EP3092288A1 - Procédé d'élimination de composés soufrés de flux d'hydrocarbures - Google Patents

Procédé d'élimination de composés soufrés de flux d'hydrocarbures

Info

Publication number
EP3092288A1
EP3092288A1 EP15700193.4A EP15700193A EP3092288A1 EP 3092288 A1 EP3092288 A1 EP 3092288A1 EP 15700193 A EP15700193 A EP 15700193A EP 3092288 A1 EP3092288 A1 EP 3092288A1
Authority
EP
European Patent Office
Prior art keywords
transition metal
sulfur
metal sulfide
sulfide
hydrocarbon stream
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.)
Withdrawn
Application number
EP15700193.4A
Other languages
German (de)
English (en)
Inventor
Steffen WAGLÖHNER
Michael Bender
Andreas Kuschel
Wolfgang RÜTTINGER
Philipp Brüggemann
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP15700193.4A priority Critical patent/EP3092288A1/fr
Publication of EP3092288A1 publication Critical patent/EP3092288A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/08—Inorganic compounds only
    • 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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/485—Sulfur compounds containing only one sulfur compound other than sulfur oxides or hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/30—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
    • C10G25/09—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil according to the "fluidised bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/12—Recovery of used adsorbent
    • 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
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • 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
    • C10L3/12—Liquefied petroleum 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
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1128—Metal sulfides
    • 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
    • B01D2257/304—Hydrogen sulfide
    • 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
    • B01D2257/30—Sulfur compounds
    • B01D2257/308—Carbonoxysulfide COS
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/12—Regeneration of a solvent, catalyst, adsorbent or any other component used to treat or prepare a fuel
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel

Definitions

  • the invention relates to a process for the removal of sulfur compounds from hydrocarbon streams using an absorbent containing a transition metal sulfide.
  • the removal of sulfur compounds from hydrocarbon streams may be necessary for a variety of reasons. If the hydrocarbon stream is to be combusted as fuel, removal of sulfur is required to prevent the release of polluting exhaust gases. Even if the hydrocarbon stream is to be further processed, a removal of sulfur is often required, for example, to prevent poisoning of sulfur-sensitive catalysts or to protect metallic components from corrosion.
  • Adsorption / absorption desulfurization is based on the ability of the sorbent material to selectively bind sulfur compounds. Depending on how the sulfur is bound, two different groups of desulfurization processes can be used
  • Sulfur is usually bound to the sorbent material as a sulfide.
  • the desulfurized or sulfur-free compound is released. How effective the desulfurization of the hydrocarbon streams is depends critically on the properties of the sorbent material and the nature of the sulfur compounds.
  • Sorption materials commonly used for desulfurization contain one
  • Transition metal oxide component such as ZnO
  • a promoter metal component such as Ni.
  • the removal of sulfur is accomplished by reacting the transition metal oxide on the surface of the sorbent material (e.g., ZnO) with the
  • Transition metal sulfide eg ZnS
  • the resulting sulfur-loaded sorbent material can be regenerated by contacting it with an oxygen-containing regeneration stream.
  • the transition metal sulfide (eg ZnS) located on the surface of the sorption material becomes again in the Transition metal oxide (eg ZnO) transferred. After the regeneration, it must be oxidized
  • Sorption material can then be treated with a hydrogen-containing reduction stream to reduce the promoter metal component and the sorbent material in his
  • US 2009/0193969 A1 discloses a desulfurization process in which (a) a gas stream containing sulfur compounds in a sorption zone is contacted with a sorbent material based on zinc and a promoter metal and (b) the sulfur-laden sorbent material is regenerated in a regeneration zone, by first drying at elevated temperature under inert gas and then regenerating with an oxygen-containing Regeneriergasstrom.
  • sulfur compounds such as hydrogen sulfide (H S)
  • US 2008/0190852 A1 describes a process for the removal of sulfur compounds, such as hydrogen sulfide, carbon oxysulfide, mercaptans (R-SH) and organic disulfides (RSS-R '), from hydrocarbon-containing gas streams in which a sorption material based on Iron carbonate (FeCO-3) is used.
  • the regeneration of the sorbent material is possible by means of a regeneration stream containing oxygen and water.
  • a disadvantage of the known methods is, for example, the fact that the regeneration of the sorption material used often requires several steps and is therefore complicated and expensive.
  • Another disadvantage is that the bound to the sorbent sulfur in the regeneration usually oxidized to gaseous sulfur oxides or reduced to hydrogen sulfide. As a rule, these gaseous sulfur compounds must be further reacted, for example in a Claus process to elemental sulfur. It is therefore an object of the present invention to provide an improved process for removing sulfur compounds from hydrocarbon streams.
  • the process should be economically viable and not have the disadvantages of the prior art processes described above, ie the regeneration of the absorbent should be comparatively simple and the formation of sulfur oxides and hydrogen sulfide should be avoided as far as possible.
  • transition metal sulfides such as Fe (II) sulfide FeS
  • H2S hydrogen sulfide
  • DE 32 24 870 A1 discloses a process for recovering hydrogen and elemental sulfur from hydrogen sulfide (H 2 S) by first contacting a transition metal sulfide-containing particulate absorbent in a fluidized bed reactor with hydrogen sulfide gas at operating temperatures of 350 ° C to 550 ° C, wherein with simultaneous loading of the absorbent particles with sulfur gaseous hydrogen is formed, and subsequently the loaded absorbent particles are regenerated at temperatures of 600 ° C to 950 ° C with the release of elemental sulfur. Also the
  • US 2,979,384 discloses a process for producing hydrogen and elemental sulfur from hydrogen sulfide using transition metal sulfides such as iron (II) sulfide.
  • transition metal sulfides can undergo reactions with sulfur compounds such as mercaptans (R-SH), organic sulfides (R-S-R '), organic disulfides (R-S-S-R') and carbon oxysulfide (COS) under suitable reaction conditions. And this even if the sulfur compounds are present only in small amounts or in traces in a hydrocarbon mixture. Further, it has been found that at least a portion of the sulfur contained in the sulfur compound or compounds is bonded as additional sulfur in the transition metal sulfide as additional sulfur.
  • sulfur compounds such as mercaptans (R-SH), organic sulfides (R-S-R '), organic disulfides (R-S-S-R') and carbon oxysulfide (COS) under suitable reaction conditions. And this even if the sulfur compounds are present only in small amounts or in traces in a hydrocarbon mixture. Further, it has been found that at least a portion of the sulfur contained in the sulfur compound or compounds is bonded as additional sulfur
  • the object underlying the present invention is achieved by a method for removing sulfur compounds selected from mercaptans (R-SH), organic sulfides (RS-R '), organic disulfides (RSS-R') and carbon oxysulfide (COS), from a hydrocarbon stream in which the hydrocarbon stream containing one or more of the sulfur compounds is contacted in an absorption step with an absorbent containing a first transition metal sulfide, wherein at least a portion of the sulfur contained in the sulfur compound (s) is additional Sulfur is bound in the transition metal sulfide, wherein a second transition metal sulfide is formed.
  • the sulfur contained in the sulfur compounds is selectively bound to the absorbent containing a first transition metal sulfide without appreciable co-absorption of other constituents, particularly unsaturated or aromatic hydrocarbons, of the hydrocarbon stream.
  • adsorption In the context of the present invention, no distinction is made between adsorption and absorption.
  • absorption The terms “absorption”, “absorbents” and “absorbents” are used throughout.
  • the term “absorption” is used in the context of the present invention for any type of enrichment of gaseous or liquid compounds on, regardless of, on soft physical or chemical processes ultimately the enrichment of sulfur and / or sulfur compounds or used near the surface of a solid. The term therefore includes physical adsorption (physisorption), chemical adsorption (chemisorption) and absorption in the narrower sense. This applies analogously with regard to the terms “absorbent” and “absorption step”.
  • the first transition metal sulfide is selected from sulfides of chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel and copper and mixtures of these sulfides.
  • the first transition metal sulfide is particularly preferably selected from sulfides of iron, cobalt, nickel, copper and mixtures of these sulfides, most preferably iron sulfide.
  • transition metaH is to be understood as meaning a metal which is selected from one of the groups HIB, IVB, VB, VIB, VIIB VI 11 B, IB and IIB of the Periodic Table of the Elements.
  • the sulfur in the first transition metal sulfide basically has a mean oxidation number between -2 and -1.
  • the mean oxidation number of the sulfur is between -2 and -1, 2, more preferably between -2 and -1, 4, most preferably between -2 and -1, 6.
  • the first transition metal sulfide basically has a molar ratio of sulfur to transition metal (r riM) between 0.5 and 2.0 (0.5 ⁇ ns nM ⁇ 2.0).
  • the molar ratio in the first transition metal sulfide depends on the choice of transition metal or its oxidation state.
  • the molar ratio between 0.5 and 1, 6 (0.5 ⁇ ns nM ⁇ 1.6) and more preferably between 0.8 and 1.4 (0.8 ⁇ ns nM ⁇ 1.4).
  • the first transition metal sulfide contains iron (II) sulfide having the relative formula FeSo, 5 to 2, o, preferably FeSo, 5 to i, 6, more preferably FeSo, 8 to i, 4 very particularly preferably containing first transition metal sulfide iron (II) sulfide with the formula FeS.
  • the absorbent used consists of one or more first transition metal sulfides.
  • Particularly suitable as absorbent for this process variant are particles consisting of a first transition metal sulfide having an average particle diameter between 1 ⁇ m and 10 mm.
  • the mean particle diameter of the particles is preferably between 10 .mu.m and 1000 .mu.m, more preferably between 50 .mu.m and 500 .mu.m.
  • Such particles of a first transition metal sulfide are commercially available or can be prepared at least by simple, known to those skilled method of corresponding, commercially available transition metal sulfides of other forms.
  • moldings such as compacts are suitable consisting of a first transition metal sulfide for this variant.
  • the absorbent which is brought into contact with a hydrocarbon stream in the absorption step, may contain further components in a further variant of the process according to the invention in addition to the first transition metal sulphide (s).
  • Other components may be, for example, support materials on which the first transition metal sulfide is applied.
  • Suitable carrier materials are, for example, aluminum oxide, silicon oxide, aluminosilicate, magnesium silicate or carbon.
  • the absorbent is a molded body coated with the first transition metal sulfide.
  • auxiliaries such as binders, pasting agents or other additives, which are preferably added during the production of moldings.
  • type and added amount of the aid depend on the production method of the molding.
  • the absorbents used in the process according to the invention containing a first transition metal sulfide can be prepared by suitable, known preparation processes and / or brought into a specific form.
  • suitable, known preparation processes include impregnation and spray impregnation, as well as extrusion, compounding, pelleting, tableting, extrusion, coextrusion and spray drying.
  • the processes as such and the auxiliaries to be used therein are known to the person skilled in the art.
  • Suitable hydrocarbon streams include, for example, both natural gas and NGL (natural gas liquids) and various relatively low boiling crude oil rectification products such as LPG (liquefied petroleum gas), light naphtha, heavy naphtha and kerosene.
  • LPG liquefied petroleum gas
  • the hydrocarbon stream generally contains hydrocarbons selected from linear or branched C 1 -C 20 -alkanes, C 2 -C 20 -alkenes, C 2 -C 20 -alkynes; substituted or unsubstituted C 3 -C 20 cycloalkanes, C 3 -C 20 cycloalkenes, C 8 -C 20 cycloalkynes; substituted or unsubstituted, mono- or polynuclear C6-C2o-aromatics and mixtures of these hydrocarbons.
  • the hydrocarbon stream is selected from NGL and LPG.
  • LPG The most important source of LPG is crude oil. In the rectification of crude oil in refineries, LPG is commonly obtained as an overhead product. The hydrocarbons contained in LPG and their Relationship to each other depends on the crude oil source and the process parameters of the rectification. NGL is obtained from natural gas unlike LPG.
  • both LPG and NGL are composed essentially of linear or branched, acyclic or cyclic C 1 -C 6 -alkanes, C 2 -C 6 -alkenes and C 2 -C 6 -alkynes, where C 3 -C 4 -alkanes generally the main ingredients are.
  • NGL and LPG contain at least 70% by volume of C 1 -C 6 -alkanes, preferably at least 80% by volume of C 1 -C 6 -alkanes, particularly preferably at least 80% by volume of C 2 -C 5 -alkanes, very particularly preferably 90% by volume .-% C 2 -C 5 alkanes.
  • the hydrocarbon stream contains at least 80% by volume of C 1 -C 6 -alkanes, particularly preferably at least 80% by volume of C 2 -C 5 -alkanes, very particularly preferably 90% by volume of C 2 -C 5 -alkanes.
  • C 1 -C 6 -alkanes in the context of the present invention is the linear or branched, acyclic or cyclic alkanes selected from the group consisting of methane, ethane, n-propane, n-butane, n-pentane, n-hexane , 2-methylpropane, 2-methylbutane, 2,2-dimethylpropane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclobutane, cyclobutane, methylcyclopropane, cyclopentane, methylcyclobutane, 1, 1 Dimethylcyclopropane, 1,2-dimethylcyclopropane, ethylcyclopropane, cyclohexane, methylpentane, 1,1-dimethylbutane, 1,2-dimethylbutane, 1,3-dimethylbutan
  • C 2 -C 5 -alkanes stands for the linear or branched, acyclic or cyclic alkanes selected from the group consisting of ethane, n-Pr Opean, n-butane, n-pentane, 2-methylpropane, 2-methylbutane, 2,2-dimethylpropane, cyclopropane, cyclobutane, methylcyclopropane, cyclopentane, methylcyclobutane, 1, 1 -dimethylcyclopropane, 1, 2-dimethylcyclopropane, ethylcyclopropane and mixtures thereof alkanes.
  • C 2 -C 6 -alkenes in the context of the present invention represents the linear or branched, cyclic or acyclic alkenes selected from the group consisting of ethene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene , 1-hexene, 2-hexene, 3-hexene, 2-methyl-propene, 2-methylbut-1-ene, 3-methylbut-1-ene, 2-methylbut-2-ene, 2-ethylbut-1-ene , 2-methylpent-1-ene, 3-methylpent-1-ene, 4-methylpent-1-ene, 2-methylpent-2-ene, 3-methylpent-2-ene, 4-methylpent-2-ene , Cyclobutene, cyclopentene, cyclohexene, 1-methylcyclobutene, 3-methylcyclobutene, 1-methylcyclopentene, 2-methylcyclopentene, 3-methylcyclopentene, 1,
  • C 2 -C 6 -alkynes in the context of the present invention stands for the linear or branched acyclic alkynes selected from the group consisting of ethyne, propyne, 1-butyne, 2-butyne, 1-pentyne, 2-pentyne, 1 - Hexine, 2-hexyne, 3-hexyne, 3-methylbut-1-yne, 3,3-dimethylbut-1-yne, 4-methylpent-1-yne, and mixtures of these alkynes.
  • the hydrocarbon stream contains one or more sulfur compounds which can be completely or partially removed by the process according to the invention.
  • sulfur compounds such as mercaptans (R-SH), sulfides (RS-R '), organic disulfides (RSS-R'), hydrogen sulfide (HS), carbon oxysulfide (COS), carbon disulfide (CS2) and thiophenes can be included in the hydrocarbon stream be.
  • hydrocarbons and sulfur compounds it is possible for further, typically contained compounds, such as amines, alcohols or ethers, to be contained in the hydrocarbon stream, which generally do not adversely affect the process according to the invention.
  • typically contained compounds such as amines, alcohols or ethers
  • Gas constituents which adversely affect the process of removing sulfur compounds should be present in the smallest possible quantities in the hydrocarbon streams to be desulphurised.
  • oxidizing agents such as, for example, molecular oxygen, halogens and oxides of nitrogen, since these can partially oxidize the first and / or optionally the second transition metal sulfide and thus render them ineffective.
  • the content of oxidizing agents such.
  • molecular oxygen is therefore preferably a total of at most 1, 0 vol .-% and more preferably a total of at most 0.5 vol .-%.
  • vol.% refer to the total volume of the hydrocarbon stream.
  • the process of the present invention is particularly useful for removing sulfur compounds selected from mercaptans (R-SH), organic sulfides (RS-R '), organic disulfides (RSS-R') and carbon oxysulfide (COS) from hydrocarbon streams which are generally at least 0.001% by volume, preferably at least 0.01% by volume, and in general at most 5.0% by volume, preferably at most 2.0% by volume and more preferably at most 1.0% by volume Contain sulfur compounds.
  • R-SH mercaptans
  • RS-R ' organic sulfides
  • RSS-R' organic disulfides
  • COS carbon oxysulfide
  • mercaptans are usually C1-C10 mercaptans.
  • the hydrocarbon stream contains C 1 -C 6 mercaptans.
  • Ci-C6-Mercaptane comprises in particular one or more mercaptans selected from the group consisting of methylmercaptan (Me-SH), ethylmercaptan (Et-SH), vinylmercaptan, n-propylmercaptan, iso-propylmercaptan, allylmercaptan, n-butyl mercaptan, iso-butylmercaptan, sec-butylmercaptan, tert-butylmercaptan, n-pentylmercaptan, 3-methylbutylmercaptan, 2-methylbutylmercaptan, 1-methylbutylmercaptan, 1-ethylpropylmercaptan, n-hexylmercapt
  • organic sulfides are usually sulfides having two identical or different, linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 10 carbon atoms (bis (Ci-Cio) -sul - fide).
  • the hydrocarbon stream contains sulfides having two identical or different, linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 6 carbon atoms (bis (Ci-Ce) sulfides).
  • bis (C 1 -C 6) sulfides includes in particular one or more sulfides selected from the group consisting of dimethyl sulfide (Me-S-Me), ethyl methyl sulfide (Et-S-Me), methyl n-propyl sulfide , Methylisopropylsulfide, n-butylmethylsulfide, isobutylmethylsulfide, sec-butylmethylsulfide, tert-butylmethylsulfide, methyln-pentylsulfide, methyl (3-methylbutyl) sulfide, methyl (2-methylbutyl) sulfide, methyl ( 1-methylbutyl) sulphide, methyl (1-ethylpropyl) sulphide, n-hexylmethylsulphide, methyl (4-methylpentyl) sulphide, methyl (3-methyl
  • the content of organic sulfides in the hydrocarbon stream prior to the absorption step is 0.001 to 2.0% by volume.
  • the content of sulfides 0.01 to 1, 0 vol .-%, particularly preferably 0.01 to 0.5 vol .-%.
  • organic disulfides (RSS-R ') are usually disulfides having two identical or different, linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 10 carbon atoms.
  • the hydrocarbon stream contains disulfides containing two identical or different, linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 6 carbon atoms.
  • Examples of such disulfides are dimethyl disulfide (Me-SS-Me), ethyl methyl disulfide (Et-SS-Me), methyl n-propyl disulfide, methyl isopropyl disulfide, n-butyl methyl disulfide, isobutyl methyl disulfide, sec-butyl methyl disulfide, tert-butyl methyl disulfide, methyl n-pentyl disulfide, methyl (3-methylbutyl) disulfide, methyl (2-methylbutyl) disulfide, methyl (1-methylbutyl) disulfide, methyl (1-ethylpropyl) disulfide, n-hexylmethyl disulfide, methyl (4-methylpentyl) disulfide, methyl (3-methylpentyl) disulfide, methyl (2-methylpentyl) disulfide, methyl (2-
  • the content of organic disulfides (R-S-S-R ') in the hydrocarbon stream prior to carrying out the absorption step 0.001 to 1, 0 vol .-%.
  • the content of carbon oxysulfide (COS) in the hydrocarbon stream before carrying out the absorption step is 0.001 to 1.0% by volume.
  • the hydrocarbon stream to be liberated from sulfur compounds is contacted with the absorbent containing a first transition metal sulfide in one or more reaction vessels.
  • a reaction vessel There are no particular restrictions with regard to the selection of a reaction vessel.
  • the method can be carried out in batch mode or in continuous mode.
  • the respectively used reaction vessel in such a way that it has at least two different reaction zones which differ, for example, in temperature and / or pressure. If the process is carried out in two or more reaction vessels, these may consist of the same type of reactor or of different reactor types.
  • the reaction vessel used in the process of the invention is a tubular reactor or shell-and-tube reactor.
  • the absorbent containing a first transition metal sulfide is in a preferred embodiment in the one or more reaction vessels in the form of a fixed bed of charge before.
  • the absorbent may also be present in a fluidized bed.
  • the fixed bed alone consist of the absorbent containing a first transition metal sulfide, or contain one or more other components in addition to the absorbent.
  • the fixed bed alone consists of the absorbent containing a first transition metal sulfide.
  • Particularly suitable for this purpose are moldings coated with the first transition metal sulfide, preferably shaped bodies of ceramic.
  • the fixed bed contains, in addition to the absorbent one or more other components. These other components can be added to specifically influence certain process parameters or to suppress the aging of the absorbent.
  • Other components that may be included in the fixed bed for example, packing of different shape and size. Packings have, for example, ball, ring, cylinder or saddle shape. The packing can serve to regulate the heat dissipation, but also to prevent the agglomeration of Studentsgangsmetallsulfid- particles.
  • the first and second transition metal sulfides are in a fluidized bed.
  • Suitable absorbers for use in a fluidized bed are, in particular, particles consisting of first transition metal sulfide having an average particle diameter between 10 ⁇ m and 1000 ⁇ m, more preferably between 50 ⁇ m and 500 ⁇ m.
  • the temperature in the absorption step of the process according to the invention can generally be varied over a wide range.
  • the hydrocarbon stream is contacted with the first transition metal sulfide at a temperature of 200 to 600 ° C, preferably from 200 to 400 ° C, more preferably from 250 to 400 ° C and most preferably from 300 to 400 ° C in contact.
  • the pressure prevailing in the absorption step can also be varied over a wide range.
  • the hydrocarbon stream is contacted with the first transition metal sulfide at a pressure of 10 to 150 bar.
  • the pressure is preferably from 20 to 100 bar, more preferably from 30 to 70 bar.
  • the contact times can vary greatly. In general, the contact times are in the range of 0.5 to 120 s, preferably 1 to 60 s, particularly preferably 1 to 10 s.
  • the process of the invention allows between 50 and 100% by weight of the sulfur compounds selected from mercaptans (R-SH), organic sulfides
  • R-S-R ' (R-S-S ') and carbon oxysulfide (COS), based on the total weight of these sulfur compounds to remove from a hydrocarbon stream.
  • the degree of desulfurization may differ. Desulfurization levels of between 60 and 100% by weight, preferably between 80 and 100% by weight, more preferably between 90 and 100% by weight, can preferably be achieved.
  • the desulfurization is accomplished by having the sulfur compounds contained in the stream undergo at least partially a chemical reaction with the first transition metal sulfide (s) of the absorbent upon contacting the absorbent with the hydrocarbon stream.
  • the percentage by weight of sulfur in the transition metal sulfide increases.
  • the evidence can be provided by elemental analysis by determining the weight percentage of sulfur of the transition metal sulfide contained in the absorbent at two different times and comparing the percentage of sulfur to each other.
  • first transition metal sulfide first transition metal sulfide
  • second transition metal sulfide second transition metal sulfide
  • the increase in the percentage by weight of sulfur in the transition metal sulfide as the process progresses is associated with the increase in the molar ratio of sulfur to transition metal (ns nM).
  • At least part of the sulfur contained in the sulfur compound (s) is bound as additional sulfur in the transition metal sulfide.
  • Transition metal sulfide a second transition metal sulfide, which differs in particular from the first transition metal sulfide in that it has a higher percentage by weight of sulfur or a larger molar ratio of sulfur to transition metal.
  • n-butyl mercaptan at least partially forms n-butane in the process of the present invention.
  • the sulfur-laden absorbent containing a second transition metal sulfide can be regenerated by heating in a regeneration step after completion of the absorption step.
  • the first transition metal sulfide is completely or partially re-formed from the second transition metal sulfide contained in the absorbent, and elemental sulfur is liberated.
  • the forming in the regeneration step consists essentially of elemental sulfur S2, S3, S4 - S5 S6, S7 and Ss molecules whose relative frequency of temperature and pressure depends on the regeneration step.
  • the second transition metal sulfide is regenerated by heating in a regeneration step to form the first transition metal sulfide and elemental sulfur.
  • the present invention thus also provides a process for the removal of sulfur compounds selected from mercaptans (R-SH), organic sulfides (RS-R ') and carbon oxysulfide (COS), from a hydrocarbon stream in which the hydrocarbon stream containing a or more of the sulfur compounds is contacted in an absorption step with an absorbent containing a first transition metal sulfide, wherein at least a portion of the sulfur contained in the sulfur compound (s) is bonded as additional sulfur in the transition metal sulfide to form a second transition metal sulfide, and the second transition metal sulfide is regenerated by heating in a regeneration step to form the first transition metal sulfide and elemental sulfur.
  • R-SH mercaptans
  • RS-R ' organic sulfides
  • COS carbon oxysulfide
  • the second transition metal sulfide is regenerated by heating to a temperature of 500 to 1000 ° C.
  • the pressure prevailing in the regeneration step is generally variable over a wide range. The only thing that matters is that elemental sulfur is released.
  • the regeneration step is preferably carried out at a pressure of at most 10 bar, more preferably at most 5 bar, most preferably at most 2 bar, and a pressure of at least 0.001 bar, more preferably at least 0.005 bar, most preferably at least 0.01 bar performed.
  • the absorbent containing a second transition metal sulfide is regenerated in a hot inert gas stream.
  • the hot inert gas stream is passed over the absorbent.
  • the term "inert gas stream” is to be understood as meaning a gas stream which consists of at least 75% by volume of a gas which is inert in the regeneration step and this inert gas, in particular, neither reacts with the sulfur which forms Suitable inert gases are, for example, nitrogen, methane, flue gas (carbon dioxide and water), carbon dioxide and noble gases such as argon
  • the inert gas stream is preferably at least 80% by volume, more preferably at least 90% by volume.
  • a "hot inert gas stream" in the context of the present invention means an inert gas stream which is heated prior to use in the regeneration step.
  • the hot inert gas stream in the process according to the invention has a temperature between 200 and 1000.degree. C., preferably between 300 and 800.degree. C. and particularly preferably between 400 and 800.degree.
  • the elemental sulfur is usually discharged with the hot inert gas stream.
  • This sulfur-containing inert gas stream can then be easily cooled, for example, with a heat exchanger, wherein the state of matter of the elemental sulfur changes, so that it can be easily separated in liquid or solid form from the inert gas.
  • the absorbent to be regenerated containing a second transition metal sulfide can be additionally heated.
  • the absorbent is heated and brought into contact with a hot inert gas stream.
  • the process is carried out in at least two fixed bed reactors, wherein the regeneration step is carried out alternately in a fixed bed reactor, the absorption step and in another fixed bed reactor.
  • the process is carried out in at least two fluidized bed reactors, wherein the absorption step in a first fluidized bed reactor and the regeneration step are carried out continuously in a second fluidized bed reactor.
  • Figure 1 shows a schematic flow diagram of a particularly preferred embodiment of the present invention, in which the desulfurization is carried out in two fixed bed reactors, wherein alternately carried out in a fixed bed reactor, the absorption step and in another fixed bed reactor, the regeneration step.
  • FIG. 2 shows a schematic flow diagram of a further particularly preferred embodiment in which the desulfurization process is carried out in two fluidized-bed reactors, wherein the absorption step in a first fluidized bed reactor and the regeneration step are carried out continuously in a second fluidized bed reactor.
  • FIG. 3 shows a schematic flow diagram of a test setup with which the suitability of the transition metal sulfides as an absorbent has been demonstrated.
  • a supply reservoir 1 is shown from which a hydrocarbon stream contaminated with sulfur compounds emerges and is passed to an evaporation device 2 where it evaporates and is finally introduced into a flow tube reactor 3 containing an absorbent comprising transition metal sulfide as a fixed bed.
  • FIG. 4 shows a diagram which indicates the mercaptan conversion achieved at different temperatures in a flow tube reactor which contains an absorbent comprising a first transition metal sulfide as a fixed bed.
  • Figure 5 shows the graphically superimposed X-ray diffractograms of fresh FeS used as absorbent and of used sulfur-loaded FexSy absorbent.
  • FIG. 6 shows the change in the mass of pure pyrite (FeS 2) used as a function of the temperature.
  • the desulfurization is carried out in two fixed bed reactors (see FIG. 1), wherein the absorption step is carried out alternately in one of the two fixed bed reactors, while the other fixed bed reactor is regenerated.
  • the hydrocarbon stream 1 provided contains sulfur compounds such as mercaptans (R-SH), sulfides (RS-R '), disulfides (RSS-R'), hydrogen sulfide (H 2 S), carbon oxysulfide (COS) and / or thiophenes.
  • R-SH sulfur compounds
  • RS-R ' sulfides
  • RSS-R' disulfides
  • H 2 S hydrogen sulfide
  • COS carbon oxysulfide
  • thiophenes thiophenes.
  • the hydrocarbon stream 1 is optionally passed to the reaction vessel 3 or to the reaction vessel 4.
  • Each of the reaction vessels 3 and 4 can be alternately operated as an absorber and as a regenerator, so that a continuous desulfurization process is ensured. Both reactors can, for example, be executed in the form of a fixed bed. If the absorption of the sulfur compounds in reactor 3, the hydrocarbon stream 1 is passed through the reactor 3. By means of the heater 5,
  • the absorbent can be regenerated in the reaction vessel 4.
  • the regeneration gas i. e.g. Methane, flue gas (CO2 and H2O), nitrogen or other inert gas (e.g., noble gases) are fed to the reaction vessel 4 by means of the distributor 10.
  • the regeneration gas i. e.g. Methane, flue gas (CO2 and H2O), nitrogen or other inert gas (e.g., noble gases
  • the temperature can be applied either by the heater 6 or by the heat content of the regeneration gas 9.
  • the exhaust gas 11, which is composed of the regeneration gas 9 and desorbed sulfur, leaves the reactor.
  • the manifold 12 the exhaust gas 11 is discharged from the process and cooled in the heat exchanger 13, wherein the sulfur condenses out, so that it can be finally separated from the regeneration gas in the separator 14.
  • the regeneration gas can then be returned to the process (9). Due to the process structure, the operating mode, i. Absorption or regeneration of the reaction vessels 3 and 4 can be adjusted by means of
  • the desulfurization is achieved by means of two fluidized bed reactors, wherein the absorption step in a first fluidized bed reactor and the regeneration step are carried out continuously in a second fluidized bed reactor.
  • a hydrocarbon stream 1 containing sulfur compounds such as mercaptans (R-SH), disulfides (RSS-R '), hydrogen sulfide (H2S), carbon oxysulfide (COS) and thiophenes is introduced together with an absorbent 12 into the reaction vessel 2, which for example in the form of a solid-conveying reactor is initiated.
  • the reaction vessel is designed as a fluidized-bed reactor (discharging fluidized bed).
  • a solids-conveying reactor concept eg screw reactor
  • the reaction temperature can be adjusted, which is typically between 200 and 400 ° C.
  • the desulfurized hydrocarbon stream and the absorbent which has taken up the sulfur leave the reactor and are fed to a separation device 4, in which a separation of the sulfur-laden absorbent from the desulfurized hydrocarbon stream takes place.
  • a separation device 4 After a heat recovery in the heat exchanger 5, the desulfurized hydrocarbon stream is led out of the process.
  • the sulfur-laden absorbent is regenerated in the reaction vessel 6, which in an advantageous variant of the particularly preferred embodiment is designed as a solids-conveying reactor.
  • the regeneration gas 7, for example methane, flue gas (CO2 and H2O), nitrogen or another inert gas (eg noble gases) is passed through the regenerator 6. At high temperatures (> 600 ° C) the regeneration of the absorbent takes place.
  • the temperature is thereby applied by the heat content of the regeneration gas, which can be heated by means of the heat exchanger 8.
  • the exhaust gas 9 is cooled by means of a heat exchanger 10, wherein the state of matter of the elemental sulfur changes, so that it can finally be separated in liquid or solid form from the regeneration gas 7 in a separating device 11.
  • the regeneration gas 7 can then be returned to the process.
  • the regenerated absorbent 12 is finally returned to the reaction vessel 2.
  • the absorption step was carried out in a continuous tubular reactor, the structure of which is shown in FIG. 50 g / h of the hydrocarbon stream 1, consisting of
  • This reactor was filled with a total of 50 g of FeS particles (average particle diameter: 150 ⁇ m, purity: 99.9%, confirmed by elemental and X-ray structural analysis).
  • 50 g of FeS particles average particle diameter: 150 ⁇ m, purity: 99.9%, confirmed by elemental and X-ray structural analysis.
  • 37 g of A O ⁇ spheres average diameter: 0.6 mm were added to the fixed bedding for dilution. This resulted in a fixed bed volume of a total of 70 ml.
  • the butanethiol (C4HgSH) conversion was determined at various temperatures.
  • FIG. 4 shows that the butanethiol conversion is about 32% at 230 ° C. and about 49% at 250 ° C. According to kinetic evaluation of this data, full turnover, i. a BuTanthiol conversion of 100% from a temperature of 350 ° C can be achieved.
  • the formation of butane (C4H10) could be detected by means of a qualitative GC analysis of the gas phase.
  • FIG. 5 shows the X-ray diffractograms of fresh iron (II) sulfide FeS (black) and the sulfur-loaded iron sulfide Fe x S y (red) obtained after a reaction time of 220 h.
  • Table 1 lists the weight fractions of iron and sulfur as determined by elemental analysis of both the fresh iron (II) sulfide FeS and the sulfur-loaded iron sulfide Fe x S y . It can be clearly seen that an increase in the sulfur / iron ratio has occurred during the reaction runtime. The weight proportions of Fe and S determined for the sulfur-loaded iron sulfide Fe x S y likewise confirm the presence of FezSs phases.
  • the Fe and S contents of the sulfur-loaded iron sulfide Fe x S y determined by elemental analysis also show that the run time of the 220 h experiment was insufficient to exhaust the full capacity of the absorbent and ultimately to terminate with pure FeS 2 .
  • transition metal sulfide Fe (II) S is thus suitable for use as an absorbent for the removal of sulfur compounds from hydrocarbon streams.
  • Example 2 Desorption step
  • the sulfur-laden absorbent Fe x S y which was removed according to Example 1 after a reaction time of 220 h from the fixed bed, was exposed for 30 min at 700 ° C a regeneration stream consisting of nitrogen. The release of elemental sulfur and at the same time a regeneration of the sulfur-laden absorbent Fe x S y achieved. Simplified for a pure FezSs phase, the following reaction takes place:
  • this (regeneration) treatment reduced the sulfur / iron ratio to approximately reach the ratio of the fresh iron (II) sulfide FeS used.
  • transition metal sulfide Fe (II) S can be regenerated after use as an absorber to remove sulfur compounds from hydrocarbon streams.
  • Example 3 Desorption step using pure pyrite (FeS2)
  • FIG. 6 shows the mass change as a function of the temperature. That the mass change ends at about 27%, thus the remaining solid has a mass of about 73% based on the mass of the pyrite used (FeS 2 ), is not surprising and corresponds exactly to the ratio of the molar masses of FeS to FeS 2 (see Figure 6). It is therefore clear that even if the absorbent FeS was completely loaded with sulfur, so that a sulfur-laden absorbent of the formula FeS 2 vorläge, carried a desorption of sulfur and a regeneration of FeS can take place. Further Details can also be found in the following literature: L. Charpenart, P. Masset, "Thermal Decomposition of Pyrite FeS2 under Reducing Conditions", Materials Science Forum, 654-656 (2010) 2398.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Gas Separation By Absorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé d'élimination de composés soufrés choisis parmi les mercaptans (R-SH), les sulfures organiques (R-S-R'), les disulfures organiques (R-S-S-R') et l'oxysulfure de carbone (COS), d'un flux d'hydrocarbures, dans lequel le flux d'hydrocarbures, qui contient un ou plusieurs composés soufrés, est mis en contact dans une étape d'absorption avec un absorbant contenant un premier sulfure de métal de transition, au moins une partie du soufre contenu dans les un ou plusieurs composés soufrés est lié en tant que soufre supplémentaire dans le sulfure de métal de transition, un deuxième sulfure de métal de transition étant formé.
EP15700193.4A 2014-01-10 2015-01-08 Procédé d'élimination de composés soufrés de flux d'hydrocarbures Withdrawn EP3092288A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP15700193.4A EP3092288A1 (fr) 2014-01-10 2015-01-08 Procédé d'élimination de composés soufrés de flux d'hydrocarbures

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP14150812 2014-01-10
PCT/EP2015/050189 WO2015104304A1 (fr) 2014-01-10 2015-01-08 Procédé d'élimination de composés soufrés de flux d'hydrocarbures
EP15700193.4A EP3092288A1 (fr) 2014-01-10 2015-01-08 Procédé d'élimination de composés soufrés de flux d'hydrocarbures

Publications (1)

Publication Number Publication Date
EP3092288A1 true EP3092288A1 (fr) 2016-11-16

Family

ID=49920201

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15700193.4A Withdrawn EP3092288A1 (fr) 2014-01-10 2015-01-08 Procédé d'élimination de composés soufrés de flux d'hydrocarbures

Country Status (7)

Country Link
US (1) US20160333277A1 (fr)
EP (1) EP3092288A1 (fr)
JP (1) JP2017512216A (fr)
KR (1) KR20160107253A (fr)
CN (1) CN106103665A (fr)
CA (1) CA2936295A1 (fr)
WO (1) WO2015104304A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107185462B (zh) * 2017-06-23 2021-04-06 中国科学院过程工程研究所 一种适于高so2冶金烟气还原生产s的流化床反应器及工艺
CN108380001B (zh) * 2018-05-09 2023-11-21 安徽实华工程技术股份有限公司 一种储罐区保护氮气回收处理循环利用系统及方法
CN110772876B (zh) * 2019-10-31 2022-04-15 深圳市环保科技集团股份有限公司 Rgb废液的处理方法
EP4180386A1 (fr) 2021-11-16 2023-05-17 TotalEnergies OneTech Procédé de conversion continue de h2s en h2 et en soufre

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2979384A (en) * 1958-12-22 1961-04-11 Parsons Co Ralph M Process for production of hydrogen and sulfur
US3591489A (en) * 1969-01-24 1971-07-06 Exxon Research Engineering Co Two-stage desulfurization utilizing hydrogen in the second stage reaction
CA1134596A (fr) * 1981-07-06 1982-11-02 Leo A. Behie Methode pour obtenir de l'hydrogene a partir de sulfure d'hydrogene dans un reacteur a lit fluidise au gaz
US5659109A (en) * 1996-06-04 1997-08-19 The M. W. Kellogg Company Method for removing mercaptans from LNG
US5843300A (en) * 1997-12-29 1998-12-01 Uop Llc Removal of organic sulfur compounds from FCC gasoline using regenerable adsorbents
FR2882941B1 (fr) * 2005-03-08 2007-12-21 Inst Francais Du Petrole Procede de purification d'un gaz naturel par adsorption des mercaptans
US7744841B2 (en) * 2005-09-15 2010-06-29 New Technology Ventures, Inc. Sulfur removal using ferrous carbonate absorbent
US8133302B2 (en) * 2007-06-14 2012-03-13 Exxonmobil Upstream Research Company Process for purification of hydrocarbons
US9017627B2 (en) * 2011-09-21 2015-04-28 Shell Oil Company Process for removing hydrogen sulfide from very sour hydrocarbon gas streams using metal sulfide

Also Published As

Publication number Publication date
CA2936295A1 (fr) 2015-07-16
WO2015104304A1 (fr) 2015-07-16
CN106103665A (zh) 2016-11-09
KR20160107253A (ko) 2016-09-13
JP2017512216A (ja) 2017-05-18
US20160333277A1 (en) 2016-11-17

Similar Documents

Publication Publication Date Title
DE69312559T2 (de) Absorption von Schwefelwasserstoff und Absorptionszusammensetzung dafür
DE69004622T2 (de) Selektive Entfernung von Schwefelwasserstoff mit einem einen Nickelpromotor enthaltenden Sorbentmittel.
DE68907498T2 (de) Entschwefelung.
DE69932362T2 (de) Entschwefelungsmittel und verfahren zur entschwefelung von kohlenwasserstoffen
DE60303373T2 (de) Verfahren zur entschwefelung von erdgas.
DE2754118C2 (de) Verfahren zur Aufarbeitung von Schwefelwasserstoff enthaltenden Gasen, die außerdem einen hohen Gehalt an Kohlendioxid aufweisen
DE69122217T2 (de) Sorption von Trialkylarsinen
DE69106000T2 (de) Entfernung von schwefelverunreinigungen aus kohlenwasserstoffen mittels n-halogenverbindungen.
WO2015104304A1 (fr) Procédé d'élimination de composés soufrés de flux d'hydrocarbures
DE3047825C2 (fr)
BRPI0802431B1 (pt) processo de remoção de compostos de silício de correntes de hidrocarbonetos
DE69004341T2 (de) Selektive Entfernung von Schwefelwasserstoff durch ein Zinkoxyd und Kieselgut enthaltendes Sorbentmittel.
EP0499095A1 (fr) Catalyseurs pour la séparation de composés sulfurés de gaz techniques, procédé de préparation et application
DE68903180T2 (de) Entschwefelung.
EP3789102B1 (fr) Procédé et installation permettant de séparer des impuretés d'un courant de gaz de synthèse brut et de fabriquer un produit de naphtha exempt de soufre
WO2009019238A1 (fr) Catalyseur et procédé de désulfuration de gaz contenant des hydrocarbures
EP3079809A1 (fr) Nettoyage de courants d'hydrocarbures liquides au moyen d'un sorbant contenant du cuivre
EP2773443A1 (fr) Procédé pour éliminer des composés soufrés d'un mélange gazeux contenant des hydrocarbures
CH454814A (de) Verfahren zum Reinigen von Kohlenwasserstoffen oder Kohlenwasserstoffe enthaltenden Gemischen
DE3780742T2 (de) Entschwefelung.
EP3506995A1 (fr) Procédé et dispositif permettant d'éliminer des composés de soufre organiques contenus dans des gaz riches en hydrogène
TWI403361B (zh) 從烴類原料中移除硫化合物之方法
CH646453A5 (de) Verfahren zum veredeln von kohlenstoffhaltigem material.
DE1719482A1 (de) Verfahren zur Entschwefelung von Gasen
CN117757537A (zh) 一种液化石油气深度脱硫方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160810

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20170207