EP0880395A1 - Procede pour eliminer les contaminants a teneur en soufre, les aromatiques et les hydrocarbures contenus dans un gaz - Google Patents

Procede pour eliminer les contaminants a teneur en soufre, les aromatiques et les hydrocarbures contenus dans un gaz

Info

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
Application number
EP97900807A
Other languages
German (de)
English (en)
Inventor
Jan Adolf Lagas
Theodorus Joseph Petrus Van Pol
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stork Engineers and Contractors BV
Original Assignee
Stork Engineers and Contractors BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Stork Engineers and Contractors BV filed Critical Stork Engineers and Contractors BV
Publication of EP0880395A1 publication Critical patent/EP0880395A1/fr
Ceased legal-status Critical Current

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%.

Abstract

Cette invention se rapporte à un procédé pour éliminer les contaminants à teneur en soufre, sous la forme de mercaptans et H2S, contenus dans un gaz d'hydrocarbures, qui peut également renfermer du CO2 et des hydrocarbures aliphatiques et aromatiques supérieurs, puis à récupérer le soufre élémentaire. Dans une première phase d'absorption de ce procédé, les contaminants à teneur en soufre sont retirés du gaz, pour former d'une part un courant de gaz purifié et d'autre part un gaz sulfureux, lequel est hydrogéné pour convertir la majeure partie des mercaptans en H2S, puis le gaz sulfureux hydrogéné est amené à une seconde phase d'absorption, dans laquelle le gaz sulfureux est séparé en un premier courant de gaz enrichi en H2S, qui est amené à une installation de Claus, suivie par une étape d'oxydation sélective de H2S en soufre élémentaire dans le gaz de queue, et en un second courant de gaz à teneur réduite en H2S, ce second courant de gaz étant brûlé.
EP97900807A 1996-01-19 1997-01-20 Procede pour eliminer les contaminants a teneur en soufre, les aromatiques et les hydrocarbures contenus dans un gaz Ceased EP0880395A1 (fr)

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 (fr) 1996-01-19 1997-01-20 Procede pour eliminer les contaminants a teneur en soufre, les aromatiques et les hydrocarbures contenus dans un gaz

Publications (1)

Publication Number Publication Date
EP0880395A1 true EP0880395A1 (fr) 1998-12-02

Family

ID=19762183

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97900807A Ceased EP0880395A1 (fr) 1996-01-19 1997-01-20 Procede pour eliminer les contaminants a teneur en soufre, les aromatiques et les hydrocarbures contenus dans un gaz

Country Status (10)

Country Link
EP (1) EP0880395A1 (fr)
JP (1) JP2000503293A (fr)
KR (1) KR19990077361A (fr)
CN (1) CN1208360A (fr)
AU (1) AU1321397A (fr)
CA (1) CA2241790A1 (fr)
NL (1) NL1002134C2 (fr)
TW (1) TW381043B (fr)
WO (1) WO1997026069A1 (fr)
ZA (1) ZA97370B (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
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
EP1773473B1 (fr) * 2004-08-02 2010-10-20 Shell Internationale Research Maatschappij B.V. Procédé pour l'élémination des mercaptans d'un courant de gaz inerte
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
WO2014106770A2 (fr) * 2012-12-10 2014-07-10 Total Sa Procédé intégré de récupération de co2 natif de haute qualité à partir de gaz acide comprenant h2s et co2
WO2016112371A1 (fr) * 2015-01-09 2016-07-14 Sr20 Holdings Llc Procédé et système de pyrolyse de pneus en combustibles et autres produits
WO2018115919A1 (fr) * 2016-12-23 2018-06-28 Total Sa Procédé intégré de traitement de soufre élémentaire

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9726069A1 *

Also Published As

Publication number Publication date
NL1002134C2 (nl) 1997-07-22
TW381043B (en) 2000-02-01
AU1321397A (en) 1997-08-11
WO1997026069A1 (fr) 1997-07-24
CN1208360A (zh) 1999-02-17
CA2241790A1 (fr) 1997-07-24
JP2000503293A (ja) 2000-03-21
KR19990077361A (ko) 1999-10-25
ZA97370B (en) 1997-07-17

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