WO1998017374A1 - Method and agent for desulphurisation - Google Patents
Method and agent for desulphurisation Download PDFInfo
- 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
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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Gas Separation By Absorption (AREA)
- Industrial Gases (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9712408-7A BR9712408A (en) | 1996-10-21 | 1997-10-06 | Method and agent for desulfurization |
AU45664/97A AU4566497A (en) | 1996-10-21 | 1997-10-06 | Method and agent for desulphurisation |
EP97944019A EP0946259A1 (en) | 1996-10-21 | 1997-10-06 | Method and agent for desulphurisation |
CA002266458A CA2266458A1 (en) | 1996-10-21 | 1997-10-06 | Method and agent for desulphurisation |
JP10519058A JP2001502236A (en) | 1996-10-21 | 1997-10-06 | Sulfur removal method and chemicals |
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 (en) | 1998-04-30 |
Family
ID=10801748
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1997/002735 WO1998017374A1 (en) | 1996-10-21 | 1997-10-06 | Method and agent for desulphurisation |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0946259A1 (en) |
JP (1) | JP2001502236A (en) |
AU (1) | AU4566497A (en) |
BR (1) | BR9712408A (en) |
CA (1) | CA2266458A1 (en) |
GB (2) | GB9621906D0 (en) |
WO (1) | WO1998017374A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008040966A1 (en) | 2006-10-02 | 2008-04-10 | M-I Drilling Fluids Uk Limited | Method of forming an agent and its use in desulphurisation |
WO2018156006A1 (en) * | 2017-02-22 | 2018-08-30 | Instituto Nacional De Investigación Forestales, Agrícolas Y Pecuarias | Low-temperature removal of h2s using large-surface-area nano-ferrites obtained using a modified chemical coprecipitation method |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7105140B2 (en) * | 2002-03-04 | 2006-09-12 | Conocophillips Company | Desulfurization compositions |
Citations (2)
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 (en) * | 1981-10-30 | 1983-05-11 | Nederlandse Organisatie voor toegepast-natuurwetenschappelijk onderzoek TNO | Process for removing hydrogen sulphide from process gases using solid acceptors, process for cyclic regenerating the used acceptors at high temperature, as well as process for preparing acceptors, which are suitable for this process |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5430398B2 (en) * | 1975-01-29 | 1979-09-29 | ||
US4017586A (en) * | 1975-08-06 | 1977-04-12 | Reeves Adam A | Stack gas treatment |
SU825133A1 (en) * | 1978-12-20 | 1981-04-30 | Институт Газа Ан Украинской Сср | Catalyst for conversion of sulfur-containing gases to elemental sulfur |
JPS56100622A (en) * | 1980-01-17 | 1981-08-12 | Hitachi Zosen Corp | Dry desulfurizing method in reducing atmosphere |
DE3228481A1 (en) * | 1982-07-30 | 1984-02-02 | VEG-Gasinstituut N.V., 7300 Apeldoorn | REACTION MEASURES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
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 (en) * | 1984-02-06 | 1985-08-29 | Mitsubishi Heavy Ind Ltd | Desulfurizing agent |
US5417946A (en) * | 1993-12-30 | 1995-05-23 | Shell Oil Company | Process for removing total reduced sulfur compounds from gaseous stream |
-
1996
- 1996-10-21 GB GBGB9621906.8A patent/GB9621906D0/en active Pending
-
1997
- 1997-10-06 JP JP10519058A patent/JP2001502236A/en active Pending
- 1997-10-06 AU AU45664/97A patent/AU4566497A/en not_active Abandoned
- 1997-10-06 WO PCT/GB1997/002735 patent/WO1998017374A1/en not_active Application Discontinuation
- 1997-10-06 CA CA002266458A patent/CA2266458A1/en not_active Abandoned
- 1997-10-06 BR BR9712408-7A patent/BR9712408A/en not_active Application Discontinuation
- 1997-10-06 GB GB9721228A patent/GB2318309B/en not_active Expired - Fee Related
- 1997-10-06 EP EP97944019A patent/EP0946259A1/en not_active Withdrawn
Patent Citations (3)
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 (en) * | 1981-10-30 | 1983-05-11 | Nederlandse Organisatie voor toegepast-natuurwetenschappelijk onderzoek TNO | Process for removing hydrogen sulphide from process gases using solid acceptors, process for cyclic regenerating the used acceptors at high temperature, as well as process for preparing acceptors, which are suitable for this process |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008040966A1 (en) | 2006-10-02 | 2008-04-10 | M-I Drilling Fluids Uk Limited | Method of forming an agent and its use in desulphurisation |
EP2402069A1 (en) | 2006-10-02 | 2012-01-04 | M-I Drilling Fluids UK Limited | Porous articles |
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 (en) * | 2017-02-22 | 2018-08-30 | Instituto Nacional De Investigación Forestales, Agrícolas Y Pecuarias | Low-temperature removal of h2s using large-surface-area nano-ferrites obtained using a modified chemical coprecipitation method |
Also Published As
Publication number | Publication date |
---|---|
CA2266458A1 (en) | 1998-04-30 |
JP2001502236A (en) | 2001-02-20 |
GB9621906D0 (en) | 1996-12-11 |
EP0946259A1 (en) | 1999-10-06 |
GB2318309B (en) | 2001-05-16 |
GB2318309A (en) | 1998-04-22 |
AU4566497A (en) | 1998-05-15 |
BR9712408A (en) | 1999-10-19 |
GB9721228D0 (en) | 1997-12-03 |
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