JP5329397B2 - ガスから重金属を除去する方法 - Google Patents
ガスから重金属を除去する方法 Download PDFInfo
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- JP5329397B2 JP5329397B2 JP2009513773A JP2009513773A JP5329397B2 JP 5329397 B2 JP5329397 B2 JP 5329397B2 JP 2009513773 A JP2009513773 A JP 2009513773A JP 2009513773 A JP2009513773 A JP 2009513773A JP 5329397 B2 JP5329397 B2 JP 5329397B2
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- Prior art keywords
- palladium
- mercury
- gas
- absorbent
- absorbent material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 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
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Description
2Hg+S2=2HgS
に170℃以下の温度で触媒作用する触媒(白金またはパラジウムでよい)を使用し、ガスから水銀を除去する方法を開示している。
様々なパラジウム系吸収材及び1種類の白金系吸収材を調製した。各試料を2つに分け、半分を、N2中1%H2中の40 ppmSO2のガス流中、300℃で20時間の処理により予備硫化した。一つの場合、試料を、予備硫化と同じ条件下で、但しN2中1%H2中だけを含み、SO2を含まないガスを使用して処理することにより、予備還元した。
金属装填量/ 様々な炉温度及び試料前処理におけるHg含有量/重量%
重量%†
204℃ 288℃ 204℃予備 288℃予備 204℃予備
硫化§ 硫化§ 還元 *
2Pd 0.63 0.35 1.53 0.8
5Pd 1.28 0.71 2.09 1.05
10Pd 2.7 1.59 5.15
2Pt 0.14 0.06 0.08
†試料は全てγAl2O3上に担持
§300℃、40 ppmSO2、1%H2/N2で20時間予備硫化
* 300℃、1%H2/N2で20時間予備還元、
予備還元を5重量%Pd吸収材に行ったが、未処理吸収材と比較して容量の低下を示した。
予備硫化した5%Pd/Al2O3及び10%Pd/Al2O3及び2%Pd/Al2O3を全て従来の温度プログラム化された還元(「TPR」)により試験した。XRD試験も下記の表2に示すように行った。
前処理 2-シータ Pd相
予備硫化した§+Hg * 75.5 HgPd
Hg * 79.5 Pd中Hgの固溶体
還元204℃、Hg無し 82.1 Pd
§300℃、40 ppmSO2、1%H2/N2で20時間予備硫化
* 204℃でHg吸着
Pd4Sは、2-シータ範囲72〜81で幾つかの明らかなピークを与える。
各種試料の、合成ガスのメタン化に対する活性をマイクロ反応器で試験した。粒子径250〜355ミクロンの吸収材試料0.5 gの床に、420 ml/分のモデル合成ガスを大気圧で通過させ、ガス分析装置を使用してメタンをマイクロ反応器出口ガス中で検出した。モデル合成ガスは、約21%H2、27%CO、3%CO2、45%N2及び4%水蒸気から構成されていた。触媒床を通るガスの空間速度は、50,400 ml/gcat/時間と計算された。硫化された試料(2%、5%及び10%Pd)は全て480℃まで、無視できる程度のメタン形成を示したのに対し、試験した硫化されていない両方の試料(2%及び10%Pd)では、出口ガス中で、480℃で1%までの大量のメタン形成があり、550℃では5%に上昇した。
アルミナ担体に2重量%及び5重量%のパラジウムまたは2重量%の白金を従来の様式で装填した。次いで、各試料を、窒素中100 ppmH2Sを使用し、温度204℃で、H2Sが漏出するまで、予備硫化した。例1に記載する方法を使用し、試料を204℃及び288℃で試験し、水銀の装填量を測定し、下記の結果を得た。
金属装填量重量% 204℃でのHg含有量重量% 288℃でのHg含有量重量%
2Pd 0.94 ND
5Pd 3.54 1.96
2pt 0.12 ND
Claims (12)
- 高温ガスの重金属含有量を減少させる方法であって、
前記高温ガスを吸収材上に通すことを含んでなり、
前記吸収材が、金属として測定した際に、1.5重量%超過のパラジウムを含む、硫化されたパラジウム含有吸収材であり、
前記ガスにおける前記高温が、200℃超過の温度である、方法。 - 前記吸収材が担体上に担持されてなる、請求項1に記載の方法。
- 前記担体が、シリカ、チタニア、ジルコニア、アルミノケイ酸塩、イットリア、不活性炭素系材料及びこれらの組合せからなる群から選択されてなる、請求項2に記載の方法。
- 前記担体が、アルミナである、請求項2に記載の方法。
- 前記担体がγ-アルミナである、請求項2に記載の方法。
- 前記担体上のパラジウム装填量が2重量%である、請求項2〜5の何れか一項に記載の方法。
- 前記硫化されたパラジウム含有吸収材が、還元雰囲気中で硫黄供給源を使用して予備硫化されたパラジウム含有吸収材である、請求項1〜6のいずれか一項に記載の方法。
- 前記硫黄供給源として、H2Sが使用されてなる、請求項7に記載の方法。
- 前記硫化されたパラジウム含有吸収材がPd4Sを含んでなる、請求項1〜8のいずれか一項に記載の方法。
- 前記重金属が、水銀、ヒ素、セレン、及びカドミウムからなる群から選択されてなるものである、請求項1〜9の何れか一項に記載の方法。
- 前記重金属が、水銀である、請求項1〜9の何れか一項に記載の方法。
- 前記水銀がHgPd相を形成してなるものである、請求項11に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0611316.1A GB0611316D0 (en) | 2006-06-09 | 2006-06-09 | Improvements in the removal of metals from fluid streams |
GB0611316.1 | 2006-06-09 | ||
PCT/GB2007/050321 WO2007141577A1 (en) | 2006-06-09 | 2007-06-06 | Method for removing heavy metals from gases |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2009539580A JP2009539580A (ja) | 2009-11-19 |
JP2009539580A5 JP2009539580A5 (ja) | 2010-07-29 |
JP5329397B2 true JP5329397B2 (ja) | 2013-10-30 |
Family
ID=36745491
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009513773A Expired - Fee Related JP5329397B2 (ja) | 2006-06-09 | 2007-06-06 | ガスから重金属を除去する方法 |
Country Status (11)
Country | Link |
---|---|
US (1) | US8366807B2 (ja) |
EP (1) | EP2026898B1 (ja) |
JP (1) | JP5329397B2 (ja) |
KR (1) | KR20090031553A (ja) |
CN (1) | CN101466456A (ja) |
AU (1) | AU2007255151B2 (ja) |
CA (1) | CA2654787C (ja) |
GB (1) | GB0611316D0 (ja) |
RU (1) | RU2438762C2 (ja) |
WO (1) | WO2007141577A1 (ja) |
ZA (1) | ZA200810232B (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0616343D0 (en) * | 2006-08-17 | 2006-09-27 | Johnson Matthey Plc | Mercury removal |
US7998898B2 (en) | 2007-10-26 | 2011-08-16 | Corning Incorporated | Sorbent comprising activated carbon, process for making same and use thereof |
US8563092B2 (en) | 2010-09-14 | 2013-10-22 | Jawaharial Nehru Centre For Advanced Scientific Research | Formation of palladium sulfide |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2656803C2 (de) | 1975-12-18 | 1986-12-18 | Institut Français du Pétrole, Rueil-Malmaison, Hauts-de-Seine | Verfahren zur Entfernung von in einem Gas oder in einer Flüssigkeit vorhandenem Quecksilber |
US4814152A (en) | 1987-10-13 | 1989-03-21 | Mobil Oil Corporation | Process for removing mercury vapor and chemisorbent composition therefor |
US5401392A (en) * | 1989-03-16 | 1995-03-28 | Institut Francais Du Petrole | Process for eliminating mercury and possibly arsenic in hydrocarbons |
FR2644472B1 (fr) * | 1989-03-16 | 1991-06-21 | Inst Francais Du Petrole | Procede pour l'elimination du mercure et eventuellement d'arsenic dans les hydrocarbures |
US5080799A (en) * | 1990-05-23 | 1992-01-14 | Mobil Oil Corporation | Hg removal from wastewater by regenerative adsorption |
GB9022060D0 (en) | 1990-10-10 | 1990-11-21 | Ici Plc | Mercury removal |
US5281258A (en) * | 1992-12-21 | 1994-01-25 | Uop | Removal of mercury impurity from natural gas |
FR2701270B1 (fr) | 1993-02-08 | 1995-04-14 | Inst Francais Du Petrole | Procédé d'élimination du mercure dans les hydrocarbures par passage sur un catalyseur présulfuré. |
FR2701269B1 (fr) | 1993-02-08 | 1995-04-14 | Inst Francais Du Petrole | Procédé d'élimination d'arsenic dans des hydrocarbures par passage sur une masse de captation présulfurée. |
JPH11104432A (ja) * | 1997-09-30 | 1999-04-20 | Kawasaki Heavy Ind Ltd | ガス処理方法及び装置 |
US7033419B1 (en) | 2003-09-16 | 2006-04-25 | The United States Of America As Represented By The United States Department Of Energy | Method for high temperature mercury capture from gas streams |
-
2006
- 2006-06-09 GB GBGB0611316.1A patent/GB0611316D0/en not_active Ceased
-
2007
- 2007-06-06 WO PCT/GB2007/050321 patent/WO2007141577A1/en active Application Filing
- 2007-06-06 CN CNA2007800213491A patent/CN101466456A/zh active Pending
- 2007-06-06 CA CA2654787A patent/CA2654787C/en not_active Expired - Fee Related
- 2007-06-06 JP JP2009513773A patent/JP5329397B2/ja not_active Expired - Fee Related
- 2007-06-06 EP EP07733742.6A patent/EP2026898B1/en not_active Not-in-force
- 2007-06-06 RU RU2008152116/05A patent/RU2438762C2/ru not_active IP Right Cessation
- 2007-06-06 KR KR1020097000275A patent/KR20090031553A/ko not_active Application Discontinuation
- 2007-06-06 AU AU2007255151A patent/AU2007255151B2/en not_active Ceased
- 2007-06-06 US US12/304,063 patent/US8366807B2/en not_active Expired - Fee Related
- 2007-06-06 ZA ZA200810232A patent/ZA200810232B/xx unknown
Also Published As
Publication number | Publication date |
---|---|
AU2007255151A1 (en) | 2007-12-13 |
RU2008152116A (ru) | 2010-07-20 |
RU2438762C2 (ru) | 2012-01-10 |
AU2007255151B2 (en) | 2011-12-08 |
CA2654787A1 (en) | 2007-12-13 |
EP2026898B1 (en) | 2014-10-01 |
US8366807B2 (en) | 2013-02-05 |
JP2009539580A (ja) | 2009-11-19 |
KR20090031553A (ko) | 2009-03-26 |
GB0611316D0 (en) | 2006-07-19 |
WO2007141577A1 (en) | 2007-12-13 |
US20100229722A1 (en) | 2010-09-16 |
CA2654787C (en) | 2014-09-16 |
CN101466456A (zh) | 2009-06-24 |
ZA200810232B (en) | 2010-03-31 |
EP2026898A1 (en) | 2009-02-25 |
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