acid gas treating agent S used for the test (unit: weight) %) Was calculated. It shows that the caking property of an acidic gas processing agent is so small that the ratio of this sieve residue is small. Using the ratio of the sieve residue as an index, the caking property of each acid gas treating agent was evaluated. The case where the ratio of the sieve residue is 20% or less is “、”, the case where it exceeds 20% and 50% or less is “◯”, and the case where it is 50% or more and 90% or less is “Δ”, which exceeds 90% The case was set as “x”. The results are shown in Table 1.

〔結果〕

Figure 2018122248
〔result〕
Figure 2018122248

メジアン径（Ｄ５０）が１１μｍ以上２５μｍ以下であり、メジアン径に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）が２．０以下である炭酸水素ナトリウムは、いずれも、高い酸性ガス処理性能を有していた（実施例１−１〜１−３）。酸性処理性能に優れることから、煤塵量削減による最終処分場の延命化、浸出水のＣＯＤ低減等、環境負荷の低減も期待される。 Sodium hydrogen carbonate having a median diameter (D 50 ) of 11 μm or more and 25 μm or less and a ratio of the mode diameter (D m ) to the median diameter (D m / D 50 ) of 2.0 or less is a high acid gas. It had processing performance (Examples 1-1 to 1-3). Because of its excellent acid treatment performance, it is expected to reduce the environmental burden such as extending the life of the final disposal site by reducing the amount of dust and reducing the COD of leachate.

また、上記炭酸水素ナトリウムは、固結防止性にも優れる（実施例１−１〜１−３）。中でも、メジアン径（Ｄ５０）が１５μｍ以上であると、よりいっそう固結防止性に優れ（実施例１−２、１−３）、１７μｍ以上であると、さらに固結防止性に優れる（実施例１−３）。 Moreover, the said sodium hydrogencarbonate is excellent also in anti-caking property (Examples 1-1 to 1-3). Among them, when the median diameter (D 50 ) is 15 μm or more, the anti-caking property is further improved (Examples 1-2 and 1-3), and when it is 17 μm or more, the anti-caking property is further improved (implementation). Example 1-3).

また、炭酸水素ナトリウムのメジアン径（Ｄ５０）を１１μｍ未満にまで微粒子化しないことから、製造コストの削減にも繋がる。加えて、粗重曹の粉砕時間の短縮や粉砕量を増やすことも可能となり、酸性ガス処理剤を安定して供給することが可能である。 In addition, since the median diameter (D 50 ) of sodium hydrogencarbonate is not reduced to less than 11 μm, the manufacturing cost is reduced. In addition, the grinding time of the crude baking soda can be shortened and the amount of grinding can be increased, so that the acidic gas treating agent can be stably supplied.

これに対し、メジアン径（Ｄ５０）が１１μｍ未満であると、酸性ガス処理剤が固結し易く、装置のハンドリング性に影響を及ぼし得ることが確認された（比較例１−１）。 On the other hand, it was confirmed that when the median diameter (D 50 ) is less than 11 μm, the acidic gas treating agent is easily consolidated and can affect the handling properties of the apparatus (Comparative Example 1-1).

また、メジアン径（Ｄ５０）が１１μｍ以上２５μｍ以下の範囲内にあっても、メジアン径に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）が２．０を超えていると、十分な酸性ガス処理性能を得られないことが確認された（比較例１−２，１−３）。 Even if the median diameter (D 50 ) is in the range of 11 μm or more and 25 μm or less, the ratio of the mode diameter (D m ) to the median diameter (D m / D 50 ) is more than 2.0. It was confirmed that the acidic gas treatment performance could not be obtained (Comparative Examples 1-2 and 1-3).

＜実施例２＞ 固結防止剤の比較
〔酸性ガス処理剤の固結性〕
表２に記載の粒度をもつ炭酸水素ナトリウム１００重量％に対し、表２に記載の固結防止剤を表２に記載の割合で混合し、各種の酸性ガス処理剤を得た。そして、実施例１と同じ手法にて酸性ガス処理剤の固結性をした。結果を表２に示す。 <Example 2> Comparison of anti-caking agents [caking property of acid gas treating agent]
The anti-caking agent shown in Table 2 was mixed in the proportion shown in Table 2 with respect to 100% by weight of sodium hydrogen carbonate having the particle size shown in Table 2 to obtain various acid gas treating agents. Then, the acid gas treating agent was consolidated by the same method as in Example 1. The results are shown in Table 2.

〔バグフィルタにおける差圧試験〕
図１に示す酸性ガス処理装置１０を、以下の試験条件で運転した。なお、バグフィルタの圧力損失は、圧力計Ｐ１によって測定される圧力と、圧力計Ｐ２によって測定される圧力との差から求めた。
ガス風量：０．４３ｍ３／ｍｉｎ
バグフィルタ１５の濾過面積：０．４３ｍ２
バグフィルタ１５の濾過速度：１ｍ／ｍｉｎ
バグフィルタ１５の集塵速度：１７０℃
酸性ガス処理剤の添加量：１１６ｇ／ｍ３
圧力設定：０．５ｋＰａ（バグフィルタの圧力損失が０．５ｋＰａに到達すると、自動逆洗となる。）
試験時間：６０分間 [Differential pressure test in bag filter]
The acid gas treatment device 10 shown in FIG. 1 was operated under the following test conditions. The pressure loss of the bag filter was obtained from the difference between the pressure measured by the pressure gauge P1 and the pressure measured by the pressure gauge P2.
Gas flow rate: 0.43m 3 / min
Filtration area of the bag filter 15: 0.43 m 2
Filtration speed of bag filter 15: 1 m / min
Dust collection speed of bag filter 15: 170 ° C
Addition amount of acid gas treating agent: 116 g / m 3
Pressure setting: 0.5 kPa (When the pressure loss of the bag filter reaches 0.5 kPa, automatic backwashing is performed.)
Test time: 60 minutes

［評価］
酸性ガス処理剤を６０分間連続添加する間に、バグフィルタの圧力損失が０．５ｋＰａに到達し、自動逆洗となった回数を数えた。この回数が少ないほど、酸性ガス処理剤のバグフィルタからの剥離性が良好で、バグフィルタの圧力損失の上昇を防止できることを示す。結果を表２に示す。 [Evaluation]
While the acid gas treatment agent was continuously added for 60 minutes, the number of times that the pressure loss of the bag filter reached 0.5 kPa and automatic backwashing was performed was counted. The smaller the number of times, the better the peelability of the acidic gas treating agent from the bag filter, and the higher the pressure loss of the bag filter can be prevented. The results are shown in Table 2.

〔結果〕

Figure 2018122248
〔result〕
Figure 2018122248

メジアン径（Ｄ５０）が１１μｍ以上２５μｍ以下であり、メジアン径に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）が２．０以下である炭酸水素ナトリウムに固結防止剤を加えると、固結防止剤を加えない場合に比べ、固結防止性によりいっそう優れる（実施例２−２〜２−５、２−１２〜２−１５、２−２２〜２−２５）。中でも、固結防止剤がステアリン酸カルシウムを含んでいると、特に優れた固結防止性を有する（実施例２−４、２−５、２−１４、２−１５、２−２４、２−２５）。 When an anti-caking agent is added to sodium bicarbonate having a median diameter (D 50 ) of 11 μm or more and 25 μm or less and a ratio of the mode diameter (D m ) to the median diameter (D m / D 50 ) of 2.0 or less The anti-caking property is even better than when no anti-caking agent is added (Examples 2-2 to 2-5, 2-12 to 2-15, 2-22 to 2-25). Among these, when the anti-caking agent contains calcium stearate, it has particularly excellent anti-caking properties (Examples 2-4, 2-5, 2-14, 2-15, 2-24, 2-25). ).

メジアン径（Ｄ５０）が１１μｍ以上２５μｍ以下であり、メジアン径に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）が２．０以下である炭酸水素ナトリウムは、固結防止剤の種類に関わらず、バグフィルタの圧力損失が０．５ｋＰａに到達し、自動逆洗となった回数が少なく、酸性ガス処理剤のバグフィルタからの剥離性に優れ、バグフィルタの圧力損失の上昇を防止できることが確認された（実施例２−１〜２−５、２−１１〜２−１５、２−２１〜２−２５）。これは、炭酸水素ナトリウム粒子や固結防止剤の粒子が濾布の内部に入り込むのを抑えられ、濾布表面に安定した濾過層が形成されたためであると考えられる。 Sodium bicarbonate having a median diameter (D 50 ) of 11 μm or more and 25 μm or less and a ratio of the mode diameter (D m ) to the median diameter (D m / D 50 ) of 2.0 or less is a kind of anti-caking agent. Regardless, the pressure loss of the bag filter reaches 0.5 kPa, the number of times of automatic backwashing is small, the acid gas treatment agent is excellent in peelability from the bag filter, and the increase in the pressure loss of the bag filter is prevented. It was confirmed that it was possible (Examples 2-1 to 2-5, 2-11 to 2-15, 2-21 to 2-25). This is presumably because sodium bicarbonate particles and anti-caking agent particles were prevented from entering the filter cloth, and a stable filtration layer was formed on the filter cloth surface.

中でも、メジアン径（Ｄ５０）が１７μｍ以上であると、バグフィルタの圧力損失の上昇をよりいっそう効果的に防止できる（実施例２−２１〜２−２５）。 In particular, when the median diameter (D 50 ) is 17 μm or more, an increase in the pressure loss of the bag filter can be more effectively prevented (Examples 2-21 to 2-25).

これに対し、メジアン径（Ｄ５０）が１１μｍ未満であると、バグフィルタの圧力損失の上昇を十分に抑えられない（比較例２−１〜２−５、２−１１〜２−１５）。これは、炭酸水素ナトリウム粒子や固結防止剤の粒子が濾布の内部に入り込んだためであると考えられる。 On the other hand, when the median diameter (D 50 ) is less than 11 μm, an increase in the pressure loss of the bag filter cannot be sufficiently suppressed (Comparative Examples 2-1 to 2-5, 2-11 to 2-15). This is presumably because sodium bicarbonate particles and anti-caking agent particles entered the filter cloth.

１０ 酸性ガス処理装置
１１ ヒーター
１３ 酸性ガス供給剤供給機
１５ バグフィルタ
１７ 冷却塔
１８ 中和塔
１９ 誘引送風機
Ｐ１，Ｐ２ 圧力計

DESCRIPTION OF SYMBOLS 10 Acid gas processing apparatus 11 Heater 13 Acid gas supply agent supply device 15 Bag filter 17 Cooling tower 18 Neutralization tower 19 Induction blower P1, P2 Pressure gauge

＜実施例１＞ 炭酸水素ナトリウムの粒度と酸性ガス処理性能及び固結性との関係
〔酸性ガス処理性能の比較〕
［試験条件］
図１に記載の酸性ガス処理装置１０を用いて、表１に記載された６種類の炭酸水素ナトリウムについて、酸性ガス処理性能を比較した。なお、炭酸水素ナトリウムの径は、島津製作所株式会社製のＳＡＬＤ−７５００ｎａｎｏを用いて測定した。 <Example 1> Relationship between particle size of sodium hydrogen carbonate and acid gas treatment performance and solidification properties
[Test conditions]
Using the acidic gas treatment apparatus 10 shown in FIG. 1, the acidic gas treatment performance was compared for the six types of sodium hydrogen carbonate shown in Table 1. The diameter of sodium hydrogen carbonate was measured using SALD-7500 nano manufactured by Shimadzu Corporation.

Claims (5)

メジアン径（Ｄ５０）が１１μｍ以上２５μｍ以下であり、前記メジアン径に対するモード径（Ｄｍ）の比（Ｄｍ／Ｄ５０）が２．０以下である炭酸水素ナトリウムを含有する酸性ガス処理剤。 An acid gas treating agent containing sodium hydrogen carbonate having a median diameter (D 50 ) of 11 μm or more and 25 μm or less and a ratio of the mode diameter (D m ) to the median diameter (D m / D 50 ) of 2.0 or less . 前記炭酸水素ナトリウムの前記メジアン径（Ｄ５０）と積算重量３０％径（Ｄ３０）との差が１５μｍ以下であり、
前記炭酸水素ナトリウムの積算重量７０％径（Ｄ７０）と前記メジアン径（Ｄ５０）との差が１５μｍ以下である、請求項１に記載の酸性ガス処理剤。 The difference between the median diameter (D 50 ) of the sodium hydrogen carbonate and the 30% cumulative weight (D 30 ) is 15 μm or less,
The acid gas treating agent according to claim 1, wherein a difference between an accumulated weight 70% diameter (D 70 ) of the sodium hydrogen carbonate and the median diameter (D 50 ) is 15 µm or less. 固結防止剤をさらに含有し、
前記固結防止剤は、親水性物質、疎水性物質、及び粘土鉱物から選択される少なくとも１種以上を含む、請求項１又は２に記載の酸性ガス処理剤。 Further containing an anti-caking agent,
The acid gas treating agent according to claim 1 or 2, wherein the anti-caking agent includes at least one selected from a hydrophilic substance, a hydrophobic substance, and a clay mineral. 前記固結防止剤は、湿式シリカ、ステアリン酸カルシウム、ゼオライト、疎水性シリカ、親水性ヒュームドシリカ、ホワイトカーボン、塩基性炭酸マグネシウム、カーボンブラックのいずれか１種以上を含む、請求項３に記載の酸性ガス処理剤。   4. The anti-caking agent according to claim 3, comprising at least one of wet silica, calcium stearate, zeolite, hydrophobic silica, hydrophilic fumed silica, white carbon, basic magnesium carbonate, and carbon black. Acid gas treatment agent. 請求項１から４のいずれかに記載の酸性ガス処理剤を酸性ガスに添加した後、飛灰を集塵する、酸性ガス処理方法。

The acid gas processing method of collecting fly ash after adding the acid gas processing agent in any one of Claim 1 to 4 to acid gas.

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