WO2003011436A1 - Desulfuration - Google Patents
Desulfuration Download PDFInfo
- Publication number
- WO2003011436A1 WO2003011436A1 PCT/GB2002/003112 GB0203112W WO03011436A1 WO 2003011436 A1 WO2003011436 A1 WO 2003011436A1 GB 0203112 W GB0203112 W GB 0203112W WO 03011436 A1 WO03011436 A1 WO 03011436A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- units
- process according
- hydrolysis catalyst
- absorbent
- sulphide
- Prior art date
Links
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 26
- 230000007062 hydrolysis Effects 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 23
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000002745 absorbent Effects 0.000 claims abstract description 20
- 239000002250 absorbent Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000012530 fluid Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000011872 intimate mixture Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 235000014692 zinc oxide Nutrition 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
-
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
Definitions
- This invention relates to desulphurisation and in particular to the removal of sulphur compounds from fluid streams containing carbonyl sulphide.
- Carbonyl sulphide can be converted to hydrogen sulphide and carbon dioxide by hydrolysis with water.
- carbonyl sulphide is removed by passing the fluid (to which water has been added if necessary) through a bed of a suitable hydrolysis catalyst and then passing the effluent through a bed of a hydrogen sulphide absorbent or through an alternative hydrogen sulphide removal system. If the feedstock fluid contains hydrogen sulphide as well as carbonyl sulphide, in order to shift the equilibrium towards removal of the carbonyl sulphide, the fluid may be passed through a bed of a hydrogen sulphide absorbent prior to contact with the carbonyl sulphide hydrolysis catalyst.
- the present invention provides a process for the removal of carbonyl sulphide from a fluid stream comprising passing the fluid through a fixed bed of an intimate mixture of shaped units formed from particles of a carbonyl sulphide hydrolysis catalyst and shaped units formed from particles of an absorbent for hydrogen sulphide.
- Both types of shaped units in the mixture may be pellets, granules or extrudates having maxima and minima dimensions in the range 0.5 to 6 mm. They each preferably have an aspect ratio, i.e. the ratio of the maximum dimension to the minimum dimension, below 2. Preferably the maximum dimension of the absorbent units is 0.5 to 2 times the maximum dimension of the hydrolysis catalyst units.
- the relative proportions of the absorbent and hydrolysis catalyst units will depend on the activity of the hydrolysis catalyst units under the relevant process conditions. The greater the activity, the smaller is the proportion of hydrolysis catalyst units that is required, and hence the greater the overall sulphur removal capacity of the fixed bed.
- the use of a mixture of shaped units is advantageous compared to the use of shaped units formed from a mixture of particles of the hydrolysis catalyst and hydrogen sulphide absorbent as it is more versatile since the proportions of the units employed can be tailored to the specific application.
- the hydrolysis catalyst units form 5 to 50% by volume of the mixture of units.
- the hydrolysis catalyst units preferably comprise granules, pellets or extrudates of an activated alumina composition. They may contain 0% to 10% by weight of a suitable binder, for example calcium aluminate cement, to enable shaped units of adequate strength to be produced.
- the shaped units preferably have a BET surface area of above 50 m 2 /g, particularly over 00 m 2 /g, for example 150-400 m 2 /g.
- the hydrogen sulphide absorbent is preferably formed from a composition containing copper and/or zinc oxides, hydroxides, carbonates or hydroxycarbonates, and preferably has a BET surface area above 50 m 2 /g.
- the absorbent may also contain other components such as alumina and may contain up to about 10% by weight of a binder such as a calcium aluminate cement. Particularly suitable hydrogen sulphide absorbents are described in US 4871710.
- shaped units e.g. agglomerates, made from a precipitated composition containing copper, zinc and aluminium compounds and a binder can themselves be used for carbonyl sulphide removal
- the fluid stream being treated may be passed through the bed in the liquid or gaseous state at any convenient temperature ranging from ambient, i.e. about 20°C to about 200°C and at any convenient pressure, for example ranging from atmospheric to 100 bar abs.
- fluid streams to which the present invention may be applied include hydrocarbon streams such as natural gas; nitrogen and/or oxygen-containing streams such as air; carbon oxides streams such as carbon dioxide; and hydrogen-containing streams such as hydrogen/carbon oxides synthesis gas mixtures.
- the concentration of carbonyl sulphide in the fluid stream may vary within a wide range. Where it is more than about 100 ppm by weight, it may be desirable to decrease its concentration, prior to use as the feedstock to the process of the present invention, by an initial hydrolysis step followed by a hydrogen sulphide removal stage using for example a liquid absorbent.
- the feedstock also contains some water, preferably in an amount of at least three moles per mole of carbonyl sulphide.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Abstract
La présente invention concerne un procédé pour retirer du sulfure de carbonyle d'un courant liquide. Ce procédé consiste à faire passer le liquide à travers un lit fixe d'un mélange intime d'unités façonnées, constituées de particules d'un catalyseur d'hydrolyse de sulfure de carbonyle, et d'unités façonnées, constituées de particules d'un absorbant de sulfure d'hydrogène.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0118416A GB0118416D0 (en) | 2001-07-30 | 2001-07-30 | Desulphurisation |
| GB0118416.7 | 2001-07-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2003011436A1 true WO2003011436A1 (fr) | 2003-02-13 |
Family
ID=9919352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB2002/003112 WO2003011436A1 (fr) | 2001-07-30 | 2002-07-08 | Desulfuration |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB0118416D0 (fr) |
| WO (1) | WO2003011436A1 (fr) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006008317A1 (fr) * | 2004-07-22 | 2006-01-26 | Shell Internationale Research Maatschappij B.V. | Procede d'elimination de cos dans un flux de gaz de synthese contenant h2s et cos |
| WO2006065459A1 (fr) | 2004-12-17 | 2006-06-22 | Exxonmobil Research And Engineering Company | Systemes et procedes destines a reduire la teneur en soufre de flux d'hydrocarbures |
| WO2007082896A1 (fr) * | 2006-01-18 | 2007-07-26 | Shell Internationale Research Maatschappij B.V. | Procede d’elimination du sulfure de carbonyle et du sulfure d’hydrogene d’un courant gazeux de synthese |
| CN113426289A (zh) * | 2021-06-29 | 2021-09-24 | 松山湖材料实验室 | 一种水解吸附剂、一种高炉煤气脱硫方法及脱硫设备 |
| EP4497805A1 (fr) * | 2023-07-24 | 2025-01-29 | Bloom Energy Corporation | Systèmes de désulfuration comprenant de milieux mixtes et systèmes de pile à combustible les comprenant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2574310A1 (fr) * | 1984-12-12 | 1986-06-13 | Elf Aquitaine | Procede d'elimination des composes cos et cs2 contenus dans un gaz industriel |
| EP0218153A2 (fr) * | 1985-09-28 | 1987-04-15 | BASF Aktiengesellschaft | Procédé pour éliminer des composés sulfurés de courants gazeux |
| EP0698577A1 (fr) * | 1994-08-25 | 1996-02-28 | The Boc Group, Inc. | Procédé de purification de dioxyde de carbone |
| US5853681A (en) * | 1994-03-17 | 1998-12-29 | Imperial Chemical Industries Plc | Absorbents |
-
2001
- 2001-07-30 GB GB0118416A patent/GB0118416D0/en not_active Ceased
-
2002
- 2002-07-08 WO PCT/GB2002/003112 patent/WO2003011436A1/fr not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2574310A1 (fr) * | 1984-12-12 | 1986-06-13 | Elf Aquitaine | Procede d'elimination des composes cos et cs2 contenus dans un gaz industriel |
| EP0218153A2 (fr) * | 1985-09-28 | 1987-04-15 | BASF Aktiengesellschaft | Procédé pour éliminer des composés sulfurés de courants gazeux |
| US5853681A (en) * | 1994-03-17 | 1998-12-29 | Imperial Chemical Industries Plc | Absorbents |
| EP0698577A1 (fr) * | 1994-08-25 | 1996-02-28 | The Boc Group, Inc. | Procédé de purification de dioxyde de carbone |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2005263776B2 (en) * | 2004-07-22 | 2008-07-31 | Shell Internationale Research Maatschappij B.V. | Process for the removal of COS from a synthesis gas stream comprising H2S and COS |
| US7846325B2 (en) | 2004-07-22 | 2010-12-07 | Shell Oil Company | Process for the removal of COS and H2S from a synthesis gas stream comprising H2S and COS |
| WO2006008317A1 (fr) * | 2004-07-22 | 2006-01-26 | Shell Internationale Research Maatschappij B.V. | Procede d'elimination de cos dans un flux de gaz de synthese contenant h2s et cos |
| EA010025B1 (ru) * | 2004-07-22 | 2008-06-30 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Способ удаления cos из потока синтез-газа, включающего hs и cos |
| US7427385B2 (en) | 2004-12-17 | 2008-09-23 | Exxonmobil Research And Engineering Company | Systems and processes for reducing the sulfur content of hydrocarbon streams |
| JP2008524377A (ja) * | 2004-12-17 | 2008-07-10 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | 炭化水素ストリームの硫黄含有量を低減するためのシステムおよび方法 |
| WO2006065459A1 (fr) | 2004-12-17 | 2006-06-22 | Exxonmobil Research And Engineering Company | Systemes et procedes destines a reduire la teneur en soufre de flux d'hydrocarbures |
| CN101080482B (zh) * | 2004-12-17 | 2011-09-14 | 埃克森美孚研究工程公司 | 降低烃流中硫含量的系统和方法 |
| TWI382873B (zh) * | 2004-12-17 | 2013-01-21 | Exxonmobil Res & Eng Co | 用於減低烴流之硫含量的系統與方法 |
| WO2007082896A1 (fr) * | 2006-01-18 | 2007-07-26 | Shell Internationale Research Maatschappij B.V. | Procede d’elimination du sulfure de carbonyle et du sulfure d’hydrogene d’un courant gazeux de synthese |
| US8043589B2 (en) | 2006-01-18 | 2011-10-25 | Shell Oil Company | Process for removing carbonyl sulphide and hydrogen sulphide from a synthesis gas stream |
| CN113426289A (zh) * | 2021-06-29 | 2021-09-24 | 松山湖材料实验室 | 一种水解吸附剂、一种高炉煤气脱硫方法及脱硫设备 |
| EP4497805A1 (fr) * | 2023-07-24 | 2025-01-29 | Bloom Energy Corporation | Systèmes de désulfuration comprenant de milieux mixtes et systèmes de pile à combustible les comprenant |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0118416D0 (en) | 2001-09-19 |
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