WO2003011436A1 - Desulfuration - Google Patents

Desulfuration Download PDF

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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
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
PCT/GB2002/003112
Other languages
English (en)
Inventor
Colin Woodward
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.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
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 Johnson Matthey PLC filed Critical Johnson Matthey PLC
Publication of WO2003011436A1 publication Critical patent/WO2003011436A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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.
PCT/GB2002/003112 2001-07-30 2002-07-08 Desulfuration Ceased WO2003011436A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0118416.7 2001-07-30
GB0118416A GB0118416D0 (en) 2001-07-30 2001-07-30 Desulphurisation

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 Ceased 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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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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