WO2004099351A1 - Procede de desulfuration de courants de gaz combustible - Google Patents

Procede de desulfuration de courants de gaz combustible Download PDF

Info

Publication number
WO2004099351A1
WO2004099351A1 PCT/NL2004/000307 NL2004000307W WO2004099351A1 WO 2004099351 A1 WO2004099351 A1 WO 2004099351A1 NL 2004000307 W NL2004000307 W NL 2004000307W WO 2004099351 A1 WO2004099351 A1 WO 2004099351A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorbent
support material
metal salt
metal
adsorbents
Prior art date
Application number
PCT/NL2004/000307
Other languages
English (en)
Inventor
Paulus Johannes De Wild
Erwin Roderick Stobbe
Rudolph George Nyqvist
Cornelis Petrus Jong
Original Assignee
Stichting Energieonderzoek Centrum Nederland
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 Stichting Energieonderzoek Centrum Nederland filed Critical Stichting Energieonderzoek Centrum Nederland
Publication of WO2004099351A1 publication Critical patent/WO2004099351A1/fr

Links

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
    • B01D53/02—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
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0218—Compounds of Cr, Mo, W
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0222—Compounds of Mn, Re
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/024—Compounds of Zn, Cd, Hg
    • B01J20/0244—Compounds of Zn
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0277—Carbonates of compounds other than those provided for in B01J20/043
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0288—Halides of compounds other than those provided for in B01J20/046
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/14—Diatomaceous earth
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/11—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/018—Natural gas engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/414—Further details for adsorption processes and devices using different types of adsorbents
    • B01D2259/4141—Further details for adsorption processes and devices using different types of adsorbents within a single bed
    • B01D2259/4143—Further details for adsorption processes and devices using different types of adsorbents within a single bed arranged as a mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/414—Further details for adsorption processes and devices using different types of adsorbents
    • B01D2259/4141—Further details for adsorption processes and devices using different types of adsorbents within a single bed
    • B01D2259/4145—Further details for adsorption processes and devices using different types of adsorbents within a single bed arranged in series

Definitions

  • the invention relates to a method for the removal of gaseous organic sulphur compounds, in particular tetrahydrothiophene (THT), from a stream of fuel gas, in particular natural gas.
  • the method according to the invention can be used, for example, in a gas filter for the removal of organic sulphur compounds from natural gas for a PEMFC fuel cell.
  • the invention also relates to a method for depositing metal salts on a support material to prepare the adsorbent.
  • the 'polymer electrolyte (or proton exchange) membrane fuel cell' (PEMFC) is an important candidate for relatively small scale applications as stationary micro combined heat and power ( ⁇ -CHP) and in electric transport.
  • the fuel for the PEMFC is hydrogen.
  • successful use of PEMFCs is dependent on the availability of hydrogen, for which there is as yet no (large scale) infrastructure.
  • logistical fuels such as diesel, petrol, naphtha, LPG and natural gas where the fuel cell is installed.
  • natural gas offers many advantages in this regard. For instance, natural gas has a high energy density, is relatively clean and can easily be stored in liquid form. Moreover, natural gas (still) occurs all over the world, frequently in appreciable quantities.
  • natural gas contains a greater or lesser amount of sulphur, for example in the form of naturally occurring compounds such as mercaptans and other organosulphur compounds, hydrogen sulphide and carbonyl sulphide.
  • sulphur for domestic use natural gas is first desulphurised at the source, after which a sulphur-containing odorant is added on the grounds of safety considerations with regard to leaks. This is subject to statutory regulations in various countries.
  • odorants are, inter alia, ethyl mercaptan (EM), normal-propyl mercaptan (NPM), iso-propyl mercaptan (IPM), secondary-butyl mercaptan (SBM), tertiary-butyl mercaptan (TBM), dimethyl sulphide (DMS), dimethyl disulphide, diethyl sulphide, diethyl disulphide, tetrahydrothiophene (THT) and mixtures of these odorants.
  • EM ethyl mercaptan
  • NPM normal-propyl mercaptan
  • IPM iso-propyl mercaptan
  • SBM secondary-butyl mercaptan
  • TBM tertiary-butyl mercaptan
  • DMS dimethyl sulphide
  • DTS dimethyl disulphide
  • diethyl sulphide diethyl disulphide
  • TTT
  • THT cyclic sulphide tetrahydrothiophene
  • tetramethylene sulphide which is widely used in the Netherlands and in the rest of Europe, offers many advantages for use as a natural gas odorant, such as a low odour limit, a typical 'gas' odour, not being readily oxidisable in gas distribution systems and a relatively good soil permeability.
  • THT cyclic sulphide tetrahydrothiophene
  • tetramethylene sulphide which is widely used in the Netherlands and in the rest of Europe, offers many advantages for use as a natural gas odorant, such as a low odour limit, a typical 'gas' odour, not being readily oxidisable in gas distribution systems and a relatively good soil permeability.
  • approximately 18 mg THT is added per m 3 natural gas. This corresponds to approximately 5 ppm sulphur.
  • Dutch natural gas naturally contains little sulphur.
  • a typical conversion system for natural gas comprises the following process steps:
  • a natural gas processor for converting natural gas to synthesis gas via, for example, catalytic partial oxidation
  • the catalysts that are used in such a natural gas conversion chain (steps 1 - 3) and in the polymer fuel cell are sensitive to sulphur in the fuel. This applies in particular to the low- temperature shift catalyst based on copper and zinc oxide and the platinum-based anode catalyst of the polymer fuel cell.
  • the sensitivity of the other catalytic process steps to sulphur is uncertain, but is probably high. As a precaution it is therefore best to remove sulphur compounds from the natural gas with the aid of a suitable filter material before the gas is used in the conversion chain.
  • a ⁇ -CHP installation will use approximately 1,200 m natural gas for the production of electricity and heat. This quantity will have to be desulphurised to protect the natural gas conversion chain and to protect the fuel cell.
  • a quantity of 1,200 m natural gas to be purified corresponds to approximately 21.6 g THT.
  • the capacity of the filter material must be at least 4.32 g THT per litre.
  • a bulk density of the filter material of 0.6 kg/1 this corresponds to a sulphur adsorption capacity of approximately 0.6 % (m/m) (as S).
  • a ⁇ -CHP installation can consume distinctly more than 1,200 m 3 natural gas. For instance, additional heat demand is met by a peak burner. THT does not have to be removed from the natural gas that is burned in this burner. This also applies for the natural gas that is used for cooking and producing hot tap water.
  • a THT filter For successful use in a natural gas-fired micro combined heat and power installation, a THT filter must preferably meet the following conditions:
  • HDS hydrodesulphurisation
  • H 2 S hydrodesulphurisation
  • adsorption capacity of such adsorbents for odorants such as THT in natural gas is so low that for annual use in a domestic ⁇ -CHP installation a large volume of adsorbent is required (typically more than 10 litres). This is not desirable in a small scale installation. It is also necessary that the zeolite is exchanged with specific cations, washed to remove salt residues and then calcined at temperatures between 250-500 °C.
  • a novel zeolite is described as adsorbent for the removal of sulphur compounds from, for example, natural gas.
  • the zeolite is of the X, Y or ⁇ type and contains - ion-exchanged - silver, copper, zinc, iron, cobalt or nickel.
  • the silver-exchanged Y zeolite (Ag(Na)-Y) is found to be very effective in the removal of a mixture of 1.2 ppm TBM and 1.8 ppm DMS from town gas (87.8 % methane, 5.9 % ethane, 4.6 % propane, 0.8 % n-pentane and 0.8 % i-pentane).
  • the aim of the invention is therefore to find a method for the removal of naturally occurring and/or deliberately added sulphur-containing organic compounds, such as the odorant THT from a fuel gas like natural gas, in which an inexpensive and environmentally friendly material is used that has a high activity and high capacity for the removal of sulphur-containing organic odorants, such as THT from natural gas, at relatively low temperatures.
  • a further aim of this invention is to find a method that is able to remove naturally occurring and/or deliberately added sulphur-containing organic compounds, such as odorants, from fuel gases at room temperature and operating temperature.
  • a further aim is to find a method with which use is made of adsorbents that are easy and inexpensive to prepare.
  • the invention therefore relates to a method for the removal of organosulphur compounds from a fuel gas stream wherein the gas stream is brought into contact with an adsorbent, characterised in that the adsorbent is a support material comprising a metal salt.
  • the invention relates to a method for the removal of organosulphur compounds from a fuel gas stream wherein the gas stream is brought into contact with an adsorbent, characterised in that the adsorbent is a support material on which a metal salt has been deposited, and wherein no heat treatment of the support material is carried out after the deposition of the metal salt, except for a heat treatment at temperatures below 100 °C.
  • the invention also relates to a method for depositing a metal salt on a support material, comprising:
  • the invention also relates to adsorbents that have been obtained or can be obtained in this way and to the use of such adsorbents for the removal of organosulphur compounds from fuel gas streams, and wherein no heat treatment of the support material is carried out after the deposition of the metal salt, except for a heat treatment at temperatures below 100 °C.
  • the invention also relates to a combination of a gas filter based on an adsorbent and a (PEMFC) fuel cell, characterised in that the adsorbent is a support material on which a metal salt has been deposited (and wherein no heat treatment of the support material is carried out after the deposition of the metal salt, except for a heat treatment at temperatures below 100 °C.
  • adsorbent is a support material on which a metal salt has been deposited (and wherein no heat treatment of the support material is carried out after the deposition of the metal salt, except for a heat treatment at temperatures below 100 °C.
  • the support material on which metal salts have been deposited and that is used as adsorbent in the method of the invention can be a material chosen from the group consisting of natural or synthetic clay mineral, (active) charcoal, natural or synthetic zeolite, molecular sieve, (active) alumina, (active) silica, silica gel, diatomaceous earth and pumice, or other adsorbents known to those skilled in the art (such as, for example, monolites constructed from the abovementioned support materials).
  • the support material has a BET surface area of at least approximately 1 m 2 /g, for example between approximately 1 and 1,500 m 2 /g, like approximately 5 and 1,500 m 2 /g.
  • the BET surface area is between approximately 10 and 500 m 2 /g.
  • the support materials are adsorbents, that is to say the support materials are also already able to adsorb organosulphur compounds without the deposited metal salt.
  • the support materials are porous, such as is the case with, for example, zeolites or aluminas.
  • the support material is one of the materials as described above, with the exception of zeolite, or one of the materials as described above with the exception of a clay mineral from the hormite group, or one of the materials as described above with the exception of zeolite and a clay mineral from the hormite group, or one of the materials as described above with the exception of sepiolite.
  • Clay minerals that are suitable and do not belong to the hormite group are, for example, bentonite, montmorillonite, vermiculites, smectites, halloysites, hydrotalcites, kaolinites, illites, saponites and hectorites.
  • the support material is chosen from one of these clay minerals.
  • Suitable metals are transition metals, lanthanides and also some alkali metals or alkaline earth metals, such as metals from the groups la, lb, lib, nib, IVb, Vb, VTIb, VHI of the periodic system.
  • this embodiment comprises a method where the metal is chromium, manganese, iron, cobalt, nickel or copper.
  • Suitable metal salts are, for example, chlorides, nitrates, sulphates, chlorates, phosphates, formates, carbonates, oxalates, acetates, etc.
  • an adsorbent is used where the support material is impregnated or mixed with an iron(II) salt or iron(ffl) salt.
  • metal chlorides are used and the invention comprises, for example, a method where the metal salt is iron(H) chloride or iron(III) chloride.
  • the salts can also be coordinated by water molecules.
  • the support material can also be provided with combinations of metal salts, for example salts of iron and chromium, or copper and chromium, copper and iron, etc., more particularly, for example, sepiolite impregnated with a copper salt (such as copper acetate) and an iron salt (such as iron(L ⁇ ) chloride).
  • the loading with the metal in the form of a metal salt will depend on the metal chosen, hi general, the amount of metal will be approximately 0.2 - 50 % (m/m) (based on the metal with respect to the support material), for example approximately 0.2 - 40 % (m/m), preferably between 0.5 and 20 % (m m), for example 2, 5 or 10 % (m m).
  • the support material can be physically mixed with the metal salt, with or without the addition of a small amount of liquid (for example water, ethanol or another low-boiling liquid).
  • a suitable adsorbent for the method of the invention can be obtained by this means.
  • a method is used with which the metal salt is applied to the support material by means of impregnation.
  • this is carried out using aqueous solutions or suspensions at temperatures of up to approximately 60 - 80 °C, for example at room temperature.
  • use can be made of the incipient wetness technique ('dry impregnation').
  • a method is used with which the support material, for example sepiolite, is impregnated with iron(III) chloride.
  • the adsorbent can be loaded with the metal salt (depositing of metal salts) with means known to the person skilled in the art, like e.g.
  • wet impregnation the volume of a liquid with (solved) salt is larger than the pore volume of the adsorbent
  • dry impregnation or "incipient wetness”: volume of liquid with (partially solved) salt is equal to pore volume of adsorbent
  • ion-exchange exchange in the liquid phase, wherein the metals (ions) to be exchanged are at least partially solved in the liquid as ions (or as complexed ions) and wherein the adsorbent is stirred in the liquid with the metals to be exchanged
  • dry mixing as mentioned above (without liquid).
  • the incipient wetness method can be employed.
  • the invention also comprises a method for the deposition of metal salts on a support material, comprising mixing the desired amount of metal salt of approximately 0.2 - 50 % (m m) (based on the metal with respect to the support material) with a liquid, mixing the solution or suspension with the support material at temperatures of up to approximately 60 - 80 °C, with stirring and/or ultrasound waves, and drying the product obtained at temperatures of up to approximately 60 - 80 °C.
  • the person skilled in the art may also combine steps for loading the support material.
  • the method for loading the support material according to the invention can generally be described by:
  • step 3 mixing the metal salt, metal salt solution or metal salt suspension of step 1 and the support material or support material suspension of step 2, at temperatures of up to approximately 60 - 80 °C, and optionally admixing a liquid, 4. the whole is dried at temperatures of up to approximately 60 - 80 °C.
  • this mixing will mean stirring, but e.g. also a ball mill can be used for mixing the solution or suspension with the support material.
  • ultrasound waves can be used. Ultrasound waves can also be used to improve or speed up solving and/or suspending the desired amount of metal salt in liquid.
  • the adsorbent obtained can be subjected to a subsequent heat treatment (inter alia drying).
  • This heat treatment should preferably be carried out at relatively low temperatures, hi one embodiment the invention comprises a method with which a heat treatment is carried out on the support material after the deposition of the metal salts, at temperatures below 100 °C.
  • a method is employed with which a heat treatment is carried out on the support material after the deposition of the metal salts, at temperatures below 80 °C, for example at 30, 40 or 50 °C, for a few hours in air.
  • metal salts are not converted, or are not substantially converted, to metal oxides.
  • metal salts are not converted, or are not substantially converted, to metal oxides.
  • a substantial proportion of the metal salt remains in its original form, as it was deposited, or optionally is partially oxidised, for example to an oxychloride.
  • a substantial proportion, for example 50 % (m/m) or more will not continue to oxidise to a metal oxide (M x O y ) but will remain on the support material in the form of a metal salt or optionally metal oxy-salt.
  • the person skilled in the art will understand that the above described temperatures may depend upon the kind of metal salt and on the used atmosphere.
  • the invention is also directed to a method wherein one does not heat to or above temperatures where the metal salt is not thermally stable anymore.
  • the heat treatment (like drying) can also be performed in a reducing (e.g. H 2 ) or neutral (e.g. N 2 ) atmosphere.
  • a reducing (e.g. H 2 ) or neutral (e.g. N 2 ) atmosphere e.g.
  • the maximal temperatures as mentioned above will then be the same or may be larger, but only up to temperatures to which the metal salts are thermally stable.
  • the heat treatment is performed at temperatures lower than 100 °C, more preferably at or below 80 °C.
  • Mixing metal salts with another material to obtain an adsorbent for sulphur compounds is disclosed in US 5 853 681.
  • This document describes low temperature ( ⁇ 150 °C) sulphur adsorbents which in the active form consist of copper carbonate, basic copper carbonate and/or copper hydroxide together with a small amount of alumina and a binder.
  • This adsorbent for low temperature desulphurisation contains a much larger amount of metal salt than the adsorbents according to the invention and that are used in the method according to the invention.
  • the adsorbent according to US 5 853 681 contains a minimum of 75 % (m/m) metal salts. A specific support is not employed. It is thus a bulk adsorption material and as such differs from a porous support loaded with the (much) smaller amount of metal salt according to the invention.
  • US 5 853 681 is targeted at desulphurisation of a different class of sulphur compounds, specifically H 2 S.
  • the impregnated support materials according to the invention for example impregnated clay minerals from the hormite group, or, for example, bentonite or alpha-alumina, that have been impregnated and dried at relatively low temperatures, have good adsorptions for THT, even at adsorption temperatures of approximately 30 - 50 °C.
  • Mercaptans are also better adsorbed when a support material has been impregnated with a, for example, copper salt, such as copper acetate. Therefore, according to the invention an adsorbent is obtained which has a good capacity for organosulphur compounds in the fuel gas stream even at higher temperatures (for example approximately 30 - 50 °C).
  • This adsorbent is easy and inexpensive to prepare.
  • An adsorbent can also be obtained that is able to adsorb various organosulphur compounds.
  • merely impregnating support materials (at low temperatures) already yields the result that adsorbents for organosulphur compounds are obtained that are suitable for removing these sulphur compounds from fuel gas streams.
  • the clay mineral that has been provided with a metal salt in particular a clay mineral impregnated with a metal salt, has advantages.
  • the invention works over a broad temperature range.
  • the invention comprises a method with which the organosulphur compounds are removed at a temperature of between -40 and 120 °C, more preferentially between -10 - 60 °C, for example 10 - 50 °C.
  • the temperature that is chosen will depend on the adsorbent (for example also on the metal salt deposited) and on the application.
  • the relatively low temperature that can be used is advantageous compared with adsorption methods that work only at high temperature, for example > 200 °C.
  • the adsorbents according to the invention are able to remove sulphur compounds that occur naturally and/or are added as odorant to natural gas streams, such as carbonyl sulphide, mercaptans, thiophenes and thiophanes, etc. Particularly good results are obtained in the case of the removal of gaseous organosulphur compounds that belong to the group of mercaptans and thiophenes.
  • organic sulphur compounds are understood to be sulphur compounds containing at least one -Cs hydrocarbon group, the sulphur atom being in the divalent state and not bonded to oxygen or another hetero-atom.
  • the compounds concerned are compounds having the general formula C m H n S s , where m is 1 - 8, in particular is 2 - 6, n is an even number of at least 4 and between 2m-6 and 2m+2, in particular 2m or 2m+2, and s is 1 or 2.
  • These compounds include alkyl mercaptans, dialkyl sulphides, dialkyl disulphides and the cyclic analogues thereof. Examples are dimethyl sulphide, dimethyl disulphide, tert-butyl mercaptan and in particular tetrahydrothiophene (THT).
  • the invention therefore comprises a method for the removal of gaseous organosulphur compounds such as mercaptans, sulphides or cyclic sulphides.
  • gaseous organosulphur compounds such as mercaptans, sulphides or cyclic sulphides.
  • Thiophene and thiophenol can also be bound by the adsorbents according to the invention.
  • a specific problem with adsorption filters is competitive adsorption.
  • natural gas also contains an appreciable quantity of higher hydrocarbons and, for example, the amount of pentane in Dutch natural gas for commercial use is higher than the amount of THT added.
  • the adsorbents according to the invention adsorb the THT very- well, despite the competitive presence of pentane and higher alkanes in the natural gas.
  • the method according to the invention can therefore also be used for the adsorption of organic sulphur compounds from streams of fuel gas other than natural gas, such as LPG or town gas, and other light hydrocarbons, such as propane, butane, pentane, etc., or combinations thereof.
  • the present invention also comprises a combination of (1) a gas filter based on an adsorbent, characterised in that this adsorbent is a support material on which metal salts have been deposited, and (2) a fuel cell, in particular of the PEMFC type.
  • a combination comprises, respectively, (a) an adsorbent for removal of, in particular, organosulphur compounds from fuel gases (in particular natural gas), (b) a fuel conversion chain (in which, as described above, the fuel gases (in particular natural gas) are converted to synthesis gas) and (c) the actual PEMFC unit and an afterburner.
  • the fuel gas stream can e.g. be natural gas, LPG, etc, and is fed via lines or other means known by the person skilled in the art from (a) via (b) to (c).
  • the present invention also comprises the use of an adsorbent according to the invention for removal of, in particular, organosulphur compounds from fuel gases (in particular natural gas), in applications where also one or more catalysts are used, which can be deteriorated by the presence of such organosulphur compounds, e.g. one or more catalysts for the removal of one or more of CO, NO, NO 2 (etc.), N O and hydrocarbons (which are left in the fuel gas stream).
  • organosulphur compounds e.g. one or more catalysts for the removal of one or more of CO, NO, NO 2 (etc.), N O and hydrocarbons (which are left in the fuel gas stream).
  • the invention is also directed to a use of the adsorbent of the invention for diminishing deterioration of one or more selected of the group consisting of a catalyst, a material and a device by direct or indirect presence of an organosulphur compound in a fuel gas stream.
  • the catalyst, device or material positioned downstream of the adsorbent of the invention may be deteriorated by organosulphur compounds in the fuel gas stream (direct) but may also or alternatively be deteriorated by reaction products or derivatives of organosulphur compounds (e.g. due to a reaction or decomposition of the organosulphur compound in a means that used the fuel gas stream) (indirect).
  • the adsorbent according to the invention is positioned upstream in the fuel gas stream, and the other catalyst, material or device is position downstream with respect to the adsorbent according to the invention.
  • Such materials or devices can e.g. be steel, lines, pipes, other adsorbents, detectors, etc., which may e.g. be deteriorated by the presence of compounds like sulphuric acid, SO x , H 2 S etc..
  • the amount of the adsorbent to be used will have to be determined depending on the amount of natural gas to be purified. As described above, for the consumption by an average household, a volume of 1200 m 3 natural gas per year will have to be purified.
  • the method can be carried out using approximately 0.25 - 3 gram adsorbent (for example based on sepiolite) per m 3 (Dutch) natural gas, preferably 0.5 - 2.5 gram.
  • a natural gas flow rate of approximately 0.2 m 3 /h approximately 0.15 - 0.5 gram adsorbent will have to be used. In practice it is found that approximately 35 - 150 gram adsorbent is sufficient for the adsorption of 1 gram THT.
  • a method is used that is characterised in that a clay mineral from the hormite group is used as support material.
  • Minerals from the hormite group are, for example, palygorskite, attapulgite, sepiolite and paramontmorillonite. Combinations of minerals or combinations with other adsorbents can optionally also be used.
  • sepiolite is used as clay mineral.
  • the minerals from the hormite group are known from the literature. Sepiolite and palygorskite are, for example, described by Galan (Clay Minerals (1996), 31, 443-453).
  • Adsorbents according to the invention that are based on clay minerals from the hormite group, and in particular sepiolite, can cope with large volumes without becoming saturated and have a high activity and selectivity for the organosulphur compounds. This makes these adsorbents exceptionally suitable for the removal of organosulphur compounds from fuel gas streams that, for example, are intended for membrane fuel cells.
  • the sepiolite that is used is natural sepiolite, such as, for example, is mined in Spain. This means that the sepiolite may be 'contaminated' with other minerals, such as bentonite, attapulgite, dolomite, etc. and also zeolites.
  • the adsorbent that is based on a clay mineral from the hormite group contains 50 % (m/m), for example 80 or 90 % (m/m) or more sepiolite. More generally this means that the adsorbent preferably contains more than 50 % (m/m), for example 80 or 90 % (m m), of the clay mineral from the hormite group.
  • the adsorbent preferably contains more than 50 % (m/m), for example 80 or 90 % (m m), of the clay mineral from the hormite group.
  • adsorbent comprising 80 % (m/m) sepiolite may be a natural sepiolite comprising 80 % (m/m) of the pure mineral, as can e.g. be detected by X-ray, etc.
  • the adsorbents also have to be sieved, i.e. treated in such a way that particles are obtained with a desired particle size.
  • This particle size will depend on the geometry used for the reactor. As a rule of thumb, the rule that is known to those skilled in the art of at least 10 particles over the diameter of the reactor bed and at least 50 particles over the length of the reactor bed can be adopted. A good 'plug flow' is obtained if this rule is maintained.
  • a person skilled in the art will size the reactor such that the residence time of the gas in the reactor is maximum in order thus to enable an efficient as possible adsorption of the organosulphur compounds on the adsorbent.
  • a suitable filter is, for example, of the packed-bed type; a cylindrical pot in which the adsorbent can be placed.
  • Stainless steel for example grade 316L
  • 316L is the preferred structural material because of the strength, the ease with which it can be processed and the relatively high chemical inertia.
  • various plastics can also be used (PVC, Teflon, polycarbonate, PET).
  • the absorbent can be kept in a fixed position in said cylindrical pot by mounting it between grids or perforated plates, which on their turn are fixed by means of rims within the pot and/or springs.
  • an analogous glass filter on top of which a specific amount of inert, spherical fill material is deposited (for example glass beads with approximately the same dimensions as the adsorbent grains). This bed of glass beads serves to distribute the stream of natural gas uniformly over the diameter of the reactor (plug flow) so that optimum contact with the adsorbent grains is guaranteed.
  • the fill in the cylindrical filter pot can be held in place via a (stainless steel) spring fixed at the top (natural gas inlet) with a perforated stainless steel gas distribution plate thereon.
  • the dimensions of the filter pot of course depend on the quantity of natural gas to be filtered per year. For 1200 m 3 a total volume of approximately 4 1 could suffice, depending on the adsorbent. Suitable dimensions are, for example, a height of the filter pot of 30 cm and a diameter of 13 cm. However, other ratios are also possible, provided that the criteria for good plug flow are met. In this context it is important that the combination of particle size, height of the filter pot and the natural gas stream to be treated must not give rise to a distinct pressure drop over the bed containing adsorbent grains.
  • the gas filter herein can be any volume like a reactor, vessel, pot, etc., comprising the adsorbent of the invention, through which or over which the fuel gas stream is led.
  • This can e.g. be a single-bed adsorption system, or a packed-bed system, etc., like e.g. described in Hydrocarbon Processing, May 1996, 129; US 2004/0031841; US 2003/0099875, US 2003/047078; WO 2004/014520 etc.
  • the term gas filter in the invention describes in general a closed volume, comprising at least one opening as inlet and at least one opening as outlet for the fuel gas stream, and comprising the adsorbent of the invention, e.g.
  • the fuel gas stream behind the gas filter comprises advantageously less or no organosulphur compounds, thereby e.g. saving the catalysts to remove e.g. CO, NO, NO 2 (etc.), N 2 O and hydrocarbons, which may be positioned downstream of the adsorbent in the fuel gas stream, or other materials and devices.
  • the invention therefore also relates to the use of an adsorbent for the removal of organosulphur compounds from fuel gas streams, characterised in that the adsorbent is a support material on which metal salts have been deposited.
  • Another embodiment of the invention relates to the method according to the invention where the adsorbent is combined with a second adsorbent.
  • This has the advantages that more (different) organosulphur compounds can be adsorbed or that, for example, mixtures of organosulphur compounds can be better removed from fuel gas streams. What is achieved by this means is, as a further aim, that as broad as possible a spectrum of organosulphur compounds can be efficiently removed from fuel gas streams with the aid of the method of the invention.
  • This second adsorbent can be chosen from the abovementioned group of support materials, or other materials that are known as adsorbents to those skilled in the art.
  • combination of adsorbents man made combination of adsorbents are meant, either as mixtures or as combination in series.
  • natural sepiolite may comprise other material than sepiolite, that may also be able to adsorb organosulphur compounds.
  • second adsorbent When reference is made to a second adsorbent this means that in any event a second (different) adsorbent is present in addition to the adsorbent according to the invention (that is based on a support material on which metal salts have been deposited).
  • the term 'second adsorbent' can also be used to refer to a combination of adsorbents, just as the term 'both' does not have to relate to only one additional adsorbent, but can also signify a number of adsorbents, in addition to an adsorbent according to the invention (e.g. from the hormite group).
  • ('second') adsorbents can, for example, be used in the form of mixtures, or as filters placed in series (that is to say spatially separated).
  • the second adsorbent can be a different adsorbent in that the percentage by weight of metal salt loaded is different or because the metal salt (or combination of metal salts) is different or because the support material is a different type, or combinations thereof.
  • the second adsorbent can be a loaded or non-loaded material. If reference is made to the loading of a second adsorbent, this means that if several adsorbents are present, in addition to the adsorbent according to the invention, at least one of these additional adsorbents has been loaded with (i.e. provided with) a metal (salt and/or oxide). The manner in which this can be carried out has been described above in connection with the loading of support materials with metal salts. Metal oxides can be obtained by oxidising suitable salts (see, for example, US 2002/005229) or, for example, by physically mixing with suitable oxides.
  • these zeolites can also be ion-exchanged with metal salts and the zeolites can then be washed, dried and calcined (see, e.g. EP 1121977).
  • the invention comprises a combination of adsorbents consisting of a clay mineral from the hormite group that has been provided with a metal salt (loaded hormite, for example sepiolite impregnated with iron(III) chloride) and a clay mineral from the hormite group that has not been provided with a metal salt (non-loaded hormite, for example sepiolite).
  • adsorbents consisting of a clay mineral from the hormite group that has been provided with a metal salt (loaded hormite, for example sepiolite impregnated with iron(III) chloride) and a clay mineral from the hormite group that has not been provided with a metal salt (non-loaded hormite, for example sepiolite).
  • the combination of adsorbents can be arranged in various ways.
  • the invention comprises both a combination of adsorbents, where the adsorbents are mixed (for example by physically mixing the adsorbents) and a combination where the adsorbents are arranged in series.
  • a pressed filter or a filter arrangement in which loaded sepiolite (for example sepiolite impregnated with iron(IIT) chloride), non-loaded sepiolite and active charcoal are present one after the other.
  • loaded sepiolite for example sepiolite impregnated with iron(IIT) chloride
  • active charcoal active charcoal
  • the volume of the gas filter of the invention comprises this mixture of adsorbents.
  • the adsorbents can be mixed before the volume of the gas filter is loaded with these adsorbents.
  • the adsorbents are arranged in series, one can e.g. load the gas filter sequentially with the adsorbents, such that the fuel gas stream can first be led over and/or through the first adsorbent and then be led over and/or through the second adsorbent (or further adsorbents).
  • One may however also use two volumes, e.g. two gas filters, which are arranged in series.
  • the combination preferably contains 30 % (m/m) or more of the adsorbent according to the invention (that is based on a support material on which metal salts have been deposited), for example 50, 60 or 70 % (m/m) or more.
  • account can be taken of the loading of one or more of the adsorbents with the metal salt and of the intended application.
  • the invention relates to a combination of adsorbents, where at least one of the adsorbents has been impregnated with iron( ⁇ i) chloride.
  • these above combinations of adsorbents can also be used in the method of the invention.
  • the gas stream is first fed through a loaded adsorbent and then fed through an optionally non-loaded adsorbent.
  • the invention also relates to a combination of adsorbents, characterised in that at least one of the adsorbents is a support material on which metal salts have been deposited.
  • the invention also comprises the use of a combination of adsorbents, as described above, for the removal of organosulphur compounds from fuel gas streams, for example from natural gas, town gas or LPG.
  • the invention also relates to a combination of a gas filter based on a combination of adsorbents according to the invention (see above) and a fuel cell.
  • metals from the groups la, lb, Kb, mb, IVb, Vb, Vllb, VLTI of the periodic system comprise metals like K, Rb, Cs; Cu, Ag, Au; Zn; Sc, Y, La and lanthanides like e.g. Ce, Pr, Gd, Tb, Dy, Tm, Yb and Lu; Ti. Zr and Hf; V, Nb and Ta; Mn, Re; Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt.
  • metals from groups mb, IVb, Vb, VDh, Vm of the periodic system i.e. groups 3-12 of the IUPAC periodic table of the elements).
  • the adsorbent of the invention comprises salts like chlorides, nitrates, sulphate ' s, chlorates, phosphates, formates, carbonates, oxalates and acetates of chromium, manganese, iron, cobalt, nickel, copper or Zn (or combinations thereof).
  • adsorbent is also directed to combinations of adsorbents.
  • support material on which metal salts have been deposited means the same as support material on which a metal salt has been deposited, and wherein no heat treatment of the support material is carried out after the deposition of the metal salt, except for a heat treatment at temperatures below 100 °C.
  • the adsorption experiments were carried out in a manually operated flow apparatus constructed from - for THT adso ⁇ tion - inert materials such as Teflon (pipes, taps, flow meters) and glass (reactor).
  • the apparatus operates under virtually atmospheric pressure and ambient temperature and has a connection to the local natural gas network.
  • the total amount of natural gas fed through is measured using a standard dry gas meter.
  • the natural gas or air flow through the apparatus can be adjusted by means of a flow meter positioned downstream of the reactor.
  • THT in natural gas is automatically measured by a Shimadzu gas chromatograph equipped with a flame photometric detector which has a detection limit of approximately 20 ppb for THT.
  • the apparatus furthermore has an electrochemical THT detector for indicative measurements (resolution and detection limit approximately 0.2 ppm) of the THT content in the natural gas.
  • An adso ⁇ tion experiment starts with placing approximately 70 ml adsorbent material (particle size 1 - 3 mm) in the glass reactor (internal diameter 2.5 cm, height of the bed approximately 15 cm), after which the apparatus can be checked for leaks.
  • the automatic analysis is then started and the natural gas is fed via the reactor bypass to the gas chromatograph to determine the input concentration of THT in the natural gas (approximately 5 ppm).
  • the natural gas is fed through the reactor via the gas meter. During this operation the temperature in the bed of adsorbent is measured using a thermocouple. The experiment is terminated when the THT concentration in the filtered natural gas is found to be greater than or equal to 0.1 ppm. Table 1 lists the samples tested and the test conditions.
  • Example 1 (not according to the invention)
  • sepiolite (obtainable as dust-free granules; > 18 % (m/m) sepiolite and ⁇ 20 % (m/m) zeolite) is compared with various conventional adsorbents such as active charcoal (Norit, code RBI; based on turf, steam-activated, extruded, not impregnated); copper- and chromium-impregnated active charcoal (Norit, code RGM1; based on turf, steam-activated and impregnated); and copper oxide / zinc oxide / alumina (BASF R3-12; metal / metal oxide).
  • active charcoal Non-it, code RBI; based on turf, steam-activated, extruded, not impregnated
  • copper- and chromium-impregnated active charcoal (Norit, code RGM1; based on turf, steam-activated and impregnated)
  • copper oxide / zinc oxide / alumina BASF
  • Table 1 List of samples tested and test conditions for Examples 1 and 2
  • Composition of natural gas (% (V/V)) 78.4 % methane, 4.13 % ethane, 0.95 % propane, 0.30 % butane (n- and iso-), 0.04 % pentane, 0.05 % hexane, 13.8 % nitrogen, 2.21 % carbon dioxide 18 mg/m 3 THT
  • Table 2 List of capacity results for THT adso ⁇ tion experiments (Example 1)
  • the material prepared in this way contains approximately 10 % (m/m) Fe 3+ and is ready for use for adso ⁇ tion tests.
  • the Fe 2 O on gamma-alumina adsorbent (DYCAT; code D-021) was prepared via dry impregnation of the gamma-alumina with a water-soluble iron salt, drying and calcination at high temperature (> 200 °C). The resulting adsorbent contains approximately 9 % (m/m) iron.
  • Fuel gas for Test 1-4, 6 (% (V/V)): 78.4 % methane, 4.13 % ethane, 0.95 % propane, (natural gas from local gas supply) 0.30 % butane (n- and iso-), 0.04 % pentane, 0.05 % hexane, 13.8 % nitrogen, 2.21 % carbon dioxide, 18 mg/m 3 THT
  • Fuel gas composition for Test 5 (% (V/V)): 81.33 % methane, 2.80 % ethane, 0.40 %
  • Adsorption capacity in gram/litre adsorbent at 0.1 ppm breakthrough Adsorbent (test no.) Support Metal salt + support Test, fuel gas (sulphur compound)
  • the apparatus is also connected via an on/off tap and a pressure regulator to the central compressed air facility.
  • the apparatus was connected to an LPG vaporiser via an outflow safety device and a pressure regulator.
  • the vaporiser was provided with flexible and stainless-steel-reinforced LPG feed and discharge lines. Both gaseous and liquid LPG can be supplied from the tanks intended for these (a 25 1 heating gas tank for supplying LPG vapour and a 36 1 tank for supplying LPG liquid), hi the case of supply of liquid LPG, the pressurised (approximately 5 - 8 bara) (liquid) LPG is vaporised in the vaporiser with the aid of hot water at 50 °C. A pressure regulator integrated in the vaporiser then reduces the LPG vapour pressure to approximately 0.1 - 0.2 bar(o).
  • the LPG pressure is brought down to 0.1 bar(o) via a pressure regulator fitted in the feed line to the reactors.
  • the gas flow rate and the total amount of gas fed in are controlled by means of a flow meter fitted downstream of the reactors and by means of a gas meter fitted upstream of the reactors, respectively.
  • sulphur- containing odorants for example tetrohydrothiophene, tertiary-butyl mercaptan and ethyl mercaptan
  • the apparatus was provided with two glass packed- bed reactors with an internal volume of approximately 0.1 1 (Reactor 1) and approximately 0.05 1 (Reactor 2) , respectively.
  • the temperature in the reactor bed of the larger reactor which is not thermostat-controlled, can be measured during an adso ⁇ tion test using a type K thermocouple.
  • the smaller reactor is partially submerged in a water bath, by means of which the temperature can be set to between -5 °C and 80 °C.
  • Downstream of the reactor the sulphur concentration in the fuel gas is determined automatically using a Shimadzu gas chromatograph equipped with a flame photometric detector which has a detection limit of approximately 20 ppb for organic sulphur compounds.
  • the apparatus also has a facility for manual determination of the concentration of sulphur compounds via two electrochemical monitors (THT and mercaptans). The gas flowing out of the apparatus is fed to the open air via a separate off-gas pipe.
  • a small side stream of the gas flowing out is tapped off for analysis by the GC-FPD.
  • the apparatus is as far as possible constructed of materials inert to adso ⁇ tion, such as Teflon (pipes, taps, flow meters) and glass (reactors). Table 5 lists the samples tested and the test conditions.
  • Adsorbents tested Example 3: 5 % (m/m) Cu-impregnated sepiolite Example 4: 2 % (m/m) Cu-impregnated sepiolite Example 5: 2 % (m/m) Cu-impregnated sepiolite
  • volume of bed of adsorbent 10 ml Weight of bed of adsorbent: 5 - 6 g Particle size: 0.5 - 1 mm Gas flow rate: 0.5 1/min (standard temperature and pressure: 20 °C; 1 atm)
  • each of the above gas mixtures was also tested with the untreated sepiolite that is commercially available as dust-free granules.
  • An adso ⁇ tion experiment starts with placing approximately 10 ml adsorbent material (particle size 0.5 - 1 mm) in the smaller glass reactor, after which the apparatus is checked for leaks. The automatic analysis is then started and the natural gas is fed via the reactor bypass to the gas chromatograph to determine the input concentration of sulphur in the fuel gas (approximately 1 - 5 ppm). Once this input concentration is stable, the natural gas is fed via the gas meter through the reactor, which is thermostat-controlled at 40 °C. The experiment is terminated when the concentration of sulphur compounds in the filtered fuel gas is found to be greater than or equal to 0.1 ppm.
  • the impregnated sepiolite was dried in air for a minimum of 24 hours in a drying oven at 40 °C.
  • the material dried in this way contains approximately 2 % (m/m) Cu 2+ and is ready for use for adso ⁇ tion tests.
  • a sample containing 5 % (m/m) Cu 2+ was prepared in the same way as described above.
  • the fuel gas from Examples 3 and 5 also contains a small amount of DMS.
  • the capacity results for DMS have not been included in Table 6. Because the available amount of the gas mixture in Example 3 ran out, no clear breakthrough of TBM was detected in this example. The capacity shown therefore relates to the total amount of gas fed through.
  • a 'temporary' breakthrough (maximum approximately 0.2 ppmv) of an unknown sulphur compound was detected for a relatively short time during the adso ⁇ tion test. This compound was identified via a GC-MS analysis of a gas sample as the dimer of TBM (C 4 H 9 -S-S-C H 9 , di-tertiary-butyl disulphide).
  • Example 5 diethyl disulphide (C H 5 -S-S-C 2 H 5 , the oxidation product of ethyl mercaptan) was found to break through at a certain point in time.
  • the capacity in Table 6 therefore also relates to the amount of filtered LPG vapour (gas mixture in Example 5) on breakthrough of approximately 0.05 ppmv diethyl disulphide (corresponds to 0.1 ppmv 'S'). Breakthrough of ethyl mercaptan was not detected before the LPG heating gas tank ran out.
  • test equipment and test conditions are as described for Examples 3 - 6.
  • the adso ⁇ tion test was carried out using the natural gas from the local gas supply, h addition to the sepiolite loaded with iron, untreated sepiolite and active charcoal impregnated with copper and chromium (Norit, code RGM-1) were also tested under the same conditions for reference. Results
  • THT capacity determined for the sepiolite loaded with iron is given in Table 7.
  • THT capacities of untreated sepiolite and of active charcoal impregnated with copper and chromium are also included in the table.
  • Table 7 THT capacity of untreated sepiolite, active charcoal impregnated with copper and chromium and sepiolite loaded with Fe 3+
  • THT can be removed from the annual consumption of natural gas (approximately 1200 m 3 ) with a volume of only about 2 litres of iron-sepiolite.
  • Table 8 lists combinations of adsorbents according to the invention that can be used to remove (organo)sulphur compounds from fuel gas streams.
  • Table 8 Examples of filter composition for odorised fuel gases where the odorant mixture contains THT
  • adsorbents can be combined, but they can also be arranged in series (spatially separated).
  • Sepiolite that has been impregnated with FeCl 3 according to the invention was dried in air at 40 °C and 80 °C for a few days.
  • the material that was dried at 80 °C discoloured (dark brown), whilst this was not detected with the material that was dried at 40 °C.
  • Example 9 Comparison examples chlorides vs. oxides for adsorption of THT
  • Support material was placed into a beaker and mixed with an amount of metal chloride, necessary to obtain a loading of approximately 10 % (m m) after drying. Subsequently, under stirring, water was added to the mixture till the resulting paste showed the first traces of wetness. Finally, the moistened substance was dried for a minimum of 24 hours in an oven under air. The resulting material contains approximately 10 % (m m) of the metal and is ready to use as an adsorbent. To investigate the effect of a higher drying temperature on the adso ⁇ tion performance for THT in natural gas, part of the material has been dried for 24 hours at 120 °C under air. It is assumed that at least part of the metal chloride is converted into the corresponding metal oxide. According to the abovementioned procedure iron (IJJ) chloride, iron (111) oxide, copper (11) chloride and copper (IT) oxide have been prepared. Overview tested samples and test conditions for THT-adsorption experiments
  • Tested adsorbents Test 1: 10 % (m/m) Fe (as FeCl 3 ) on sepiolite Test 2: at 120 °C air-dried adsorbent of Test 1 Test 3: 10 % (m/m) Cu (as CuCl 2 ) on sepiolite Test 4: at 120 °C air-dried adsorbent Test 3
  • volume and weight adsorbent bed 10 ml; 6 g
  • Fuel gas (vol.%): 78.4 % methane, 4.13 % ethane, 0.95 % propane, 0.30 %
  • Adsorbent (test nr.) Uptake capacity in gram THT / liter adsorbent at
  • FeCl 3 on sepiolite (1) 12.5 FeCl 3 on sepiolite dried at 120 °C (2) 3.2
  • the metal chloride loaded samples adsorb more THT than the samples that were dried at 120 °C.
  • the adsorbents according to the invention have better adso ⁇ tion properties that those of the prior art adsorbents, wherein the adsorbent, after loading with the metals, is subjected to a heat treatment at temperatures above 100 °C, e.g. 120°C or higher.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

L'invention porte sur un procédé visant à éliminer des composés d'organo-sulfure de courants de gaz combustible, le courant gazeux étant mis en contact avec un adsorbant qui est un matériau de support sur lequel ont été déposés des sels métalliques. L'invention porte également sur un procédé visant à déposer des sels métalliques sur un matériau de support, et consistant à mélanger la quantité désirée de sel métallique comprise entre approximativement 0,2 et 50 % (m/m) (sur la base du métal par rapport au matériau de support) avec un liquide; mélanger la solution ou la suspension avec le matériau de support à des températures pouvant monter entre approximativement 60 et 80 °C, par brassage et/ou ondes ultrasonores; et sécher le produit obtenu à des températures pouvant monter entre approximativement 60 et 80 °C. L'invention porte également sur des adsorbants qui ont été obtenus ou peuvent être obtenus de cette façon et sur l'utilisation de ces adsorbants pour éliminer les composés d'organo-sulfure de courants de gaz combustible. L'invention porte encore sur une combinaison d'un filtre à gaz à base de cet adsorbant et d'une pile à combustible (PEMFC).
PCT/NL2004/000307 2003-05-08 2004-05-07 Procede de desulfuration de courants de gaz combustible WO2004099351A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1023360A NL1023360C2 (nl) 2003-05-08 2003-05-08 Werkwijze voor het ontzwavelen van brandstofgasstromen.
NL1023360 2003-05-08

Publications (1)

Publication Number Publication Date
WO2004099351A1 true WO2004099351A1 (fr) 2004-11-18

Family

ID=33432522

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2004/000307 WO2004099351A1 (fr) 2003-05-08 2004-05-07 Procede de desulfuration de courants de gaz combustible

Country Status (2)

Country Link
NL (1) NL1023360C2 (fr)
WO (1) WO2004099351A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2916149A1 (fr) * 2007-05-15 2008-11-21 Inst Francais Du Petrole Procede de desacidification d'un gaz naturel mettant en oeuvre des hydroxydes doubles lamellaires.
EP2066417A2 (fr) * 2006-09-29 2009-06-10 Honeywell International Inc. Filtre à carburant
EP2217683A1 (fr) * 2007-11-01 2010-08-18 Ralph T. Yang Désulfuration du gaz naturel
WO2018083063A1 (fr) * 2016-11-02 2018-05-11 Lehmann & Voss & Co. Kg Dispositif de filtration
WO2018231551A1 (fr) * 2017-06-11 2018-12-20 Msa Technology, Llc Filtre pour composés soufrés

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02157039A (ja) * 1988-12-08 1990-06-15 Tosoh Corp 脱臭剤
EP0482818A1 (fr) * 1990-10-17 1992-04-29 Sumitomo Metal Mining Company Limited Méthode pour la préparation des catalyseurs d'hydrogénation d'huiles hydrocarbonées
WO2001021288A1 (fr) * 1999-09-06 2001-03-29 Stichting Energieonderzoek Centrum Nederland Reduction des emissions de n2o
EP1121977A2 (fr) * 2000-02-01 2001-08-08 Tokyo Gas Co., Ltd. Adsorbant pour éliminer les composés soufrés des gaz combustibles et méthode d'élimination
WO2003095594A1 (fr) * 2002-05-08 2003-11-20 Stichting Energieonderzoek Centrum Nederland Procede de desulfuration d'un gaz naturel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02157039A (ja) * 1988-12-08 1990-06-15 Tosoh Corp 脱臭剤
EP0482818A1 (fr) * 1990-10-17 1992-04-29 Sumitomo Metal Mining Company Limited Méthode pour la préparation des catalyseurs d'hydrogénation d'huiles hydrocarbonées
WO2001021288A1 (fr) * 1999-09-06 2001-03-29 Stichting Energieonderzoek Centrum Nederland Reduction des emissions de n2o
EP1121977A2 (fr) * 2000-02-01 2001-08-08 Tokyo Gas Co., Ltd. Adsorbant pour éliminer les composés soufrés des gaz combustibles et méthode d'élimination
WO2003095594A1 (fr) * 2002-05-08 2003-11-20 Stichting Energieonderzoek Centrum Nederland Procede de desulfuration d'un gaz naturel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199030, Derwent World Patents Index; Class D22, AN 1990-228548, XP002171152 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2066417A2 (fr) * 2006-09-29 2009-06-10 Honeywell International Inc. Filtre à carburant
EP2066417A4 (fr) * 2006-09-29 2010-11-24 Honeywell Int Inc Filtre à carburant
US7938960B2 (en) 2006-09-29 2011-05-10 Honeywell International Inc. Fuel filter and method of adding fuel additive to diesel fuel
US8216461B2 (en) 2006-09-29 2012-07-10 Farm Group IP LLC Method of adding fuel additive to diesel fuel
FR2916149A1 (fr) * 2007-05-15 2008-11-21 Inst Francais Du Petrole Procede de desacidification d'un gaz naturel mettant en oeuvre des hydroxydes doubles lamellaires.
WO2009004132A2 (fr) * 2007-05-15 2009-01-08 Ifp Procédé de désacidification d'un gaz naturel mettant en oeuvre des hydroxydes doubles lamellaires
WO2009004132A3 (fr) * 2007-05-15 2009-03-12 Inst Francais Du Petrole Procédé de désacidification d'un gaz naturel mettant en oeuvre des hydroxydes doubles lamellaires
EP2217683A1 (fr) * 2007-11-01 2010-08-18 Ralph T. Yang Désulfuration du gaz naturel
EP2217683A4 (fr) * 2007-11-01 2011-11-23 Univ Michigan Désulfuration du gaz naturel
US8187366B2 (en) 2007-11-01 2012-05-29 Yang Ralph T Natural gas desulfurization
WO2018083063A1 (fr) * 2016-11-02 2018-05-11 Lehmann & Voss & Co. Kg Dispositif de filtration
WO2018231551A1 (fr) * 2017-06-11 2018-12-20 Msa Technology, Llc Filtre pour composés soufrés

Also Published As

Publication number Publication date
NL1023360C2 (nl) 2004-11-09

Similar Documents

Publication Publication Date Title
CA2484713C (fr) Procede de desulfuration d'un gaz naturel
CA2735082C (fr) Materiau adsorbant et procede pour desulfurer des gaz renfermant des hydrocarbures
Ferella et al. Separation of carbon dioxide for biogas upgrading to biomethane
Satokawa et al. Adsorptive removal of dimethylsulfide and t-butylmercaptan from pipeline natural gas fuel on Ag zeolites under ambient conditions
De Wild et al. Removal of sulphur-containing odorants from fuel gases for fuel cell-based combined heat and power applications
CN101347708B (zh) 一种储罐逸散含硫恶臭废气的处理方法
JP5016037B2 (ja) 脱硫吸着剤の寿命判断用変色指示体、並びにこれを含む脱硫反応器および脱硫システム
Chen et al. CuFe2O4/activated carbon adsorbents enhance H2S adsorption and catalytic oxidation from humidified air at room temperature
Taheri et al. Methyl mercaptan removal from natural gas using MIL-53 (Al)
EP2804692B1 (fr) Méthode pour la séparation de composés de soufre de courants de combustibles fluides
Menezes et al. Insights on the mechanisms of H2S retention at low concentration on impregnated carbons
JPH0511487B2 (fr)
CN101262926A (zh) 纯化气体的方法和设备
Zhao et al. Regenerable sorbent pellets for the removal of dilute H2S from claus process tail gas
JP2010535613A (ja) 炭化水素含有ガスの脱硫触媒及び脱硫方法
WO2004099351A1 (fr) Procede de desulfuration de courants de gaz combustible
KR100235113B1 (ko) 황화물 가스를 제거하기 위한 첨착활성탄및 이의 제조방법
KR20140088890A (ko) 탄화수소성 기체 혼합물로부터 황-포함 화합물을 제거하는 방법
Ngo et al. Hydrogen sulfide removal from simulated synthesis gas using a hot gas cleaning system
Jalalvandi et al. Removal of H2S and mercaptan from outlet gases of kermanshah refinery using modified adsorbents (bentonite and sludge)
JP2013199533A (ja) 脱硫ガス体燃料の製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase