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WO2019234403A1 - Procédé et composition de piégeage de h2s comprenant une imine - Google Patents

Procédé et composition de piégeage de h2s comprenant une imine Download PDF

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Publication number
WO2019234403A1
WO2019234403A1 PCT/GB2019/051534 GB2019051534W WO2019234403A1 WO 2019234403 A1 WO2019234403 A1 WO 2019234403A1 GB 2019051534 W GB2019051534 W GB 2019051534W WO 2019234403 A1 WO2019234403 A1 WO 2019234403A1
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Prior art keywords
liquid
hydrogen sulfide
imine compound
hydrocarbon liquid
fuel
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English (en)
Inventor
Philip James MALTAS
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Innospec Ltd
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Innospec Ltd
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    • 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
    • C10G21/12—Organic compounds only
    • C10G21/20—Nitrogen-containing compounds
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
    • C10L1/2283—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
    • 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
    • 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
    • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/043—Kerosene, jet 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0453—Petroleum or natural waxes, e.g. paraffin waxes, asphaltenes

Definitions

  • the invention relates to a method of scavenging hydrogen sulfide from a liquid, such as from a hydrocarbon liquid.
  • the invention also relates to a composition comprising a liquid, such as a hydrocarbon liquid, and an imine compound.
  • hydrocarbon liquids typically contain hydrogen sulfide and other sulfur based species that can liberate hydrogen sulfide (i.e. hydrogen sulfide precursors).
  • hydrocarbon liquids such as crude oil, petroleum liquids and refinery liquids may contain hydrogen sulfide and other sulfide species that can liberate hydrogen sulfide.
  • Hydrogen sulfide is toxic and corrosive and so it is desirable to scavenge it from liquids containing hydrogen sulfide.
  • hydrogen sulfide scavengers may be used at various stages of crude oil production and/or processing operations.
  • the hydrogen sulfide scavenger may be added to the crude oil whilst downhole, during production, during above ground processing, during transportation or storage, i.e. at any point prior to entering the refinery for processing.
  • Hydrogen sulfide scavengers may also be used at the refinery for example, on receipt of the oil, during storage, during the refining process or to treat finished products or waste streams.
  • organic hydrogen sulfide scavengers examples include non amine scavengers such as aldehydes and protected aldehydes like acetals, and nitrogen based scavengers such as amines, triazines and imine compounds.
  • US 5169411 discloses the use of certain hindered monoimines as hydrogen sulfide scavengers in the sulfur containing complex media of crude oils, petroleum residues and fuels.
  • hydrogen sulfide scavengers Whilst hydrogen sulfide scavengers are known, it would be desirable to provide further hydrogen sulfide scavengers, for example which are more effective at removing or reducing amounts of hydrogen sulfide in hydrocarbon liquids than current hydrogen sulfide scavengers. In particular it would be desirable to provide imine based hydrogen sulfide scavengers which react more quickly than known scavengers and/or can consistently achieve low levels of hydrogen sulfide at low treat rates.
  • an imine compound represented by the formula R 1 -C(CH 3 ) 2 -N CH 2 , wherein R 1 represents a (1 -5C)alkyl group, to scavenge hydrogen sulfide from a liquid.
  • an imine compound represented by the formula R 1 -C(CH 3 ) 2 -N CH 2 , wherein R 1 represents a (1 -5C)alkyl group, to scavenge hydrogen sulfide from a hydrocarbon liquid.
  • a liquid product obtainable by (or obtained by) a method according to the first aspect of the present invention.
  • a hydrocarbon liquid product obtainable by (or obtained by) a method according to the second aspect of the present invention.
  • liquid means a liquid at the conditions when the imine compound is added.
  • the liquid may also be a liquid at ambient temperature (typically 20 to 25°C) and pressure (about 100 kPa), but this is not essential.
  • the imine may be added to a liquid at an elevated temperature and/or pressure, for example when adding the imine compound downhole, the temperature may be over 170°C.
  • hydrocarbon liquid means any liquid which is substantially hydrocarbon in nature, i.e. which contains predominantly carbon and hydrogen, for example less than 20 wt% of other atoms such as sulfur.
  • the liquid or hydrocarbon liquid is a liquid that contains hydrogen sulfide (and optionally other sulfur containing species such as hydrogen sulfide precursors), i.e. wherein it is desirable to remove or reduce the amount of hydrogen sulfide therein.
  • the term“crude oil” means unrefined oil. Crude oil is typically composed of a complex mixture of organic (predominantly hydrocarbon) and inorganic compounds.
  • scavenging means removing or lowering the amount of hydrogen sulfide present in a liquid.
  • alkyl includes both straight and branched chain alkyl groups.
  • alkyl does not include aryl groups. References to individual alkyl groups such as “propyl” are specific for the straight chain version only and references to individual branched chain alkyl groups such as“isopropyl” are specific for the branched chain version only.
  • “(1-5C)alkyl” includes (1-2C)alkyl, propyl, isopropyl and tert-butyl.
  • the term “comprising” or “comprises” means including the component(s) specified but not to the exclusion of the presence of other components.
  • the term“consisting essentially of” or“consists essentially of means including the components specified but excluding other components except for components added for a purpose other than achieving the technical effect of the invention.
  • the term“consisting of or“consists of means including the components specified but excluding other components.
  • the use of the term “comprises” or “comprising” may also be taken to include the meaning“consists essentially of or“consisting essentially of, and may also be taken to include the meaning“consists of or“consisting of.
  • the liquid may be a hydrocarbon liquid.
  • the liquid may, for example, contain up to 5000 mg of hydrogen sulfide per L (litre) of the liquid, for example up to 1000 mg of hydrogen sulfide per L (litre) of the liquid, or for example up to 500 mg/L.
  • the liquid may contain up to 200 mg, or up 150 mg, of hydrogen sulfide per L of liquid.
  • the liquid may contain 0.1 to 150 mg, such as 0.5 to 100 mg, of hydrogen sulfide per L of liquid.
  • the liquid may contain 10 to 50 mg of hydrogen sulfide per L of liquid.
  • the liquid may contain 0.1 to 10 mg of hydrogen sulfide per L of liquid. Such amounts refer to the amount of hydrogen sulfide present in the liquid in the liquid phase.
  • the hydrocarbon liquid (prior to addition of the imine compound) may, for example, contain up to 5000 mg of hydrogen sulfide per L (litre) of the hydrocarbon liquid, for example up to 1000 mg of hydrogen sulfide per L (litre) of the hydrocarbon liquid, or for example up to 500 mg/L.
  • the hydrocarbon liquid may contain up to 200 mg, or up 150 mg, of hydrogen sulfide per L of hydrocarbon liquid.
  • the hydrocarbon liquid may contain 0.1 to 150 mg, such as 0.5 to 100 mg, of hydrogen sulfide per L of hydrocarbon liquid.
  • the hydrocarbon liquid may contain 10 to 50 mg of hydrogen sulfide per L of hydrocarbon liquid.
  • the hydrocarbon liquid may contain 0.1 to 10 mg of hydrogen sulfide per L of hydrocarbon liquid. Such amounts refer to the amount of hydrogen sulfide present in the hydrocarbon liquid in the liquid phase.
  • the method of the first aspect may be used to treat liquids which have hydrogen sulfide present in the gas phase in amounts of up to 100,000 ppm or more.
  • the method of the second aspect may be used to treat hydrocarbon liquids which have hydrogen sulfide present in the gas phase in amounts of up to 100,000 ppm or more.
  • the imine compound is added in the first and second aspects of the invention in an amount that is effective to scavenge the hydrogen sulfide present.
  • the particular treat rate of imine compound i.e. amount of imine compound added to the liquid, for example hydrocarbon liquid
  • amount of hydrogen sulfide present in the liquid will depend on several factors including, for example, the amount of hydrogen sulfide present in the liquid; the desired final level of hydrogen sulfide to be achieved; the exact imine compound being used; the desired reaction time to achieve the desired level of hydrogen sulfide; the temperature, pressure, water content, or pH of the liquid; the mixing efficiency of the liquid and imine compound; and the variability in any of these parameters.
  • one mole of imine compound may react with one mole of hydrogen sulfide.
  • 141 mg of tert-octylimine per L of hydrocarbon liquid may be required to treat 34 mg of hydrogen sulfide per L of hydrocarbon liquid.
  • Higher treat ratios may be desirable in some circumstances, for example to achieve faster reaction times, or to provide a safety margin ensuring very low levels of hydrogen sulfide in the treated fuel.
  • Lower treat ratios may be desirable in some circumstances for example to achieve a reduction in hydrogen sulfide levels without completely removing the hydrogen sulfide.
  • 0.1 to 100 or 0.5 to 20 or 0.8 to 10 molar equivalents of imine compound may be used.
  • the hydrogen sulfide present in the liquid is converted to a less corrosive, reactive and/or toxic form, for example through chemical reaction with the imine compound.
  • the imine compound may react with the hydrogen sulfide (and optionally sulfur based species) to product a nitrogen containing compound, such as an amine residue of the imine and a hydrogen sulfide aldehyde adduct.
  • the treat rate of imine compound may be from 1 to 20000 mg, for example from 1 to 5000 mg, for example from 1 to 2500 mg, such as from 1 to 1000 mg, of imine compound per L of liquid.
  • the treat rate of imine compound may be from 1 to 500 mg of imine compound per L of liquid.
  • the treat rate of imine compound may be from 1 to 20000 mg, for example from 1 to 5000 mg, for example from 1 to 2500 mg, such as from 1 to 1000 mg, of imine compound per L of hydrocarbon liquid.
  • the treat rate of imine compound may be from 1 to 500 mg of imine compound per L of hydrocarbon liquid.
  • the treat rate/ratio of imine compound:hydrogen sulfide present in the liquid may be from 40:1 to 1 :10, preferably from 10:1 to 1 :2, more preferably from 6:1 to 1 :1 and most preferably from 5:1 to 2:1 .
  • Such treat rate ratios are on a weight basis.
  • a treat rate of 40 mg imine compound per L of liquid when used to treat an amount of 1 mg of hydrogen sulfide per L of liquid would be a ratio of 40:1 .
  • the method of the first aspect of the invention scavenges hydrogen sulfide so as to remove or lower the amount of hydrogen sulfide present in a liquid.
  • the method of the first aspect suitably lowers the amount of hydrogen sulfide present in a liquid to an amount of less than 20 mg of hydrogen sulfide per L of liquid, preferably less than 15 mg of hydrogen sulfide per L of liquid, such as less than 10 mg or less than 5 mg of hydrogen sulfide per L of liquid.
  • removing hydrogen sulfide we mean that the hydrogen sulfide is substantially removed, for example such that 1 L of the treated liquid would contain less than 5 mg, such as less than 4 mg, preferably less than 3 mg, less than 2 mg or less than 1 mg, of hydrogen sulfide.
  • the treat rate/ratio of imine compound:hydrogen sulfide present in the hydrocarbon liquid may be from 40:1 to 1 :10, preferably from 10:1 to 1 :2, more preferably from 6:1 to 1 :1 and most preferably from 5:1 to 2:1 . Such treat rate ratios are on a weight basis.
  • the method of the second aspect of the invention scavenges hydrogen sulfide so as to remove or lower the amount of hydrogen sulfide present in a hydrocarbon liquid.
  • the method of the second aspect suitably lowers the amount of hydrogen sulfide present in a hydrocarbon liquid to an amount of less than 20 mg of hydrogen sulfide per L of hydrocarbon liquid, preferably less than 15 mg of hydrogen sulfide per L of hydrocarbon liquid, such as less than 10 mg or less than 5 mg of hydrogen sulfide per L of hydrocarbon liquid.
  • removing hydrogen sulfide we mean that the hydrogen sulfide is substantially removed, for example such that 1 L of the treated hydrocarbon liquid would contain less than 5 mg, such as less than 4 mg, preferably less than 3 mg, less than 2 mg or less than 1 mg, of hydrogen sulfide.
  • the imine compound may also react with other sulfur species present in the hydrocarbon liquid, such as HS and S 2 when present.
  • R 1 represents a (1 -5C)alkyl group.
  • R 1 represents a (1 -5C)alkyl group
  • R 1 represents a methyl group or a 5C alkyl group, more particularly R 1 represents a 5C alkyl group.
  • the imine compound that is used in the method of the first and second aspects of the invention may be tert-butylimine or tert-octylimine or mixtures thereof. More particularly the imine compound that is used in the method of the first and second aspects of the invention may be tert-octylimine.
  • the imine compound used in the method of the first and second aspects of the invention may be an imine compound prepared from tert-butyl amine and formaldehyde or paraformaldehyde.
  • the imine compound used in the method of the first and second aspects of the invention may be an imine compound prepared from tert-octyl amine and formaldehyde or paraformaldehyde. Preparation of imines from amines and aldehydes is well known to those skilled in the art.
  • the imine compound When the aforementioned imine compounds are used to scavenge hydrogen sulfide from a liquid (for example hydrocarbon liquid), the imine compound reacts with the hydrogen sulfide, and may also react with other sulfur based species such as HS and S 2 when present (which species can liberate hydrogen sulfide).
  • the imine compound(s) does not remove sulfur from the liquid, but it changes the hydrogen sulfide into a different form of sulfur compound (which form is more readily tolerated).
  • the particular imine compounds used in the method of the first and second aspects of the present invention are especially effective at scavenging hydrogen sulfide (and optionally other sulfur based species when present), for example compared to other known hydrogen sulfide scavengers.
  • the first and second aspects of the invention may further comprise a method wherein the hydrogen sulfide is substantially removed, such that 1 L of the treated liquid or hydrocarbon liquid contains less than 5 mg of hydrogen sulfide.
  • the methods of the first and second aspects of the invention may comprise any further suitable steps, such as mixing (for example by stirring) the mixture of the liquid or hydrocarbon liquid with the imine compound and optionally heating.
  • the liquid for example hydrocarbon liquid
  • the liquid may be any liquid, for example that comprises hydrogen sulfide to be scavenged.
  • the liquid may also comprise other sulfur species, such as HS and S 2 .
  • the liquid may be a hydrocarbon liquid.
  • the hydrocarbon liquid may be any hydrocarbon liquid, for example that comprises hydrogen sulfide to be scavenged.
  • the hydrocarbon liquid may comprise petroleum liquids.
  • the hydrocarbon liquid may comprise refinery liquids.
  • refinery liquids we mean any hydrocarbon liquid that enters or leaves (for example following processing) a refinery.
  • the hydrocarbon liquid may comprise refinery liquids which may themselves be blends of various refinery streams.
  • the hydrocarbon liquid may comprise any one or more liquids selected from crude oil, crude oil emulsions, oil field condensate, petroleum residuals, bunker fuel oil, asphalt, bitumen, mineral oils, lubricating oils, refined fuel, distillate fuel, fuel oil, heating oil, diesel fuel, gasoline and/or jet fuel.
  • the hydrocarbon liquid does not comprise crude oil.
  • the hydrocarbon liquid may comprise any one or more liquids selected from oil field condensate, petroleum residuals, bunker fuel oil, asphalt, bitumen, mineral oils, lubricating oils, refined fuel, distillate fuel, fuel oil, heating oil, diesel fuel, gasoline and/or jet fuel.
  • the hydrocarbon liquid is selected from one or more of petroleum residuals, bunker fuel oil, asphalt, bitumen, mineral oils, lubricating oils, refined fuel, distillate fuel, fuel oil, heating oil, diesel fuel, gasoline and jet fuel.
  • the hydrocarbon liquid may comprise crude oil and/or crude oil emulsions.
  • Suitable imine compounds for including in the composition of the third and fourth aspects of the present invention are as follows:
  • R 1 represents a methyl group or a 5C alkyl group, more particularly R 1 represents a 5C alkyl group.
  • the imine compound that is included in the composition of the third or fourth aspect of the invention may be tert-butylimine or tert-octylimine or mixtures thereof. More particularly, the imine compound may be tert- octylimine.
  • the imine compound that is included in the composition of the third or fourth aspect of the invention may be an imine compound prepared from tert-butyl amine and formaldehyde or paraformaldehyde.
  • the imine compound that is included in the composition of the third or fourth aspect of the invention may be an imine compound prepared from tert-octyl amine and formaldehyde or paraformaldehyde.
  • the composition of the third or fourth aspect comprises the imine compound in an amount that is effective to scavenge the hydrogen sulfide present.
  • Suitable treat rates are as described in relation to the first and second aspects.
  • composition of the third or fourth aspect may additionally comprise a nitrogen containing derivative of the imine compound, such as an amine residue of the imine compound.
  • the particular imine compound(s) included in the composition of the third or fourth aspect of the present invention are especially effective at scavenging hydrogen sulfide (and optionally other sulfur based species when present) from a liquid or hydrocarbon liquid, for example compared to other known hydrogen sulfide scavengers.
  • R 1 represents a (1-5C)alkyl group
  • the hydrocarbon liquid comprises any one or more liquids selected from crude oil, crude oil emulsions, oil field condensate, petroleum residuals, bunker fuel oil, asphalt, bitumen, mineral oils, lubricating oils, refined fuel, distillate fuel, fuel oil, heating oil, diesel fuel, gasoline and/or jet fuel.
  • composition of the third or fourth aspect of the invention may comprise further additional components.
  • additional components are typical additives known in the petroleum industry.
  • Figure 1 shows a comparison of hydrogen sulfide scavenging efficiency for Scavenger C and Scavenger A according to Example 1 , with the concentration of hydrogen sulfide remaining (in mg/L) on the y axis and time (in minutes) on the x axis.
  • Figure 2 shows a comparison of hydrogen sulfide scavenging efficiency for Scavenger C and Scavenger A according to Example 2, with the concentration of hydrogen sulfide remaining (in mg/L) on the y axis and time (in minutes) on the x axis.
  • Figure 3 shows a comparison of hydrogen sulfide scavenging efficiency for Scavengers C, D and E according to Example 4, with the concentration of hydrogen sulfide remaining (in mg/L) on the y axis and time (in minutes) on the x axis.
  • Scavenger A is a terminal imine formed by the reaction of Primene 81 R Amine and formaldehyde (or paraformaldehyde) and is a known commercial hydrogen sulfide scavenger.
  • Primene 81 R is a primary aliphatic amine in which the amino nitrogen is linked to a tertiary carbon and the total number of carbon atoms is in the C12 -C14 range.
  • Scavenger E Comparative; N-(2.6-diisopropylphenvDmethanimine) Paraformaldehyde (1 .59 g, 53 mmol) and 2,6-diisopropylaniline (9.4 g, 53 mmol) were combined and heated to 60°C for 1 hour, with stirring. The temperature was increased to 80°C for a further 2 hours, then the reaction mixture was cooled to room temperature. The resulting oil was dissolved in ethyl acetate (50 ml_). The organics were dried (MgS0 4 ) and filtered. The filtrates were concentrated in vacuo to afford Scavenger E as a colourless oil.
  • Example 1 Hydrogen sulfide scavenging efficiency
  • the hydrogen sulfide scavengers tested were: Scavenger C and Scavenger A.
  • Figure 1 shows that for the same scavenger treat rate, Scavenger C reduces the amount of hydrogen sulfide in the system considerably faster and more effectively than Scavenger A.
  • Example 2 Hydrogen sulfide scavenging efficiency
  • FIG. 2 shows that for the same scavenger treat rate, Scavenger C reduces the amount of hydrogen sulfide in the system considerably faster and more effectively than Scavenger A.
  • Example 3 Hydrogen sulfide scavenging efficiency
  • the H 2 S scavenging efficiency of Scavengers C, D and E was compared using a slightly modified procedure.
  • Caromax 20 (20 mL) was charged to a reaction vessel fitted with a stirrer bar.
  • a stock solution of Na 2 S.xH 2 0 1000 mg/L in methanol, 2 mL was added and the reaction vessel tightly sealed.
  • H 2 S scavenger under test (5 mol eq relative to H 2 S) was injected into the system and the solution H 2 S content determined at the following time points after injection; 1 , 5, 10 and 20 minutes.
  • the results for scavengers C, D or E are shown in Figure 3.
  • Figure 3 showed that for the same scavenger treat rate, t-octyl imine (Scavenger C) reduced the amount of hydrogen sulfide in the system considerably faster and more effectively than the comparative compounds N-(2,6-dimethylphenyl)methanimine (Scavenger D) or N-(2,6- diisopropylphenyl)methanimine (Scavenger E).

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne un procédé de piégeage de sulfure d'hydrogène à partir d'un liquide (tel qu'un liquide hydrocarboné), le procédé comprenant l'ajout au liquide d'un composé imine représenté par la formule R1-C(CH3)2-N=CH2, R1 représentant un groupe alkyle C1-5.
PCT/GB2019/051534 2018-05-05 2019-06-03 Procédé et composition de piégeage de h2s comprenant une imine Ceased WO2019234403A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB798062A (en) * 1954-10-27 1958-07-16 Socony Mobil Oil Co Inc Colour stabilization in fuel oils
US4778609A (en) * 1985-04-25 1988-10-18 The Lubrizol Corporation Hydrogen sulfide suppression with amine derivative
EP0475641A1 (fr) * 1990-09-10 1992-03-18 Petrolite Corporation Produits de réaction, amine aldehyde hétérocyclique utiles pour la suppression du sulfure d'hydrogène
US5169411A (en) 1989-03-03 1992-12-08 Petrolite Corporation Suppression of the evolution of hydrogen sulfide gases from crude oil, petroleum residua and fuels
US5567213A (en) * 1995-04-27 1996-10-22 Petrolite Corporation Use of olefinic imines to scavenge sulfur species

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU630937B2 (en) * 1989-06-30 1992-11-12 Petrolite Corporation Suppression of the evolution of hydrogen sulfide gases from petroleum residua
NO20031602L (no) * 2002-04-23 2003-10-24 Rohm & Haas Oljelöselige imin-syre-reaksjonsprodukter som asfaltendispergenter i råolje

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB798062A (en) * 1954-10-27 1958-07-16 Socony Mobil Oil Co Inc Colour stabilization in fuel oils
US4778609A (en) * 1985-04-25 1988-10-18 The Lubrizol Corporation Hydrogen sulfide suppression with amine derivative
US5169411A (en) 1989-03-03 1992-12-08 Petrolite Corporation Suppression of the evolution of hydrogen sulfide gases from crude oil, petroleum residua and fuels
EP0475641A1 (fr) * 1990-09-10 1992-03-18 Petrolite Corporation Produits de réaction, amine aldehyde hétérocyclique utiles pour la suppression du sulfure d'hydrogène
US5567213A (en) * 1995-04-27 1996-10-22 Petrolite Corporation Use of olefinic imines to scavenge sulfur species

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