JP2010536573A - 酸ガス流からの硫化水素及び二酸化炭素の除去方法 - Google Patents
酸ガス流からの硫化水素及び二酸化炭素の除去方法 Download PDFInfo
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
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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
- B01D53/14—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 absorption
- B01D53/1456—Removing acid components
- B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
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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
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
- B01D53/526—Mixtures of hydrogen sulfide and carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
-
- 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
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
【選択図】なし
Description
2H2S+3O2 → 2H2O+2SO2 (1)
によるH2SのSO2への部分酸化を利用している。形成されたSO2は、クラウス(Claus)反応:
2H2S+SO2 → 2H2O+3/n Sn (2)
に従って元素状硫黄に(接触的に)転化できる。
反応(1)及び(2)の組合わせは、クラウス法として知られている。クラウス法は、製油所でも、また天然ガスから回収したH2Sの処理にも使用されることが多い。
(a)H2S及びCO2を含む酸ガス流中のH2SをSO2と反応させて硫黄蒸気及び水蒸気を形成し、これによりCO2、水蒸気、硫黄蒸気、残存SO2及び残存H2Sを含有する第一オフガス流を得る工程、
(b)第一オフガス流中の残存SO2を第一オフガス処理反応器中でH2Sに転化し、これにより第一オフガス流に比べて、SO2が枯渇し、かつH2S及びCO2に富む第二オフガス流を得る工程、
(c)第二オフガス流をH2S吸収性液体と接触させ、これにより第二オフガス流からH2SをH2S吸収性液体に移行させ、H2Sに富むH2S吸収性液体及びCO2に富む第三オフガス流を得る工程、
(d)第三オフガス流をCO2吸収器中でCO2吸収性液体と接触させ、これによりCO2を第三オフガス流からCO2吸収性液体に移行させて第三オフガス流からCO2除去し、CO2に富むCO2吸収性液体と精製ガスとを得る工程、
を含む、H2S及びCO2を含む酸ガス流からのH2S及びCO2の除去方法を提供する。
酸ガス流はCO2を、酸ガス流全体に対し好適には1容量%以上、好ましくは5容量%以上、更に好ましくは10容量%以上含有する。酸ガス流中のこのようなCO2量は、第三オフガス流中のCO2と同等量と言い換える。
工程(a)では酸ガス流中のH2SはSO2と反応して硫黄蒸気及び水蒸気を形成し、これによりCO2、水蒸気、硫黄蒸気、残留SO2及び残留H2Sを含有する第一オフガス流が得られる。
好ましいオフガス処理反応器は、例えばKohl and Riesenfeld,Gas Purification,第3版,Gulf Publishing Co.,ヒューストン,1979年による周知の教本に記載されるような、いわゆるSCOT反応器、即ち、シェル・クラウスオフガス処理反応器(Shell Claus Off−gas Treating reactor)である。
第二オフガス流はH2Sを第二オフガス流全体に対し、好適には500ppmv(容量ppm)未満、好ましくは200ppmv未満、更に好ましくは100ppmv未満含有する。
工程(c)では第二オフガス流はH2S吸収性液体と接触し、これによりH2Sを該ガス流からH2S吸収性液体に移行させ、H2Sに富むH2S吸収性液体及びCO2に富む第三オフガス流が得られる。
好適な化学溶剤は、特にヒンダードアミンを含む、第一、第二及び/又は第三アミンである。
工程(d)ではCO2吸収塔中で第三オフガス流をCO2吸収性液体と接触させ、これによりCO2を第三オフガス流からCO2吸収性液体に移行させ、CO2に富むCO2吸収性液体及び精製ガスを得ることにより、第三オフガス流からCO2が除去される。
好適な物理溶剤としては、ポリエチレングリコールのジメチルエーテル化合物がある。
好適な化学溶剤としては、アンモニア及びアミン化合物がある。
N,N’−ジ(ヒドロキシアルキル)ピペラジンは、好ましくはN,N’−ジ(2−ヒドロキシエチル)ピペラジン及び/又はN,N’−ジ(3−ヒドロキシプロピル)ピペラジンである。
N,N,N’N’−テトラキス(ヒドロキシアルキル)−1,6−ヘキサンジアミンは、好ましくはN,N,N’N’−テトラキス(2−ヒドロキシエチル)−1,6−ヘキサンジアミン及び/又はN,N,N’N’−テトラキス(2−ヒドロキシプロピル)−1,6−ヘキサンジアミンである。
吸収性液体がアンモニアを含む場合、吸収工程は好適には周囲温度未満、好ましくは0〜10℃、更に好ましくは2〜8℃の範囲で行われる。
Claims (10)
- (a)H2S及びCO2を含む酸ガス流中のH2SをSO2と反応させて硫黄蒸気及び水蒸気を形成し、これによりCO2、水蒸気、硫黄蒸気、残存SO2及び残存H2Sを含有する第一オフガス流を得る工程、
(b)第一オフガス流中の残存SO2を第一オフガス処理反応器中でH2Sに転化し、これにより第一オフガス流に比べて、SO2が枯渇し、かつH2S及びCO2に富む第二オフガス流を得る工程、
(c)第二オフガス流をH2S吸収性液体と接触させ、これにより第二オフガス流からH2SをH2S吸収性液体に移行させ、H2Sに富むH2S吸収性液体及びCO2に富む第三オフガス流を得る工程、
(d)第三オフガス流をCO2吸収器中でCO2吸収性液体と接触させ、これによりCO2を第三オフガス流からCO2吸収性液体に移行させて第三オフガス流からCO2除去し、CO2に富むCO2吸収性液体と精製ガスとを得る工程、
を含む、H2S及びCO2を含む酸ガス流からのH2S及びCO2の除去方法。 - 前記CO2吸収性液体が、1種以上のアミン、好ましくはモノエタノールアミン(MEA)、ジエタノールアミン(DEA)、ジグリコールアミン(DGA)、メチルジエタノールアミン(MDEA)及びトリエタノールアミン(TEA)の群から選ばれた1種以上のアミンである請求項1に記載の方法。
- 前記CO2吸収性液体が、モノエタノールアミン(MEA)、ジエタノールアミン(DEA)、ジグリコールアミン(DGA)、メチルジエタノールアミン(MDEA)及びトリエタノールアミン(TEA)の群から選ばれた複数のアミンの1種と、N,N’−ジ(ヒドロキシアルキル)ピペラジン、N,N,N’,N’−テトラキス(ヒドロキシアルキル)−1,6−ヘキサンジアミン及びtert−アルキルアミンスルホン酸化合物の群から選ばれた複数のアミンの1種とを組合わせた、アミンの組合わせを含む請求項1に記載の方法。
- 前記CO2吸収性液体が、N−エチルジエタノールアミン(EDEA)及び/又はピペラジンと、特にモノエタノールアミン(MEA)、ジエタノールアミン(DEA)、ジグリコールアミン(DGA)、メチルジエタノールアミン(MDEA)及びトリエタノールアミン(TEA)の群から選ばれた複数のアミンの1種との組合わせを含む請求項1に記載の方法。
- 前記CO2吸収性液体がアンモニアを含む請求項1に記載の方法。
- 前記原料酸ガス流が、サワーガス、好ましくはサワー天然ガスからH2S及びCO2を分離することにより得られる請求項1〜5のいずれか1項に記載の方法。
- 前記第三オフガス流が、CO2を第三オフガス流全体に対し、1容量%以上、好ましくは5容量%以上、更に好ましくは10容量%以上含有する請求項1〜6のいずれか1項に記載の方法。
- (d)前記CO2に富む吸収性液体を再生器中、高温でストリッピングガスと接触させて該CO2に富む吸収性液体を再生し、再生吸収性液体及びCO2に富むガス流を得る工程を更に含む請求項1〜7のいずれか1項に記載の方法。
- (d)前記CO2に富む吸収性液体を加圧する工程を更に含む請求項8に記載の方法。
- 前記CO2に富む加圧ガス流が油回収率の向上に使用される請求項9に記載の方法。
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EP07115264 | 2007-08-30 | ||
PCT/EP2008/061355 WO2009027491A1 (en) | 2007-08-30 | 2008-08-29 | Process for removal of hydrogen sulphide and carbon dioxide from an acid gas stream |
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EP (1) | EP2188040A1 (ja) |
JP (1) | JP2010536573A (ja) |
CN (1) | CN101820975A (ja) |
AU (1) | AU2008292143B2 (ja) |
CA (1) | CA2697944A1 (ja) |
WO (1) | WO2009027491A1 (ja) |
ZA (1) | ZA201001545B (ja) |
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US20100310439A1 (en) | 2010-12-09 |
ZA201001545B (en) | 2010-11-24 |
AU2008292143B2 (en) | 2011-12-08 |
CN101820975A (zh) | 2010-09-01 |
WO2009027491A1 (en) | 2009-03-05 |
EP2188040A1 (en) | 2010-05-26 |
US8765086B2 (en) | 2014-07-01 |
AU2008292143A1 (en) | 2009-03-05 |
CA2697944A1 (en) | 2009-03-05 |
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