JP5751199B2 - 酸性ガス処理剤及びその製造方法並びに酸性ガス処理剤用添加剤 - Google Patents
酸性ガス処理剤及びその製造方法並びに酸性ガス処理剤用添加剤 Download PDFInfo
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- JP5751199B2 JP5751199B2 JP2012060693A JP2012060693A JP5751199B2 JP 5751199 B2 JP5751199 B2 JP 5751199B2 JP 2012060693 A JP2012060693 A JP 2012060693A JP 2012060693 A JP2012060693 A JP 2012060693A JP 5751199 B2 JP5751199 B2 JP 5751199B2
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- treating agent
- gas treating
- aluminosilicate
- acid gas
- zeolite
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- 239000003795 chemical substances by application Substances 0.000 title claims description 82
- 239000002253 acid Substances 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000654 additive Substances 0.000 title description 13
- 230000000996 additive effect Effects 0.000 title description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 120
- 239000007789 gas Substances 0.000 claims description 95
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 87
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 72
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 60
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 60
- 230000002378 acidificating effect Effects 0.000 claims description 46
- 239000000377 silicon dioxide Substances 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 22
- 229910021536 Zeolite Inorganic materials 0.000 claims description 17
- 239000010457 zeolite Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 11
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 54
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 48
- 238000000034 method Methods 0.000 description 11
- 238000003860 storage Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- -1 ammonium ions Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 4
- 229910000278 bentonite Inorganic materials 0.000 description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000429 sodium aluminium silicate Substances 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001595840 Margarites Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052630 margarite Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- 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
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- 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
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- 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
- B01D53/06—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 with moving adsorbents, e.g. rotating beds
- B01D53/10—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 with moving adsorbents, e.g. rotating beds with dispersed adsorbents
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- 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
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- B01J20/16—Alumino-silicates
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- 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
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- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2257/20—Halogens or halogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/48—Sulfur compounds
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/83—Solid phase processes with moving reactants
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
本発明の酸性ガス処理剤は、炭酸水素ナトリウムとアルミノケイ酸塩とを含む。アルミノケイ酸塩は、炭酸水素ナトリウム由来のアンモニアガスを除去しつつ、炭酸水素ナトリウムの流動性低下を抑制する。このため、本発明の酸性ガス処理剤によれば、アンモニアガスによる問題が抑制され、流動性も維持又は向上する。
本発明の酸性ガス処理剤の使用方法は、特に限定されず、従来どおりであってよい。例えば、酸性ガス処理剤の噴霧位置は、バグフィルタ、電気集塵機等の集塵機よりも上流側であってよい。酸性ガス処理剤の添加量は、酸性ガス処理剤添加前の排ガス又は集塵機よりも下流側の排ガス中の硫黄硫化物及び/又は塩化水素濃度を計測し、この計算値に応じて制御されるのが好ましい。通常は上記燃焼施設にて発生する主要な酸性ガスである塩化水素、硫黄酸化物の合計量に対し、炭酸水素ナトリウムが0.5〜3当量となるように酸性ガス処理剤を添加するのが好ましく、0.7〜1.5当量となるように酸性ガス処理剤を添加するのがより好ましい。
本発明に係る酸性ガス処理剤の製造方法は、アルミノケイ酸塩と炭酸水素ナトリウムとを混合及び粉砕して製剤化する工程を含む。
本発明の酸性ガス処理剤用添加剤は、アルミノケイ酸塩からなり、炭酸水素ナトリウムから放出されるアンモニアガスを除去するために用いられる。
酸性ガス処理剤由来のアンモニアガス濃度低減評価:
ソルベー法(アンモニアソーダ法とも称される)により合成され、平均粒径20μm以下に粉砕された炭酸水素ナトリウムを目開き500μmで篩分け、篩下を200gビニール袋に分取した。以下に示される添加剤をそれぞれ所定の割合で混合し、250mlポリエチレン容器に50gの混合物を加え密閉し、50℃に加熱した。加熱開始後、所定時間にアンモニアガス検知管にて、ポリエチレン瓶内のアンモニアガス濃度を測定した。
1)ゼオライト(ゼオライト#70、BET比表面積2,000cm2/g、平均粒径200μm以下):日東粉化工業株式会社製、
2)ゼオライト(ゼオライト#600、BET比表面積17,800cm2/g、平均粒径1.92μm):日東粉化工業株式会社製、
3)ゼオライト(ゼオライト#2300、BET比表面積23,100cm2/g、平均粒径1.25μm):日東粉化工業株式会社製、
4)ベントナイト(クニゲルV1、BET比表面積1,500cm2/g、平均粒径60μm以下):クニミネ工業株式会社製、
5)親水性合成シリカ(トクシールU):株式会社トクヤマ製。
酸性ガス処理剤の流動性改善評価:
ソルベー法(アンモニアソーダ法とも称される)により合成され、平均粒径20μm以下に粉砕された炭酸水素ナトリウムを目開き500μmで篩分け、篩下を200gビニール袋に分取した。前記酸性ガス処理剤由来のアンモニアガス濃度低減評価において用いられた添加剤をそれぞれ所定の割合で混合し、パウダーテスター PT−D型(ホソカワミクロン社製)を用い、安息角、崩漬角を測定し、流動性改善の効果を評価した。測定手順はパウダーテスターの説明書に従い、測定値を表2に示す。
ソルベー法(アンモニアソーダ法とも称される)により合成され、平均粒径20μm以下に粉砕された炭酸水素ナトリウムを目開き500μmで篩分け、篩下を200gビニール袋に分取した。前記酸性ガス処理剤由来のアンモニアガス濃度低減評価において用いられた添加剤をそれぞれ所定の割合で混合し、ビニール袋から空気を抜いて密閉し、荷重約0.1kg/cm2をかけ、21日間静置した。圧力は均一に1t/m2かかっていることを想定している。
21日静置後のサンプルを2mm篩で10回振動し(1回につき10cm)、篩上の残分を%表示する。圧着固着性(%)より酸性ガス処理剤の保存安定性を評価した。測定値を表2に示す。
Claims (3)
- ゼオライトと炭酸水素ナトリウムとを混合及び粉砕して製剤化する工程を含み、
前記ゼオライトを前記炭酸水素ナトリウムに対して0.1〜10質量%の量で混合し、
さらに合成シリカを前記炭酸水素ナトリウムに対して0.1〜5質量%混合し、
前記ゼオライトと前記合成シリカとの比率が、ゼオライト:合成シリカ=3:2〜2:1の範囲内にある、酸性ガス処理剤の製造方法。 - 混合する前記ゼオライトが、平均粒径800μm以下又は比表面積が500cm2/g以上である請求項1記載の酸性ガス処理剤の製造方法。
- 炭酸水素ナトリウムと、
前記炭酸水素ナトリウムに対して0.1〜10質量%の量のゼオライトと、
前記炭酸水素ナトリウムに対して0.1〜5質量%の量の合成シリカとを含み、
前記ゼオライトと前記合成シリカとの比率が、ゼオライト:合成シリカ=3:2〜2:1の範囲内にある、酸性ガス処理剤。
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