EP0880395A1 - Method for removing sulfur-containing contaminants, aromatics andhydrocarbons from gas - Google Patents
Method for removing sulfur-containing contaminants, aromatics andhydrocarbons from gasInfo
- Publication number
- EP0880395A1 EP0880395A1 EP97900807A EP97900807A EP0880395A1 EP 0880395 A1 EP0880395 A1 EP 0880395A1 EP 97900807 A EP97900807 A EP 97900807A EP 97900807 A EP97900807 A EP 97900807A EP 0880395 A1 EP0880395 A1 EP 0880395A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- sulfur
- absorption
- mercaptans
- gas stream
- 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.)
- Ceased
Links
Classifications
-
- 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
- B01D53/75—Multi-step processes
-
- 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
-
- 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
- B01D53/1406—Multiple stage absorption
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0408—Pretreatment of the hydrogen sulfide containing gases
Definitions
- H2S sulfur-containing gases
- SO2 sulfur-containing gases
- the H2S content should be reduced to a value lower than 5 mg/Nm3. Requirements are also set with regard to the maximum content of other sulfur compounds. From the prior art a large number of methods are known by which the amount of sulfur compounds in a gas, such as natural gas, can be reduced.
- the following process route is usually employed.
- a first step the gas to be treated is purified, whereby sulfur- containing components are removed from the gas, followed by a recovery of sulfur from these sulfur-containing components, whereafter a sulfur purification step of the residual gas ensues.
- this sulfur purification step it is attempted to recover the last percents of sulfur before the residual gas is emitted via the stack into the atmosphere.
- aqueous solvents absorption agents
- chemical solvent processes include the so-called amine processes in which use is made of aqueous solutions of alkanolamines or of potassium carbonate solutions.
- DMPEG polyethylene glycol
- NMP N-Methyl-Pyrrolidone
- Rectisol methanol
- a frequently used process for recovering sulfur from the thus obtained sulfur compounds, in particular H2S, is the Claus process. This process is described in detail in H.G. Paskall, "Capability of the modified Claus process", Western Research Development, Calgary, Alberta, Canada, 1979.
- the Claus process consists of a thermal step followed by typically 2 or 3 reactor steps. In the thermal step one-third of the H2S is combusted to SO2 according to the reaction
- the present invention provides a simple method for purifying contaminated hydrocarbon gas with recovery of sulfur, according to which method in a first absorption step the sulfur-containing contaminants are removed from the gas, to form on the one hand a purified gas stream and on the other a sour gas, which sour gas is hydrogenated in order to convert the greater part of the mercaptans to H 2 S, whereafter the hydrogenated sour gas is fed to a second absorption step in which the sour gas is separated into an H 2 S-enriched first gas stream, which is fed to a Claus plant, followed by a selective oxidation step of H S to elemental sulfur in the tail gas, and an H 2 S-reduced second gas stream, which second gas stream is combusted.
- alumina is used with this kind of catalysts, since this material, in addition to the desired thermal stability, also enables a good dispersion of the active component.
- catalytically active material preferably a combination of cobalt and molybdenum is used.
- An alternative method of preventing COS formation, but without water vapor being supplied is the installation of a pre-absorber before the hydrogenation stage, whereby the H 2 S concentration in the gas is reduced to less than a quarter.
- the gas from this pre-absorber is then passed through a hydrogenation reactor, whereby all mercaptans are converted to H 2 S with the aid of the added hydrogen.
- the residual H S is then selectively absorbed in a second absorber, of the second absorption step. On balance, the same H 2 S enrichment is then obtained as with a single absorber.
- the H 2 S-enriched gas is fed to the thermal stage of a
- the sour gas coming from a first absorption unit (not drawn) in which contaminated natural gas has been split into, on the one hand, a gas stream with the desired specification and, on the other, the sour gas, is passed via line 1 to a pre-absorber 2 of an absorption/regeneration plant, further consisting of a second absorber and a regenerator 9.
- the gas coming from the pre-absorber 2 is passed via line 3 to the hydrogenation reactor 5 and brought to the desired hydrogenation temperature under addition of hydrogen and/or carbon monoxide via line 4.
- the invention is elucidated in and by the following non-limiting example.
- An amount of sour gas of 15545 Nm 3 /h coming from the regenerator of a gas purification plant had the following composition at 40°C and a pressure of 1.70 bar abs.
- Aromatics (Benzene, Toluene, Xylene)
- the inlet temperature of the selective oxidation reactor was 220 °C and the outlet temperature was 292 °C.
- the selective oxidation reactor was filled with catalyst as described in European patents 242.920 and 409.353 and in the International patent application WO-A 95/07856.
- the sulfur formed in the sulfur recovery plant was condensed after each stage and discharged.
- the exiting inert gas was passed via an afterburning to the stack.
- the amount of sulfur was 2094 kg/h.
- the total desulfurization efficiency based on the original sour gas, which contained 9.0 vol.% H2S, was 97.7%.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Industrial Gases (AREA)
- Gas Separation By Absorption (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1002134 | 1996-01-19 | ||
NL1002134A NL1002134C2 (nl) | 1996-01-19 | 1996-01-19 | Werkwijze voor het verwijderen van zwavelbevattende verontreinigingen, aromaten en koolwaterstoffen uit gas. |
PCT/NL1997/000018 WO1997026069A1 (en) | 1996-01-19 | 1997-01-20 | Method for removing sulfur-containing contaminants, aromatics and hydrocarbons from gas |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0880395A1 true EP0880395A1 (en) | 1998-12-02 |
Family
ID=19762183
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97900807A Ceased EP0880395A1 (en) | 1996-01-19 | 1997-01-20 | Method for removing sulfur-containing contaminants, aromatics andhydrocarbons from gas |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0880395A1 (zh) |
JP (1) | JP2000503293A (zh) |
KR (1) | KR19990077361A (zh) |
CN (1) | CN1208360A (zh) |
AU (1) | AU1321397A (zh) |
CA (1) | CA2241790A1 (zh) |
NL (1) | NL1002134C2 (zh) |
TW (1) | TW381043B (zh) |
WO (1) | WO1997026069A1 (zh) |
ZA (1) | ZA97370B (zh) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0021409D0 (en) | 2000-08-31 | 2000-10-18 | Boc Group Plc | Treatment of a gas stream containing hydrogen sulphide |
JP4837176B2 (ja) * | 2001-03-07 | 2011-12-14 | 千代田化工建設株式会社 | 天然ガスからの硫黄化合物の除去方法 |
DE10208253A1 (de) | 2002-02-26 | 2003-09-04 | Lurgi Ag | Verfahren zur Entfernung von Merkaptan aus Rohgas |
DE10219900B4 (de) * | 2002-05-03 | 2004-08-26 | Lurgi Ag | Verfahren zur Reinigung von kohlenwasserstoffhaltigem Gas |
KR20070053727A (ko) * | 2004-08-02 | 2007-05-25 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | 천연 기체 또는 불활성 기체를 포함하는 기체스트림으로부터의 메르캅탄의 제거 방법 |
JP4845438B2 (ja) * | 2005-07-08 | 2011-12-28 | 千代田化工建設株式会社 | 天然ガスからの硫黄化合物の除去方法 |
CN101576261B (zh) * | 2008-05-07 | 2011-05-11 | 北京丰汉工程咨询有限公司 | 一种酸性气燃烧及催化还原方法 |
US8808654B2 (en) * | 2009-09-29 | 2014-08-19 | Praxair Technology, Inc. | Process for sulfur removal from refinery off gas |
EA028471B1 (ru) * | 2012-12-10 | 2017-11-30 | Тоталь Са | Комплексный способ извлечения природного coвысокого качества из кислого газа, включающего hs и co |
WO2016112371A1 (en) * | 2015-01-09 | 2016-07-14 | Sr20 Holdings Llc | Process and system for pyrolysis of tires to fuels and other products |
WO2018115919A1 (en) * | 2016-12-23 | 2018-06-28 | Total Sa | Integrated process for elemental sulphur treatment |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3989811A (en) * | 1975-01-30 | 1976-11-02 | Shell Oil Company | Process for recovering sulfur from fuel gases containing hydrogen sulfide, carbon dioxide, and carbonyl sulfide |
FR2501663A1 (fr) * | 1981-03-13 | 1982-09-17 | Technip Cie | Procede et installation de traitement des gaz acides pour la recuperation et la production de soufre et de gaz carbonique |
US4356161A (en) * | 1981-08-24 | 1982-10-26 | Shell Oil Company | Process for reducing the total sulfur content of a high CO2 -content feed gas |
DE4206943A1 (de) * | 1992-03-05 | 1993-09-09 | Krupp Koppers Gmbh | Verfahren zur reinigung eines durch vergasung von kohlenstoffhaltigem material gewonnenen gases |
-
1996
- 1996-01-19 NL NL1002134A patent/NL1002134C2/nl not_active IP Right Cessation
-
1997
- 1997-01-16 ZA ZA97370A patent/ZA97370B/xx unknown
- 1997-01-17 TW TW086100467A patent/TW381043B/zh not_active IP Right Cessation
- 1997-01-20 AU AU13213/97A patent/AU1321397A/en not_active Abandoned
- 1997-01-20 WO PCT/NL1997/000018 patent/WO1997026069A1/en not_active Application Discontinuation
- 1997-01-20 JP JP9525885A patent/JP2000503293A/ja active Pending
- 1997-01-20 CN CN97191710A patent/CN1208360A/zh active Pending
- 1997-01-20 EP EP97900807A patent/EP0880395A1/en not_active Ceased
- 1997-01-20 CA CA002241790A patent/CA2241790A1/en not_active Abandoned
- 1997-01-20 KR KR1019980705510A patent/KR19990077361A/ko not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9726069A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN1208360A (zh) | 1999-02-17 |
JP2000503293A (ja) | 2000-03-21 |
WO1997026069A1 (en) | 1997-07-24 |
NL1002134C2 (nl) | 1997-07-22 |
TW381043B (en) | 2000-02-01 |
AU1321397A (en) | 1997-08-11 |
KR19990077361A (ko) | 1999-10-25 |
ZA97370B (en) | 1997-07-17 |
CA2241790A1 (en) | 1997-07-24 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19980716 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IT LI NL PT SE |
|
17Q | First examination report despatched |
Effective date: 19990804 |
|
RTI1 | Title (correction) |
Free format text: METHOD FOR REMOVING SULFUR-CONTAINING CONTAMINANTS, IN FORM OF MERCAPTANS AND H2S FROM GAS |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
18R | Application refused |
Effective date: 20010618 |