EP0946259A1 - Procede et agent de desulfuration - Google Patents

Procede et agent de desulfuration

Info

Publication number
EP0946259A1
EP0946259A1 EP97944019A EP97944019A EP0946259A1 EP 0946259 A1 EP0946259 A1 EP 0946259A1 EP 97944019 A EP97944019 A EP 97944019A EP 97944019 A EP97944019 A EP 97944019A EP 0946259 A1 EP0946259 A1 EP 0946259A1
Authority
EP
European Patent Office
Prior art keywords
agent
compound
desulphurisation
manganese
iron
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.)
Withdrawn
Application number
EP97944019A
Other languages
German (de)
English (en)
Inventor
Rodney Martin Sambrook
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.)
Imperial Chemical Industries Ltd
Original Assignee
Dytech Corp 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 Corp Ltd filed Critical Dytech Corp Ltd
Publication of EP0946259A1 publication Critical patent/EP0946259A1/fr
Withdrawn legal-status Critical Current

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Gas Separation By Absorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Industrial Gases (AREA)

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.
EP97944019A 1996-10-21 1997-10-06 Procede et agent de desulfuration Withdrawn EP0946259A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9621906 1996-10-21
GBGB9621906.8A GB9621906D0 (en) 1996-10-21 1996-10-21 Desulphurisation
PCT/GB1997/002735 WO1998017374A1 (fr) 1996-10-21 1997-10-06 Procede et agent de desulfuration

Publications (1)

Publication Number Publication Date
EP0946259A1 true EP0946259A1 (fr) 1999-10-06

Family

ID=10801748

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97944019A Withdrawn EP0946259A1 (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)

Families Citing this family (3)

* 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
GB0619396D0 (en) 2006-10-02 2006-11-08 M I Drilling Fluids Uk Ltd Porous articles
MX2017002349A (es) * 2017-02-22 2017-07-10 Inst Nac De Investig Forestales Agricolas Y Pecuarias Remocion de h2s a baja temperatura por medio de ferritas nanometricas de alta area superficial obtenidas por metodo de co-precopitacion quimica modificado.

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE759979A (fr) * 1965-02-10 1971-06-07 Grillo Werke Ag Procede d'elimination du soufre dans les gaz residuaires
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
NL8105728A (nl) * 1981-10-30 1983-05-16 Tno Werkwijze voor het verwijderen van diwaterstofsulfide uit procesgassen met behulp van vaste acceptoren, werkwijze voor het cyclisch-regenereren van de gebruikte acceptoren bij hoge temperatuur, alsmede werkwijze voor het bereiden van acceptoren, die voor deze werkwijze geschikt zijn.
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
GB2152489B (en) * 1983-05-26 1986-10-08 Azerb I Nefti Khimii Im M Aziz Method for purifying gases from sulphurous compounds
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9817374A1 *

Also Published As

Publication number Publication date
AU4566497A (en) 1998-05-15
GB9621906D0 (en) 1996-12-11
GB9721228D0 (en) 1997-12-03
CA2266458A1 (fr) 1998-04-30
WO1998017374A1 (fr) 1998-04-30
GB2318309A (en) 1998-04-22
JP2001502236A (ja) 2001-02-20
GB2318309B (en) 2001-05-16
BR9712408A (pt) 1999-10-19

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