WO1998017374A1 - Procede et agent de desulfuration - Google Patents

Procede et agent de desulfuration Download PDF

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Publication number
WO1998017374A1
WO1998017374A1 PCT/GB1997/002735 GB9702735W WO9817374A1 WO 1998017374 A1 WO1998017374 A1 WO 1998017374A1 GB 9702735 W GB9702735 W GB 9702735W WO 9817374 A1 WO9817374 A1 WO 9817374A1
Authority
WO
WIPO (PCT)
Prior art keywords
agent
compound
desulphurisation
manganese
iron
Prior art date
Application number
PCT/GB1997/002735
Other languages
English (en)
Inventor
Rodney Martin Sambrook
Original Assignee
Dytech Corporation Ltd.
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 Dytech Corporation Ltd. filed Critical Dytech Corporation Ltd.
Priority to BR9712408-7A priority Critical patent/BR9712408A/pt
Priority to CA002266458A priority patent/CA2266458A1/fr
Priority to JP10519058A priority patent/JP2001502236A/ja
Priority to AU45664/97A priority patent/AU4566497A/en
Priority to EP97944019A priority patent/EP0946259A1/fr
Publication of WO1998017374A1 publication Critical patent/WO1998017374A1/fr

Links

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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

Definitions

  • the invention relates to desulphurisation and in particular to the purification of streams (liquid or gas or both) by the partial or complete removal of sulphur compounds, e.g. hydrogen sulphide, low molecular weight mercaptans, or the like therefrom.
  • sulphur compounds e.g. hydrogen sulphide, low molecular weight mercaptans, or the like therefrom.
  • the invention may also be applied to the purification of air or other gas containing sulphur compounds.
  • the invention relates to a method and a desulphurisation agent.
  • the invention provides a method of reducing the content of a sulphur compound in stream of gas and/or liquid, the method comprising contacting the stream with a desulphurisation agent comprising at least one compound of manganese and at least one compound of iron.
  • the desulphurisation may be performed, for example, at a temperature from about ambient up to about 450°C, preferably from about 20°C to about 450°C, most preferably from about 40°C to about 150°C.
  • the compounds are the oxides, hydroxides, carbonates, e.g. hydroxycarbonate or basic carbonate or the like of both manganese and iron.
  • These active ingredients may be incorporated within a carrier of the invention by simple impregnation or impregnation/deposition, co forming, precipitation from aqueous solution or other techniques well known to those skilled in the art of catalyst preparation.
  • the carrier may be alumina, sihca, alumino silicates or the like.
  • the content of the carrier material will be in the range 1 to 40% by weight.
  • the compounds are in the relative molar proportions of 8:1 to 1 :8, most preferably about 1 :1.
  • the desulphurisation agent comprises shaped particles.
  • the particles may be presented in a variety of shapes and sizes preferably as spheres; extrudates, granules, tablets or the like.
  • a binding agent such as cement, alumina, clay, sihca, orgamc resins or the like may be present to enhance the physical properties of the shaped material.
  • the shaped material may require exposure to elevated temperatures to achieve the optimum bond strength.
  • the agent includes a promoter which is one or more of potassium hydroxide, nickel hydroxide and sodium hydroxide, optionally with a derivative of zinc.
  • the concentration of the promoter is preferably in the range of from about 1% to about 10%.
  • the inclusion of copper or copper compounds has proved to be beneficial because it will scavenge lower concentrations of sulphur compounds and also remove arsine.
  • the shaped desulphurisation agent is porous.
  • the pore volume will be in the range of 0.1 to 0.6 ml/g, preferably 0.25-0.45 ml/g. It is recognised that the shaped porous materials should exhibit a significant level of macro porosity.
  • the desulphurisation agent may be used in a fixed bed, a fluid bed or a moving bed.
  • the choice of the reactor system will depend on generated requirements and the nature of the gas stream, e.g. sour feed. Particle sizes of about 3 to about 6mm are particularly useful in a fixed bed. In a fluid bed, the particle size is preferably in the range about 20 to about 120 microns, most preferably about 30 to about 100 microns.
  • the particle size is preferably in the range about 120 to 600
  • microns most preferably about 200 to about 500 microns.
  • the method of the invention may be enhanced by the incorporation of materials with
  • Such materials may be added according to the physical form of the desulphurisation agent. They may be added on to the surface or within the pores of a porous desulphurisation agent or in the bulk phase. Such materials may be catalytically
  • the materials may be incorporated within the material of the invention by impregnation, deposition, coforming, precipitation techniques well known to those skilled in the art of catalyst
  • the content of the sorption materials may range from about 0.5 to 40%
  • One such reagent is an alkaline reagent
  • alkah metal hydroxide or silicate such as alkah metal hydroxide or silicate
  • the alkah metal is preferably sodium.
  • Such an alkaline reagent will react with halides or strongly acidic gases present in the sour
  • reagents may be impregnated into the desulphurisation agent or incorporated into the bulk phase by other means well known to those skilled in the art of catalyst preparation.
  • the spent desulphurisation agent of the invention may be regenerated by exposure to an oxidising atmosphere e.g. air at elevated temperature.
  • an oxidising atmosphere e.g. air at elevated temperature.
  • the presence of steam when regenerating may be beneficial.
  • the method of the present invention includes the further step of exposing the spent agent to oxidation at elevated temperature to remove the sulphur compounds and regenerate the agent for re-use.
  • the sulphur compound to be removed may be hydrogen sulphide gas or a low molecular weight mercaptan such as propyl mercaptan.
  • the hydrocarbon stream may be liquid or gas or both, examples being natural gas, town gas, industrial waste gas, coke oven gas, coal gas, liquid or gas from petroleum plant oil refinery. Effluent streams from biomass digesters, general industrial process may also be treated.
  • the method may be performed at pressures ranging from about atmospheric to about
  • the invention provides a desulphurisation agent comprising at least one compound of manganese and at least one compound of iron in the relative molar proportions of from about 8:1 to 1 :8 (Mn:Fe).
  • a desulphurisation agent comprising at least one compound of manganese and at least one compound of iron in the relative molar proportions of from about 8:1 to 1 :8 (Mn:Fe).
  • the invention provides such an agent incorporating a promoter and in yet a further aspect the invention provides such an agent incorporating a sorption material.
  • Pellets of varying composition were prepared by standard forming techniques, calcined at 450OC and allowed to cool.

Abstract

On élimine des composés de soufre contenus dans un flux de gaz et/ou de liquide à l'aide d'un agent comprenant au moins un composé de manganèse et au moins un composé de fer. L'agent de désulfuration contient au moins un composé de manganèse et au moins un composé de fer dans des proportions molaires d'environ 8:1 à 1:8.
PCT/GB1997/002735 1996-10-21 1997-10-06 Procede et agent de desulfuration WO1998017374A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR9712408-7A BR9712408A (pt) 1996-10-21 1997-10-06 Método e agente para dessulfurização
CA002266458A CA2266458A1 (fr) 1996-10-21 1997-10-06 Procede et agent de desulfuration
JP10519058A JP2001502236A (ja) 1996-10-21 1997-10-06 硫黄質除去の方法およびその薬剤
AU45664/97A AU4566497A (en) 1996-10-21 1997-10-06 Method and agent for desulphurisation
EP97944019A EP0946259A1 (fr) 1996-10-21 1997-10-06 Procede et agent de desulfuration

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9621906.8 1996-10-21
GBGB9621906.8A GB9621906D0 (en) 1996-10-21 1996-10-21 Desulphurisation

Publications (1)

Publication Number Publication Date
WO1998017374A1 true WO1998017374A1 (fr) 1998-04-30

Family

ID=10801748

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1997/002735 WO1998017374A1 (fr) 1996-10-21 1997-10-06 Procede et agent de desulfuration

Country Status (7)

Country Link
EP (1) EP0946259A1 (fr)
JP (1) JP2001502236A (fr)
AU (1) AU4566497A (fr)
BR (1) BR9712408A (fr)
CA (1) CA2266458A1 (fr)
GB (2) GB9621906D0 (fr)
WO (1) WO1998017374A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008040966A1 (fr) 2006-10-02 2008-04-10 M-I Drilling Fluids Uk Limited Procédé de formation d'un agent et son utilisation dans la désulfuration
WO2018156006A1 (fr) * 2017-02-22 2018-08-30 Instituto Nacional De Investigación Forestales, Agrícolas Y Pecuarias Élimination de h2s à basse température au moyen de ferrites nanométriques à grande surface obtenues par un procédé de co-précipitation chimique modifié

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7105140B2 (en) * 2002-03-04 2006-09-12 Conocophillips Company Desulfurization compositions

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1144071A (en) * 1965-02-10 1969-03-05 Grillo Werke Ag Process for the removal of sulphur-containing compounds from industrial gases
EP0078576A1 (fr) * 1981-10-30 1983-05-11 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk onderzoek TNO Procédé pour éliminer l'hydrogène sulfuré de gaz de processus utilisant des accepteurs solides, procédé pour la régénération cyclique des accepteurs utilisés, à température élevée, ainsi que procédé pour préparer les accepteurs, utilisable dans ce procédé

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5430398B2 (fr) * 1975-01-29 1979-09-29
US4017586A (en) * 1975-08-06 1977-04-12 Reeves Adam A Stack gas treatment
SU825133A1 (ru) * 1978-12-20 1981-04-30 Институт Газа Ан Украинской Сср Катализатор для конверсии сернистых газов в элементарную серу
JPS56100622A (en) * 1980-01-17 1981-08-12 Hitachi Zosen Corp Dry desulfurizing method in reducing atmosphere
DE3228481A1 (de) * 1982-07-30 1984-02-02 VEG-Gasinstituut N.V., 7300 Apeldoorn Reaktionsmasse, verfahren zu ihrer herstellung und deren verwendung
GB2125779B (en) * 1982-08-19 1986-01-29 Nippon Shokubai Kagaku Gogyo C Desulfurization of h2s-containing gases
NL8320199A (nl) * 1983-05-26 1985-04-01 Azerb I Nefti Khimii Im M Aziz Werkwijze voor verwijderen van zwavelverbindingen uit gassen.
JPS60166033A (ja) * 1984-02-06 1985-08-29 Mitsubishi Heavy Ind Ltd 脱硫剤
US5417946A (en) * 1993-12-30 1995-05-23 Shell Oil Company Process for removing total reduced sulfur compounds from gaseous stream

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1144071A (en) * 1965-02-10 1969-03-05 Grillo Werke Ag Process for the removal of sulphur-containing compounds from industrial gases
US3492083A (en) * 1965-02-10 1970-01-27 Grillo Werke Ag Process for the removal of sulphur from industrial gases and to apparatus for use in such a process
EP0078576A1 (fr) * 1981-10-30 1983-05-11 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk onderzoek TNO Procédé pour éliminer l'hydrogène sulfuré de gaz de processus utilisant des accepteurs solides, procédé pour la régénération cyclique des accepteurs utilisés, à température élevée, ainsi que procédé pour préparer les accepteurs, utilisable dans ce procédé

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008040966A1 (fr) 2006-10-02 2008-04-10 M-I Drilling Fluids Uk Limited Procédé de formation d'un agent et son utilisation dans la désulfuration
EP2402069A1 (fr) 2006-10-02 2012-01-04 M-I Drilling Fluids UK Limited Articles poreux
AU2007304053B2 (en) * 2006-10-02 2012-07-12 M-I Drilling Fluids Uk Limited Method of forming an agent and its use in desulphurisation
US8871675B2 (en) 2006-10-02 2014-10-28 M I Drilling Fluids Uk Ltd. Method of forming an agent and its use in desulphurisation
US9987625B2 (en) 2006-10-02 2018-06-05 M-I Drilling Fluids Uk Limited Desulfurization agent
WO2018156006A1 (fr) * 2017-02-22 2018-08-30 Instituto Nacional De Investigación Forestales, Agrícolas Y Pecuarias Élimination de h2s à basse température au moyen de ferrites nanométriques à grande surface obtenues par un procédé de co-précipitation chimique modifié

Also Published As

Publication number Publication date
GB9621906D0 (en) 1996-12-11
BR9712408A (pt) 1999-10-19
AU4566497A (en) 1998-05-15
JP2001502236A (ja) 2001-02-20
GB9721228D0 (en) 1997-12-03
EP0946259A1 (fr) 1999-10-06
CA2266458A1 (fr) 1998-04-30
GB2318309A (en) 1998-04-22
GB2318309B (en) 2001-05-16

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