JP5291092B2 - 活性炭を含む吸着体、それらの製造方法および利用 - Google Patents
活性炭を含む吸着体、それらの製造方法および利用 Download PDFInfo
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- JP5291092B2 JP5291092B2 JP2010508393A JP2010508393A JP5291092B2 JP 5291092 B2 JP5291092 B2 JP 5291092B2 JP 2010508393 A JP2010508393 A JP 2010508393A JP 2010508393 A JP2010508393 A JP 2010508393A JP 5291092 B2 JP5291092 B2 JP 5291092B2
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Description
ここでae(i)は区域iの有効面積であり、nは標的試験領域における試料区域の二乗の総数であり、ここでae(i)≧40μm2である。μm2における個々の二乗領域の面積ae(i)は次のように計算される:
活性炭マトリクスと、
硫黄元素として、または硫黄を含む化合物または部分において、任意の酸化状態にある硫黄と、
金属元素として、または金属を含む化合物または部分において、任意の酸化状態にある金属触媒と、
を含み、
前記金属触媒が活性炭マトリクス全体に分散されている、
吸着体である。
活性炭と、
硫黄元素として、または硫黄を含む化合物または部分において、任意の酸化状態にある硫黄と、
金属元素として、または金属を含む化合物または部分において、任意の酸化状態にある金属触媒と、
を含み、ここで、
金属触媒の少なくとも一部は、硫黄の少なくとも一部と化学結合している。
試験する吸着体を、特定の組成を有する160℃の参照燃焼排ガスが7500時間-1の空間速度で通過する、固定床内に充填する。気体流れの水銀濃度を吸着床の前後で測定する。任意の時点において、その瞬間の水銀除去効率(Eff(Hg))を次のように計算する:
活性炭と、
硫黄元素として、または硫黄を含む化合物または部分において、任意の酸化状態にある硫黄と、
金属元素として、または金属を含む化合物または部分において、任意の酸化状態にある金属触媒と、
を含み、
前記吸着体が、RFG1、RFG2および/またはRFG3に関して、少なくとも90%の初期の水銀除去効率を有する、
吸着体である。例えば、吸着体は、RFG1、RFG2および/またはRFG3に関して、少なくとも91%、少なくとも95%、少なくとも98%または少なくとも99%の初期の水銀除去効率を有しうる。硫黄および/または金属触媒は、一部の実施の形態では、活性炭マトリクス全体に分散されうる。他の実施の形態では、硫黄および/または金属触媒は、活性炭マトリクス全体に分散されない。この実施の形態の吸着体は、先に述べてきた、活性炭、硫黄、および金属触媒の特徴を含む、本発明の任意の他の吸着体について言及された、任意の1種類以上他の特徴をも有しうる。
活性炭と、
硫黄元素として、または硫黄を含む化合物または部分において、任意の酸化状態にある硫黄と、
金属元素として、または金属を含む化合物または部分において、任意の酸化状態にある金属触媒と、
を含む吸着体であって、
ここで、前記吸着体は、RFG1、RFG2および/またはRFG3に関して、少なくとも0.05mg・g-1の水銀除去能力を有する。例えば、吸着体は、RFG1、RFG2および/またはRFG3に関して、少なくとも0.10mg・g-1、少なくとも0.15mg・g-1、少なくとも0.20mg・g-1、少なくとも0.25mg・g-1、少なくとも0.30mg・g-1、少なくとも0.50mg・g-1、少なくとも1.0mg・g-1、少なくとも2.0mg・g-1、または少なくとも3.0mg・g-1の水銀除去能力を有しうる。硫黄および/または金属触媒は、一部の実施の形態では、活性炭マトリクス全体に分散されて差し支えない。他の実施の形態では、硫黄および/または金属触媒は、活性炭マトリクス全体に分散されない。この実施の形態の吸着体はまた、先に述べた、活性炭、硫黄、および金属触媒の特徴を含む、本発明の任意の他の吸着体について言及された、1種類以上の他の特徴をも含みうる。
(A)炭素源材料、硫黄源材料、金属触媒源材料および随意的な充填剤材料を含むバッチ混合材料の形状をしたバッチ混合体を提供する工程であって、前記金属触媒源材料が混合物に実質的に均質に分散する工程と、
(B)前記バッチ混合体を炭化する工程と、
(C)前記炭化されたバッチ混合体を活性化する工程と、
を有してなる。
(i)アルカリおよびアルカリ土類金属のハロゲン化物および酸化物;
(ii)貴金属およびそれらの化合物;
(iii)バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ニオブ、モリブデン、銀、タングステンおよびランタノイドの酸化物、硫化物、および塩;または
(iv)(i)、(ii)および(iii)の2つ以上の組合せおよび混合物から選択される形態で存在する。本方法の特定の実施の形態によれば、金属触媒源材料は:
(i)マンガンの酸化物、硫化物、硫酸塩、酢酸塩および塩;(ii)鉄の酸化物、硫化物、および塩;
(iii)(i)およびKIの組合せ;
(iv)(ii)およびKIの組合せ;および/または
(v)(i)、(ii)、(iii)および(iv)の任意の2つ以上の混合物および組合せから選択される形態で存在する。
(i)炭素体を離すための炭素源材料の分解;
(ii)金属触媒源材料の分解;
(iii)硫黄源材料の分解;
(iv)硫黄源材料と炭素源材料との反応;
(v)硫黄源材料と炭素との反応;
(vi)硫黄源材料と金属触媒源材料との反応;
(vii)金属触媒源材料と炭素源材料との反応;および
(viii)金属触媒源材料と炭素との反応。
(1)金属触媒源材料および/または金属触媒の再分散;
(2)硫黄の再分散;
(3)硫黄源材料(硫酸塩、亜硫酸塩など)に由来する硫黄元素の形成;
(4)硫黄源材料(硫黄元素など)に由来する硫黄含有化合物の形成;
(5)酸化物の形態の金属触媒の形成;
(6)硫化物の形態の金属触媒の形成;
(7)金属触媒源材料の一部の還元。硫黄の一部(特に元素状態のもの)および金属触媒源材料の一部(KIなど)は、炭化の間の炭化雰囲気によって一掃されうる。
(a)活性炭体上に金属触媒および/または硫黄を充填するその後の工程(含浸など)を回避し、それにより、場合によっては工程段階を減らし、すべての工程歩留まりを増大し、工程コストを軽減し、
(b)典型的には含浸によって得られるものよりも、さらに均質な活性吸着部位(金属触媒および硫黄)の分散を吸着体にもたらし、
(c)金属触媒および硫黄の、耐久性のある、強固な固定を吸着体にもたらし、前記吸着体が、長期使用の間、処理すべき流体流れの流れに耐えることができるようにする、
という利点を有する。含浸は、結果的に、外側のセル壁に含浸させた種(金属触媒および硫黄など)の選択的分散、壁表面の大きい孔隙(マイクロメートル規模のものなど)をもたらしうる。ナノスケールの孔隙の割合が高い壁表面上への含浸させた種の充填は、時間がかかり、かつ困難でありうる。400〜2000m2・g-1の高い比表面積を有する活性炭の表面積の大部分は、ナノスケールの孔隙によるものである。したがって、典型的な含浸工程にとって、このような活性炭材料の比表面積の大部分に、含浸させた種の充填をもたらすことは困難であると考えられる。さらには、典型的な含浸工程は、大きい孔隙の存在する外側のセル壁および/または壁表面上に、含浸させた種の厚い比較的緻密な層をもたらし、それによって、より小さい孔隙の内または外の流体の通路を遮断し、活性炭の吸着機能を有効に低減する結果となると考えられる。さらには、吸着体における、典型的な含浸工程での含浸させた種の固定は、主に、比較的弱い物理的力によるものであり、流体流れにおける長期使用にとって不十分な場合がある。
(I) 未硬化の、硬化可能なポリマー樹脂を含む炭素源材料と、
(II) 硫黄含有材料の粒子と、
(III) 元素または金属を含む化合物のいずれかの形態の金属触媒と、
を含み、
ここで、金属触媒は、押出成形されたバッチ混合体を形成する材料中に実質的に均質に分散される。
(IV) 結合剤材料;および/または
(V) 無機充填剤材料;および/または
(VI) 滑剤
を含む。
46%の液体フェノール性のレゾール樹脂、1%の潤滑油、13%のコージエライト粉末、9%の硫黄粉末、7%の鉄アセチルアセトナート、18%のセルロース繊維、5%のMethocel結合剤および1%のステアリン酸ナトリウムを用いて、押出成形組成物を配合した。この混合物を混合し、次いで押出成形した。押出成形されたハニカムを、次に、空気中、150℃で、乾燥および硬化させた後、窒素中で炭化し、二酸化炭素で活性化した。次に、活性炭ハニカムのサンプルを水銀除去能力について試験した。試験は、22μg・m-3の流入口の水銀元素濃度を用いて160℃で行った。水銀用のキャリアガスは、N2、SO2、O2およびCO2を含んでいた。ガスの流量は750ml/分であった。全水銀除去効率は86%であり、一方、水銀元素の除去効率は100%であった。
別の押出成形組成物を実施例1と同様に押出成形したが、13%の代わりに12%のコージエライト粉末を用い、7%の鉄アセチルアセトナートの代わりに4%の鉄アセチルアセトナートおよび4%のヨウ化カリウムを用いた。活性化後、これらのサンプルは、90%の全水銀除去および100%の水銀元素除去を示した。したがって組成中のKIの存在は、効率を向上させた。
この実験では、押出成形物の組成は、59%のフェノール性レゾール樹脂、1%のリン酸、1%の油、9%の硫黄粉末、3%の鉄酸化物、19%のセルロース繊維、7%のmethocel結合剤および1%のステアリン酸ナトリウムであった。これらのサンプルを押出成形し、硬化し、炭化し、活性化し、実施例1のように水銀除去性能について試験した。水銀除去効率は、全水銀および水銀元素について、それぞれ87%および97%であった。
この実験では、6%のMnO2、13%のコージエライト、7%の硫黄、19%のセルロース繊維、5%のmethocel結合剤、1%のステアリン酸ナトリウム、47%のフェノール性レゾール樹脂、1%のリン酸および1%の油の組成と共に、マンガン酸化物を金属触媒源として使用した。この組成に基づいたサンプルの水銀除去効率は、全水銀および水銀元素について、それぞれ92%および98%であった。
実施例では、硫黄は、マンガンと組み合わせて、硫黄元素の代わりに、MnSとして加えた。組成は、15%のコージエライト、10%のMnS、20%のセルロース繊維、5%のmethocel結合剤、1%のステアリン酸ナトリウム、47%のフェノール性レゾール樹脂、および1%の油であった。
MnSの代わりにモリブデン二硫化物(MoS2)を用いて、実施例5の実験を繰り返した。これらのサンプルは、全水銀および水銀元素について、それぞれ90%および96%の水銀除去効率を与えた。
この実験では、押出成形物の組成は、14%の木炭、47%のフェノール樹脂、7%の硫黄、7%のマンガン酸化物、18%のセルロース繊維、5%のmythical結合剤および1%のナトリウム単体(separate)であった。これらのサンプルを、押出成形し、硬化し、炭化し、実施例1のように活性化した。
この実施例では、押出成形物の組成は、16%の硬化硫黄含有フェノール樹脂、45%のフェノール樹脂、8%の硫黄、7%のマンガン酸化物、18%のセルロース繊維、4%のmythical結合剤および1%のナトリウム単体であった。これらのサンプルこれらのサンプルを、押出成形し、硬化し、炭化し、実施例1のように活性化した。
Claims (6)
- 活性炭マトリクスと、
硫黄元素として、または硫黄を含む化合物または部分において、任意の酸化状態にある硫黄と、
アルカリ土類の水酸化物と、
金属元素として、または金属を含む化合物または部分において、任意の酸化状態にある金属触媒とを含み、
前記金属触媒が、前記活性炭マトリクス全体に分散されていて、かつ、マンガン又はモリブデンの硫化物から選択される、吸着体。 - 前記硫黄の少なくとも一部が前記活性炭マトリクスの少なくとも一部の炭素に化学結合することを特徴とする、請求項1記載の吸着体。
- 硫黄元素を含むことを特徴とする、請求項1記載の吸着体。
- 前記金属触媒が前記吸着体と接触する流体からの1種類以上の次の有毒物質:
カドミウム、水銀、クロム、鉛、バリウム、ベリリウム、ニッケル、コバルト、バナジウム、亜鉛、銅、マンガン、アンチモン、銀、タリウム、ヒ素およびセレンの除去を促進し、
前記有毒物質が、任意の酸化状態、かつ、元素の形態であるかまたは前記元素を含む化合物であることを特徴とする、請求項1記載の吸着体。 - ハニカム・モノリスの形態であることを特徴とする請求項1記載の吸着体。
- 前記金属触媒の少なくとも一部が、前記硫黄の少なくとも一部と化学結合していることを特徴とする、請求項1記載の吸着体。
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JP2003192407A (ja) * | 2001-12-20 | 2003-07-09 | Taiheiyo Cement Corp | 原料中の水銀を低減させるセメント製造方法 |
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US7722705B2 (en) * | 2006-05-11 | 2010-05-25 | Corning Incorporated | Activated carbon honeycomb catalyst beds and methods for the use thereof |
US7781361B2 (en) * | 2006-05-11 | 2010-08-24 | Corning Incorporated | Method for regeneration of activated carbon catalyst beds |
US20070265161A1 (en) * | 2006-05-11 | 2007-11-15 | Gadkaree Kishor P | Activated carbon honeycomb catalyst beds and methods for the manufacture of same |
US20080207443A1 (en) * | 2007-02-28 | 2008-08-28 | Kishor Purushottam Gadkaree | Sorbent comprising activated carbon, process for making same and use thereof |
KR101516836B1 (ko) * | 2007-05-14 | 2015-04-30 | 코닝 인코포레이티드 | 활성 탄소를 포함하는 흡수체, 이의 제조방법, 및 이의 용도 |
-
2008
- 2008-05-13 KR KR1020097025996A patent/KR101516836B1/ko not_active Expired - Fee Related
- 2008-05-13 WO PCT/US2008/006082 patent/WO2008143831A2/en active Application Filing
- 2008-05-13 CA CA002686986A patent/CA2686986A1/en not_active Abandoned
- 2008-05-13 EP EP08754390A patent/EP2150337A2/en not_active Withdrawn
- 2008-05-13 JP JP2010508393A patent/JP5291092B2/ja not_active Expired - Fee Related
- 2008-05-13 CN CN2008800224132A patent/CN101687173B/zh not_active Expired - Fee Related
- 2008-05-14 TW TW097117771A patent/TW200914126A/zh unknown
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2013
- 2013-01-04 JP JP2013000083A patent/JP2013126661A/ja active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013126661A (ja) * | 2007-05-14 | 2013-06-27 | Corning Inc | 活性炭を含む吸着体、それらの製造方法および利用 |
KR101903911B1 (ko) | 2017-12-19 | 2018-10-02 | 이화여자대학교 산학협력단 | 벤조피렌 저감화 및 향기 성분 보존에 효과적인 참기름 여과 방법 |
Also Published As
Publication number | Publication date |
---|---|
KR20100017793A (ko) | 2010-02-16 |
EP2150337A2 (en) | 2010-02-10 |
CN101687173B (zh) | 2013-11-13 |
KR101516836B1 (ko) | 2015-04-30 |
CN101687173A (zh) | 2010-03-31 |
WO2008143831A2 (en) | 2008-11-27 |
JP2013126661A (ja) | 2013-06-27 |
WO2008143831A3 (en) | 2009-03-26 |
CA2686986A1 (en) | 2008-11-27 |
TW200914126A (en) | 2009-04-01 |
JP2010527288A (ja) | 2010-08-12 |
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