[go: up one dir, main page]

WO2003062177A1 - Elimination de composes sulfures dans des hydrocarbures de faible poids moleculaire - Google Patents

Elimination de composes sulfures dans des hydrocarbures de faible poids moleculaire Download PDF

Info

Publication number
WO2003062177A1
WO2003062177A1 PCT/GB2003/000132 GB0300132W WO03062177A1 WO 2003062177 A1 WO2003062177 A1 WO 2003062177A1 GB 0300132 W GB0300132 W GB 0300132W WO 03062177 A1 WO03062177 A1 WO 03062177A1
Authority
WO
WIPO (PCT)
Prior art keywords
stream
regeneration
bed
adsorbent
mercaptans
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/GB2003/000132
Other languages
English (en)
Inventor
Peter John Herbert Carnell
Nicola Young
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 WO2003062177A1 publication Critical patent/WO2003062177A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • 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
    • B01D53/04—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 with stationary adsorbents
    • 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
    • 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
    • B01J20/16—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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—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 form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • 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
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/3408—Regenerating or reactivating of aluminosilicate 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • 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
    • B01D2253/106—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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/304—Linear dimensions, e.g. particle shape, diameter
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/306—Surface area, e.g. BET-specific surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • 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
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/56—Use in the form of a bed

Definitions

  • This invention relates to hydrocarbon treating and in particular to a process for the removal of sulphur compounds from low molecular weight hydrocarbons, i.e. hydrocarbons having 1 to 6 carbon atoms per molecule.
  • Impurities such as water and sulphur compounds, and in some cases higher hydrocarbons, often contaminate streams of low molecular weight hydrocarbons.
  • Sulphur compounds such as hydrogen sulphide can be removed by a "wet" process using a regenerable amine solvent and/or by absorption with absorbents such as carbon or certain iron, copper and/or zinc compounds.
  • Carbonyl sulphide can be removed by hydrolysis to carbon dioxide and hydrogen sulphide and absorption of the hydrogen sulphide. In some cases, a separate hydrolysis step is not required, the absorbent acting as a catalyst for the hydrolysis.
  • adsorbents such as molecular sieves and silica gels may be employed.
  • adsorbents require periodic regeneration.
  • Regeneration is generally effected by passing a suitable regeneration gas stream, such as a part stream from the feed or product, at an elevated temperature, through the adsorbent bed: adsorbed components are desorbed into the gas stream. Because of the sulphur content of regeneration gas containing the desorbed impurities, disposal thereof presents problems. Normally it is normal to drain the adsorbent from the liquid, dry and then heat the adsorbent. The hydrocarbon remaining in the adsorbent is only suitable as fuel.
  • the regeneration gas is treated and recycled to the feed.
  • the present invention provides a process for the separation of mercaptans from a feed stream containing one or more low molecular weight hydrocarbons comprising passing the feed stream through a bed of a first adsorbent comprising a silica gel or molecular sieve whereby mercaptans in said feed stream are adsorbed leaving a product stream containing said one or more low molecular weight hydrocarbons, and periodically regenerating the first adsorbent by passing a heated regeneration gas comprising part of the product stream, or part of a feedstock stream from which the feed stream is separated, through the first adsorbent bed to desorb said mercaptans, passing the regeneration stream containing said desorbed mercaptans through a bed of a second absorbent that is effective to couple said mercaptans to form higher boiling sulphur compounds to give a regeneration stream containing said higher boiling sulphur compounds, adding said regeneration stream to the feed stream, or to
  • organic sulphur compounds including the lower alkyl mercaptans are adsorbed together with any water and/or higher hydrocarbons that may be present. These adsorbed materials are desorbed into the regeneration stream on passage of the heated regeneration gas through the first absorbent bed.
  • the lower alkyl mercaptans such as methyl, ethyl and propyl mercaptans, are converted to the corresponding disulphides which have atmospheric pressure boiling points well in an excess of 100°C.
  • these sulphur compounds can be readily be separated from the lower hydrocarbons by a fractional distillation process.
  • Such a fractional distillation process can also serve to separate other higher boiling components, e.g. water and higher hydrocarbons.
  • the distillation is generally effected at a pressure in the range 1 to 25 bar abs., and will determine the overheads temperature required to effect the distillation.
  • the adsorption by the bed of silica gel or molecular sieve is normally effected at a temperature in the range -10°C to +50°C, and the regeneration at a temperature at least 50°C, particularly 70°C to 300°C, above the adsorption temperature.
  • Regeneration temperatures in an excess of 250°C are generally desirable where water has been adsorbed. However it is generally not necessary that such high temperatures are employed for each regeneration. Thus satisfactory results may be obtained using regeneration temperatures below 250°C for some regenerations with temperatures above 250°C only applied periodically, e.g. for alternate regenerations or for every fourth or fifth regeneration.
  • the amount of mercaptans present in the hydrocarbon feedstock will generally be less than 2000 ppm, and typically will be in the range 1 to 1000 ppm, especially 100 to 1000 ppm, by volume. Typically about half of the total mercaptans present will be methyl and ethyl mercaptan.
  • the second absorbent is preferably in the form of shaped particles, e.g. agglomerates or extrudates, typically having maximum and minimum dimensions in the range 1 to 10 mm, having a BET surface area above 10 m 2 /g and containing an oxide or hydroxide of a bivalent or multivalent metal such as copper, silver, iron, nickel, cobalt and/or manganese.
  • hydroxide we include basic salts, such as basic carbonates, of such metals.
  • the material preferably also contains alumina, for example as a calcium aluminate cement.
  • Particularly preferred shaped particles are preferably in the form of calcined agglomerates made by agglomerating a particulate mixture of copper hydroxide and/or hydroxycarbonate with a cement as a binder, and then calcining the agglomerates to convert the copper compounds to copper oxide.
  • the particulate mixture contains zinc hydroxide, zinc carbonate, zinc hydroxycarbonate and/or aluminium compounds as well as the copper compound or compounds. On calcination such zinc and/or aluminium compounds are converted to the respective oxide.
  • the composition of the agglomerates is preferably such that the copper atoms form 30-97, preferably 50-95, % of the total number of copper zinc and aluminium atoms in the agglomerates.
  • the total weight of copper oxide and zinc oxide amounts to at least 70, preferably at least 80, % by weight of the calcined agglomerates.
  • the binder is preferably calcium aluminate cement and preferably forms 5 to 10% by weight of the calcined agglomerates.
  • the calcined agglomerates preferably have a BET surface area of at least 80 m 2 /g.
  • the copper is preferably precipitated, or copper and zinc are preferably co-precipitated as the hydroxides, carbonates or basic carbonates.
  • the aluminium compound or compounds, if used, may be incorporated by co-precipitation with the copper, or copper and zinc; and/or by mixing a separately precipitated aluminium compound, or compounds, with the copper, or copper and zinc, precipitate; and/or by precipitating the aluminium compound, or compounds, on to the copper, or copper and zinc, precipitate.
  • the precipitation is preferably effected using an alkali metal carbonate, particularly sodium carbonate, as precipitant.
  • the copper, or copper and zinc is preferably precipitated as malachite or zinc substituted malachite. After precipitation, the aforesaid precipitate, or precipitates, are generally washed and dried to give a finely divided particulate mixture.
  • the agglomerates may conveniently be made by mixing the finely divided particulate mixture with the binder and a little water, insufficient to form a slurry, and then granulating or extruding the resultant mixture to give the required size agglomerates.
  • the agglomerates preferably have maximum and minimum dimensions in the range 1 to 10 mm. After forming the agglomerates they are dried and then calcined, for example in air at a temperature in the range 300 to 500°C, for sufficient time to convert the copper and zinc (if any) compounds to the oxides. Also preferred are agglomerates as made by the above process but in which the calcination step is omitted.
  • Another suitable material for the second absorbent comprises particles of porous alumina impregnated with a copper compound and calcined to convert the latter to copper oxide.
  • Another suitable material for the second absorbent comprises agglomerates containing at least 60, especially at least 80, % by weight of zinc oxide, calculated on the constituents of the absorbent material non-volatile at 900°C.
  • the zinc oxide may be, at least initially, wholly or partly hydrated or in the form of a basic salt of a weak acid, e.g. a basic carbonate.
  • Another suitable material for the second adsorbent comprises agglomerates of manganese dioxide, alone or in admixture with a copper compound, e.g. copper oxide, bound with a suitable binder.
  • mercaptans are converted by the second absorbent into sulphides and/or disulphides.
  • some hydrogen sulphide may be produced during the regeneration of the silica gel or molecular sieve absorbent: it is therefore preferred that the second absorbent is capable of absorbing hydrogen sulphide.
  • the higher boiling sulphur compounds i.e. coupled mercaptans, i.e. sulphides and/or disulphides
  • this separation is conveniently effected by distillation, e.g. a fractional distillation step used to treat the feedstock stream used to produce the feed stream.
  • the higher boiling sulphur compounds may be separated from the regeneration gas by adsorption with e.g. a silica gel or active carbon, i.e. using a third adsorbent bed.
  • the regeneration gas should be so treated before it is added to the feedstock, or feed, stream. This alternative may be more attractive where there is no distillation of the feedstock stream.
  • the loaded third adsorbent bed can be regenerated if desired.
  • the amount of regeneration gas required to effect regeneration of the third adsorbent is much smaller than the amount required to regenerate the first adsorbent, and so, if a distillation step is used to separate the higher boiling sulphur compounds from the regeneration gas used to regenerate the third adsorbent bed, the distillation stage may be much smaller than would be required for distillation of the regeneration gas from the second adsorbent.
  • Figure 1 is a diagrammatic flowsheet of a first embodiment
  • Figure 2 is a diagrammatic flowsheet of a second embodiment.
  • FIG. 1 there is shown the flowsheet of a process for treating a hydrocarbon stream to obtain a stream of low molecular weight hydrocarbons from a feedstock containing both low molecular weight and higher molecular weight hydrocarbons.
  • the feedstock stream e.g. a liquid stream obtained by condensing hydrocarbons containing 2 or more carbon atoms per molecule from natural gas
  • a distillation column 12 wherein it is separated into an overhead gas stream 14 containing 2 to 6, especially 2 to 4, carbon atoms per molecule and a liquid bottoms stream 16 containing hydrocarbons containing 7 or more, especially 5 or more, carbon atoms per molecule.
  • the feedstock stream contains sulphur compounds such as lower alkyl mercaptans, alkyl sulphides and disulphides. If the hydrocarbon stream 10 also contains hydrogen sulphide, the latter may be absorbed by a bed (not shown) of a suitable absorbent such as a zinc oxide composition prior to feeding to the column 12. Likewise, if the feedstock contains carbonyl sulphide, the latter may be hydrolysed and the resulting hydrogen sulphide likewise absorbed in a suitable absorbent bed prior to feeding to column 12.
  • the lower alkyl mercaptans will separate into the overheads stream 14 while the higher sulphur compounds will form part of the liquid bottoms stream 16.
  • This liquid bottoms stream may be added to a gasoline hydrocarbon fraction and subjected to hydro-desulphurisation and hydrogen sulphide absorption as is well known.
  • the overheads stream 14 is then cooled in heat exchanger 18 to condense it to a liquid stream which is fed via line 20 to a bed 22a of a molecular sieve.
  • the mercaptans are adsorbed by the molecular sieve giving a product hydrocarbons stream 24a.
  • the adsorption is effected at ambient temperature.
  • the resultant product stream 24a may be separated, e.g. by de-ethaniser, de- propaniser and butanes splitter columns into its component hydrocarbons.
  • molecular sieve bed 22a While molecular sieve bed 22a is on adsorption duty, another bed 22b of molecular sieve that has previously been used for the adsorption of mercaptans is undergoing regeneration. Regeneration is effected by passage of a hot gas stream through the bed, preferably in a direction counter-current to the direction of flow during the adsorption stage. Thus a hot gas is fed via line 24b to the bed 22b.
  • the gas may be part of the product stream 24a, e.g. taken from stream 24a via line 26 and heated in heat exchanger 28 prior to feeding to bed 22b.
  • the regeneration gas may be a part stream of one or more of these components.
  • the regeneration gas may be a part stream taken from stream 10, 14 or 20 heated as necessary.
  • the hot regeneration gas desorbs the mercaptans from the molecular sieve bed
  • natural gas is often stored in large storage facilities. Over a period of time, the gas also picks up small amounts of water which can separate out and cause blockages in pipelines when the gas is subsequently transported at times of greater demand, e.g. during the winter months.
  • the gas is also liable to contain sulphur compounds such as lower alkyl mercaptans. In order to avoid the aforesaid problems the water is removed by passing the gas through a bed of a silica gel. This also serves to remove the mercaptans.
  • the natural gas is fed via line 40 to the bed 42a of silica gel adsorbent and the product leaves the bed 42a via line 44a.
  • the silica gel adsorbs not only water and mercaptans, but also other sulphur compounds present and any higher molecular weight hydrocarbons present.
  • bed 42a is on adsorption duty
  • a bed 42b that has previously been on adsorption duty is undergoing regeneration.
  • Regeneration is effected by passing hot gas through the bed 42b silica gel.
  • the hot gas is typically a part stream 46 taken from the product gas stream 44a and is heated in heat exchanger 48 before being fed to bed 42b via line 44b.
  • the adsorbed water, mercaptans and other adsorbed components are desorbed into the hot regeneration gas which is then cooled in heat exchanger 50 and passed via line 52 to a bed 54 of an absorbent capable of catalysing the coupling of mercaptans.
  • a suitable absorbent was described above in relation to the Figure 1 embodiment. It has been found that the regeneration gas leaving the bed of the silica gel adsorbent may contain some hydrogen sulphide, possibly resulting from hydrolysis or cracking of adsorbed mercaptans. In some cases the absorbent bed 54 used to effect the mercaptan coupling may absorb hydrogen sulphide. Alternatively a separate bed of a hydrogen sulphide absorbent may be provided before or after the absorbent bed 54.
  • the regeneration gas stream is then cooled as necessary and fed to a separator 56 where the desorbed water and higher molecular weight hydrocarbons condense and are separated as a liquid stream 58.
  • the disulphides formed by coupling of the mercaptans likewise condense and are separated.
  • the resultant overhead gas from separator is then recycled via line 60 to the feed 40 to adsorbent bed 42a.
  • Example 1 To illustrate the ability of copper and/or manganese compounds to couple mercaptans, the following Examples were performed.
  • Example 1 To illustrate the ability of copper and/or manganese compounds to couple mercaptans, the following Examples were performed. Example 1
  • the agglomerates were tested by charging 30 ml of agglomerates to a glass reactor of internal diameter 19 mm. A feed of nitrogen containing about 70 ppm by volume of propyl mercaptan was passed, at a rate of 18.5 l/h, down through the bed of agglomerates at ambient temperature and atmospheric pressure and the effluent gas examined by a pulsed flame photometric detector.
  • Di-propyl disulphide was detected at a level of 2.8 ppm by volume after 45 h on line.
  • the level of dipropyl disulphide rose to 58 ppm by volume after 351 h and remained at between 50-70 ppm by volume before propyl mercaptan was detected at a level of 6.5 ppm by volume after 2183 h on line. No propyl sulphide was detected in the exit gas until this point.
  • Example 2 Example 1 was repeated using agglomerates of 100 parts by weight of manganese dioxide granulated with 7 parts by weight of cement binder.
  • Di-propyl disulphide was detected at a level of 53 ppm by volume after 170 h on line.
  • the level of dipropyl disulphide remained at between 50-70 ppm by volume before propyl mercaptan was detected at a level of 5.4 ppm by volume after 2091 h on line. No propyl sulphide was detected in the exit gas until this point.
  • Example 3 Example 1 was repeated using agglomerates of 50 parts by weight of manganese dioxide and 50 parts by weight of cupric oxide granulated with 7 parts by weight of cement binder. Di-propyl disulphide was detected at a level of 36 ppm by volume after 139 h on line. The level of dipropyl disulphide rose to 59 ppm by volume after 185 h and remained at between 50-60 ppm by volume before propyl mercaptan was detected at a level of 6.8 ppm by volume after 1865 h on line. No propyl sulphide was detected in the exit gas until this point.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne un flux d'alimentation en hydrocarbures de faible poids moléculaire qui passe à travers un lit de premier adsorbant à base de gel de silice ou un tamis moléculaire, pour l'adsorption des mercaptans et l'élaboration d'un flux d'hydrocarbure résultant. Périodiquement, on régénère le premier adsorbant au moyen d'un gaz de régénération chauffé qui fait partie du flux résultant, ou d'un flux de charge d'alimentation, à partir duquel on sépare le flux d'alimentation. Les mercaptans sont désorbés dans ledit gaz, qui passe ensuite à travers un lit de second adsorbant capable de coupler les mercaptans pour former des composés sulfurés à point d'ébullition plus élevé. Le flux de régénération ainsi traité est injecté dans le flux d'alimentation ou dans une charge d'alimentation qui sert de base de séparation pour la séparation du flux d'alimentation. Les composés sulfurés à point d'ébullition plus élevé sont séparés avant ou après l'injection du flux de régénération dans la charge, la charge d'alimentation, ou le flux, mais avant le passage de la charge, de la charge d'alimentation ou du flux dans le lit à premier adsorbant.
PCT/GB2003/000132 2002-01-17 2003-01-15 Elimination de composes sulfures dans des hydrocarbures de faible poids moleculaire Ceased WO2003062177A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0201015.5 2002-01-17
GB0201015A GB0201015D0 (en) 2002-01-17 2002-01-17 Hydrocarbon treating

Publications (1)

Publication Number Publication Date
WO2003062177A1 true WO2003062177A1 (fr) 2003-07-31

Family

ID=9929232

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2003/000132 Ceased WO2003062177A1 (fr) 2002-01-17 2003-01-15 Elimination de composes sulfures dans des hydrocarbures de faible poids moleculaire

Country Status (2)

Country Link
GB (1) GB0201015D0 (fr)
WO (1) WO2003062177A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2861403A1 (fr) * 2003-10-27 2005-04-29 Inst Francais Du Petrole Procede de purification d'un gaz naturel par adsorption des mercaptans
FR2868962A1 (fr) * 2004-04-15 2005-10-21 Inst Francais Du Petrole Procede de purification d'un gaz naturel par adsorption des mercaptans.
WO2006106226A1 (fr) * 2005-04-07 2006-10-12 Institut Francais Du Petrole Procede de purification d’un gaz naturel par adsorption des mercaptans
EP2174710A1 (fr) 2008-10-10 2010-04-14 Ifp Mise en oeuvre de solides à base de ferrite de zinc dans un procédé de désulfuration profonde de charges oxygénées
WO2012076502A1 (fr) * 2010-12-06 2012-06-14 Shell Internationale Research Maatschappij B.V. Procédé d'élimination de mercaptans d'un flux gazeux
WO2012076378A1 (fr) * 2010-12-06 2012-06-14 Shell Internationale Research Maatschappij B.V. Procédé d'élimination de mercaptans d'un flux gazeux
FR2971043A1 (fr) * 2011-01-31 2012-08-03 IFP Energies Nouvelles Procede de liquefaction d'un gaz naturel a haute pression avec un pretraitement utilisant un solvant
FR3067265A1 (fr) * 2017-06-13 2018-12-14 IFP Energies Nouvelles Procede de preparation de solides a partir d'un melange d'au moins une poudre de malachite et une poudre d'oxyde et utilisation de ces solides
CN109078604A (zh) * 2017-06-13 2018-12-25 阿克森斯公司 由至少两种孔雀石粉末的混合物制备固体的方法
CN109099453A (zh) * 2018-09-29 2018-12-28 何秀锦 一种消除脱硫烟羽系统及其控制方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0262849A2 (fr) * 1986-10-01 1988-04-06 Imperial Chemical Industries Plc Désulfuration
US5114689A (en) * 1987-10-05 1992-05-19 Uop Integrated process for the removal of sulfur compounds from fluid streams

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0262849A2 (fr) * 1986-10-01 1988-04-06 Imperial Chemical Industries Plc Désulfuration
US5114689A (en) * 1987-10-05 1992-05-19 Uop Integrated process for the removal of sulfur compounds from fluid streams

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2861403A1 (fr) * 2003-10-27 2005-04-29 Inst Francais Du Petrole Procede de purification d'un gaz naturel par adsorption des mercaptans
FR2868962A1 (fr) * 2004-04-15 2005-10-21 Inst Francais Du Petrole Procede de purification d'un gaz naturel par adsorption des mercaptans.
US7311758B2 (en) * 2004-04-15 2007-12-25 Institut Francais Du Petrole Method of purifying a natural gas by mercaptan adsorption
WO2006106226A1 (fr) * 2005-04-07 2006-10-12 Institut Francais Du Petrole Procede de purification d’un gaz naturel par adsorption des mercaptans
FR2884154A1 (fr) * 2005-04-07 2006-10-13 Inst Francais Du Petrole Procede de purification d'un gaz naturel par adsorption des mercaptans
EP2174710A1 (fr) 2008-10-10 2010-04-14 Ifp Mise en oeuvre de solides à base de ferrite de zinc dans un procédé de désulfuration profonde de charges oxygénées
EA025250B1 (ru) * 2010-12-06 2016-12-30 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ удаления меркаптанов из газообразного потока
WO2012076378A1 (fr) * 2010-12-06 2012-06-14 Shell Internationale Research Maatschappij B.V. Procédé d'élimination de mercaptans d'un flux gazeux
US8894954B2 (en) 2010-12-06 2014-11-25 Shell Oil Company Process for removing mercaptans from a gas stream
US8894955B2 (en) 2010-12-06 2014-11-25 Shell Oil Cpmpany Process for removing mercaptans from a gas stream
WO2012076502A1 (fr) * 2010-12-06 2012-06-14 Shell Internationale Research Maatschappij B.V. Procédé d'élimination de mercaptans d'un flux gazeux
EA027253B1 (ru) * 2010-12-06 2017-07-31 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ удаления меркаптанов из газообразного потока
FR2971043A1 (fr) * 2011-01-31 2012-08-03 IFP Energies Nouvelles Procede de liquefaction d'un gaz naturel a haute pression avec un pretraitement utilisant un solvant
RU2567538C2 (ru) * 2011-01-31 2015-11-10 Ифп Энержи Нувелль Способ сжижения природного газа при высоком давлении с предварительной обработкой, использующей растворитель
EP3415232A1 (fr) * 2017-06-13 2018-12-19 IFP Energies nouvelles Procede de preparation de solides a partir d'un melange d'au moins une poudre de malachite et une poudre d'oxyde et utilisation de ces solides
FR3067265A1 (fr) * 2017-06-13 2018-12-14 IFP Energies Nouvelles Procede de preparation de solides a partir d'un melange d'au moins une poudre de malachite et une poudre d'oxyde et utilisation de ces solides
CN109078604A (zh) * 2017-06-13 2018-12-25 阿克森斯公司 由至少两种孔雀石粉末的混合物制备固体的方法
CN109078605A (zh) * 2017-06-13 2018-12-25 阿克森斯公司 制备固体的方法以及这些固体的用途
US11241667B2 (en) 2017-06-13 2022-02-08 Axens Method for preparing solids from a mixture of at least one malachite powder and an oxide powder and the use of said solids
CN109078604B (zh) * 2017-06-13 2023-03-14 阿克森斯公司 由至少两种孔雀石粉末的混合物制备固体的方法
CN109078605B (zh) * 2017-06-13 2023-08-22 阿克森斯公司 制备固体的方法以及这些固体的用途
CN116618004A (zh) * 2017-06-13 2023-08-22 阿克森斯公司 制备固体的方法以及这些固体的用途
CN109099453A (zh) * 2018-09-29 2018-12-28 何秀锦 一种消除脱硫烟羽系统及其控制方法
CN109099453B (zh) * 2018-09-29 2024-06-04 何秀锦 一种消除脱硫烟羽系统及其控制方法

Also Published As

Publication number Publication date
GB0201015D0 (en) 2002-03-06

Similar Documents

Publication Publication Date Title
US4865826A (en) Desulphurization
DE3886370T2 (de) Integriertes Verfahren für die Entfernung von Schwefelverbindungen aus Fluidströmen.
CA1313939C (fr) Procede de desulfuration par separation pour la production d'un flux a haute teneur en soufre
US4830734A (en) Integrated process for the removal of sulfur compounds from fluid streams
US5114689A (en) Integrated process for the removal of sulfur compounds from fluid streams
US4957715A (en) Gas treatment process
US5424051A (en) Process for the removal of carbon dioxide and mercaptans from a gas stream
CA1323321C (fr) Procede d'elimination du mercure contenu dans un hydrocarbure liquide
US8323603B2 (en) Desulfurization system and method for desulfurizing a fuel stream
US20060283780A1 (en) Desulfurization system and method for desulfurizing a fuel stream
AU2008349418B2 (en) Contaminant removal from a gas stream
US8268745B2 (en) Silicate-resistant desulfurization sorbent
WO2008082849A2 (fr) Adsorbant de soufre, système de désulfuration et procédé de désulfuration
CN1011663B (zh) 在烃转化工艺中除去烃物料中的硫化氢和/或氨的方法
WO2003062177A1 (fr) Elimination de composes sulfures dans des hydrocarbures de faible poids moleculaire
EP0335034A1 (fr) Procédé intégré pour l'élimination des composés de soufre de courants fluid
US5891323A (en) Purification process
US4946660A (en) Desulphurization
US5041693A (en) Separation of normal paraffins and the regeneration of zeolitic molecular sieves used therein
JPS63175615A (ja) 硫化水素除去方法
EP0262849B1 (fr) Désulfuration
US5145815A (en) Regeneration of zeolitic molecular sieves with sulfur oxide absorption on soda-lime bed
US3186789A (en) Method of removing hydrogen sulfide from gases
US20130047850A1 (en) Synthesis gas purification by selective copper adsorbents

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 BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE 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 NO NZ OM PH PL PT RO RU SC SD SE SG SK SL 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): GH GM KE LS MW MZ 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 PT 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
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP