WO2019234404A1 - Procédé et composition pour le piégeage du h2s comprenant une imine - Google Patents

Procédé et composition pour le piégeage du h2s comprenant une imine Download PDF

Info

Publication number
WO2019234404A1
WO2019234404A1 PCT/GB2019/051535 GB2019051535W WO2019234404A1 WO 2019234404 A1 WO2019234404 A1 WO 2019234404A1 GB 2019051535 W GB2019051535 W GB 2019051535W WO 2019234404 A1 WO2019234404 A1 WO 2019234404A1
Authority
WO
WIPO (PCT)
Prior art keywords
crude oil
imine compound
hydrogen sulfide
alkyl group
tert
Prior art date
Application number
PCT/GB2019/051535
Other languages
English (en)
Inventor
Cenk Burgazli
Philip James MALTAS
Original Assignee
Innospec Limited
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 Innospec Limited filed Critical Innospec Limited
Publication of WO2019234404A1 publication Critical patent/WO2019234404A1/fr

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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
    • 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
    • C10L2290/543—Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • the invention relates to a method of removing or lowering amounts of hydrogen sulfide in a crude oil.
  • the invention also relates to a method of forming a distillate fuel component boiling in the kerosene range from a crude oil.
  • the invention also relates to a composition comprising a crude oil and an imine compound and to a distillate fuel component boiling in the kerosene range.
  • crude oil typically contains hydrogen sulfide and other sulfur based species that can liberate hydrogen sulfide (i.e. hydrogen sulfide precursors).
  • Hydrogen sulfide is toxic and corrosive and so it is desirable to remove it from crude oil, or at least reduce the levels of hydrogen sulfide present in crude oil.
  • Hydrogen sulfide scavengers may be used at various stages of the 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 or during the refining process.
  • organic hydrogen sulfide scavengers include non amine scavengers such as aldehydes and protected aldehydes like acetals, and nitrogen based scavengers such as amines, triazines and imine compounds.
  • 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 crude oil 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.
  • the crude oil for example containing hydrogen sulfide scavenger(s)
  • the crude oil is typically treated by a desalting process and then distilled at atmospheric pressure to produce several distillation cuts or fractions including gaseous hydrocarbons, gasoline, naptha, kerosene, light gas oil and heavy gas oil.
  • a high proportion typically 40 to 60 wt% remains as a crude oil residue (also known as an atmospheric residue), which residue is then typically distilled in a vacuum distillation unit.
  • a further crude oil residue remains (also known as a vacuum residue).
  • the distillation fractions and residues may be further processed in the refinery.
  • the distillation fractions may be further processed or used as straight run distillates alone or with other blending components to produce fuels meeting appropriate fuel specifications.
  • the distillate fuel component boiling in the kerosene range may be suitable for use as a component of an aviation turbine fuel.
  • Fuels are required to meet many fuel specification properties such as boiling range, corrosion requirements, lubricity and thermal stability.
  • thermal stability requirement for example, as listed in ASTM D1655 Standard Specification for Aviation Turbine Fuels for the fuel as measured by ASTM D3241 Test Method for Thermal Oxidation Stability of Aviation Turbine Fuels.
  • a method of producing a distillate fuel component boiling in the kerosene range from a crude oil, wherein the crude oil contains 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, and/or an amine residue thereof, the method comprising distilling the crude oil to form the distillate fuel component.
  • a distillate fuel component boiling in the kerosene range obtainable by (or obtained by) a method according to the second aspect of the present invention.
  • a distillate fuel component boiling in the kerosene range according to the fourth aspect of the present invention in an aviation turbine fuel composition.
  • an aviation turbine fuel composition comprising a distillate fuel component boiling in the kerosene range according to the fourth aspect of the present invention.
  • 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 remove or lower the amount of hydrogen sulfide in a crude oil.
  • 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, in the preparation of a distillate fuel component boiling in the kerosene range.
  • Crude oil means unrefined oil. Crude oil is typically composed of a complex mixture of organic (predominantly hydrocarbon) and inorganic compounds.
  • aviation turbine fuel means any type of fuel suitable for use in aircraft powered by gas-turbine engines.
  • Aviation turbine fuel may also be commonly known as aviation kerosene, aviation turbine kerosene, aviation jet fuel or jet fuel.
  • Aviation turbine fuel typically comprises a petroleum distillate boiling in the kerosene range and is produced to a national or international aviation specification such as ASTM D1655.
  • 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 crude oil (prior to addition of the imine compound) may, for example, contain up to 5000 mg of hydrogen sulfide per L (litre) of crude oil, for example up to 1000 mg of hydrogen sulfide per L (litre) of crude oil, or for example up to 500 mg/L.
  • crude oils may contain up to 200 mg, or up 150 mg, of hydrogen sulfide per L of crude oil.
  • the crude oil may contain 1 to 150 mg, such as 1 to 100 mg, of hydrogen sulfide per L of crude oil.
  • the crude oil may contain 10 to 50 mg of hydrogen sulfide per L of crude oil. Such amounts refer to the amount of hydrogen sulfide in the crude oil in the liquid phase.
  • 1 mg of hydrogen sulfide in 1 L of in crude oil in the liquid phase may typically result in a level of 1 to 500 ppm of hydrogen sulfide in the gas phase.
  • the method of the first aspect may be used to treat crude oils 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 an amount that is effective to remove or lower the amount of hydrogen sulfide present.
  • the particular treat rate of imine compound (i.e. amount of imine compound added to the crude oil) will depend on several factors including, for example, the amount of hydrogen sulfide present in the crude oil; 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 crude oil; the mixing efficiency of the crude oil 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 crude oil may be required to treat 34 mg of hydrogen sulfide per L of crude oil.
  • 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.
  • some or all of the hydrogen sulfide present in the crude oil is converted to a less corrosive, reactive and/or toxic form, for example through chemical reaction with the imine compound.
  • 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 crude oil.
  • the treat rate of imine compound may be from 1 to 500 mg of imine compound per L of crude oil.
  • the treat rate/ratio of imine compound:hydrogen sulfide present in the crude oil 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 crude oil when used to treat an amount of 1 mg of hydrogen sulfide per L of crude oil would be a ratio of 40:1 .
  • the method of the first aspect of the invention lowers the amount of hydrogen sulfide present in a crude oil to an amount of less than 20 mg of hydrogen sulfide per L of crude oil, preferably less than 15 mg of hydrogen sulfide per L of crude oil, such as less than 10 mg or less than 5 mg of hydrogen sulfide per L of crude oil.
  • removing hydrogen sulfide we mean that the hydrogen sulfide is substantially removed, for example such that 1 L of the treated crude oil 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 hydrogen sulfide may be present in the crude oil naturally or may be liberated from sulfur based species naturally present in the crude oil.
  • the imine compound may also react with other sulfur species, such as HS and S 2 when present.
  • R 1 represents a (1 -5C)alkyl group.
  • R 1 represents a (1 -5C)alkyl group
  • Suitable imine compounds for use in the method of the first aspect 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 used in the method of the first aspect 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 aspect of the invention may be tert-octylimine.
  • the imine compound used in the method of the first aspect 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 aspect 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 reacts with the hydrogen sulfide, i.e. the imine compound acts as a hydrogen sulfide scavenger.
  • the imine compounds may also react with other sulfur based species such as HS and S 2 when present (which species can liberate hydrogen sulfide).
  • the scavenger does not remove sulfur from the crude oil, but it changes the hydrogen sulfide into a different form of sulfur compound (which form is more readily tolerated).
  • the reaction of the imine compound with hydrogen sulfide produces at least an amine compound, i.e. an amine residue of the imine compound.
  • the method of the first aspect of the invention is for removing or lowering amounts of hydrogen sulfide in a crude oil. It has advantageously been found that when an imine compound as defined herein is used in this method, both the imine compound and the amine residue (i.e.
  • the method treats the crude oil so that the hydrogen sulfide scavenger and residues thereof do not carry over into the kerosene distillate.
  • the inventors believe that this provides a kerosene distillate that may be used as a component of aviation turbine fuel, in which little or no atypical amines are present such that aviation turbine fuels including this distillate as a component thereof do not exhibit undesirable thermal instability as discussed above.
  • the method of the first aspect of the invention overcomes the thermal stability issues associated with aviation turbine fuels.
  • the particular imine compounds used in the method of the first aspect of the present invention are especially effective at removing or lowering amounts of hydrogen sulfide (and optionally other sulfur based species when present) from crude oil.
  • distillate fuel component boiling in the kerosene range we mean a distillate with a boiling range that is suitable for use as an aviation turbine fuel component. Typically, such a component may boil in the range of 150 to 300 °C, for example in the range of 190 to 270°C.
  • Suitable and preferred aspects of the second aspect of the invention for example in relation to the imine compound and amine residue thereof, are as set out above in relation to the first aspect.
  • the crude oil contains the imine compound and/or amine residue thereof.
  • the imine compound will typically have been added to the crude oil prior to distillation, as discussed herein.
  • the imine compound may have been added to the crude oil whilst it is being removed (for example pumped) from the ground and/or transported and/or stored and/or processed prior to distillation.
  • the imine compound will have been added to the crude oil in an amount that is effective to remove or reduce levels of hydrogen sulfide therein.
  • treat rates are as described in relation to the first aspect.
  • the amine residue that may be contained in the crude oil will be present as a product of the reaction between the imine compound and the hydrogen sulfide (and optionally other sulfur containing species when present) contained in the crude oil, as discussed herein.
  • the amine residue may be present at between 0 mol% and 100 mol % of the amount of imine compound originally added.
  • the amine residue may be present in an amount of 1 to 2500 mg, such as 1 to 1000 mg, of amine per L of crude oil. More typically, the amine residue may be present in an amount of 1 to 500 mg of amine per L of crude oil.
  • the method of the second aspect of the invention is advantageous as it allows the formation of a distillate fuel component boiling in the kerosene range that is substantially free of the imine compound and amine residue thereof. This is believed to provide a distillate fuel component boiling in the kerosene range that may be used as a component of aviation turbine fuel, in which little or no atypical amines are present such that aviation turbine fuels including this distillate fuel component do not exhibit undesirable thermal instability as discussed above.
  • the method of the second aspect of the invention overcomes the observed thermal stability issues associated with atypical amines being present in aviation turbine fuels.
  • the methods of the invention may comprise any further suitable steps, such as mixing (for example by stirring) the crude oil and the imine compound together and optionally heating.
  • the present invention further provides a method of producing a distillate fuel component boiling in the kerosene range from a crude oil, wherein the crude oil contains an imine compound selected from tert-butylimine and/or tert-octylimine (preferably the imine compound is tert-octylimine), and/or an amine residue thereof selected from tert-butylamine and/or tert- octylamine (preferably the amine residue is tert-octylamine), the method comprising distilling the crude oil to form the distillate fuel component.
  • an imine compound selected from tert-butylimine and/or tert-octylimine
  • an amine residue thereof selected from tert-butylamine and/or tert- octylamine
  • the method comprising distilling the crude oil to form the distillate fuel component.
  • 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 included in the composition of the third 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 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 aspect of the invention may be an imine compound prepared from tert-octyl amine and formaldehyde or paraformaldehyde.
  • the composition of the third aspect comprises the imine compound in an amount that is effective to remove or lower the amount of hydrogen sulfide present.
  • treat rates are as described in relation to the first aspect.
  • the composition of the third aspect may additionally comprise an amine residue of the imine compound.
  • the particular imine compound(s) included in the composition of the third aspect of the present invention are especially effective at removing or lowering amounts of hydrogen sulfide (and optionally other sulfur based species when present) from crude oil, for example compared to other known hydrogen sulfide scavengers.
  • composition of the third aspect of the invention is also considered to be advantageous because the particular imine compounds included in the composition are removed during the distillation of the crude oil at temperatures below the boiling range of the kerosene cut. This means that little or none of the imine and/or amine residue thereof enters the kerosene cut.
  • the inventors believe that this provides a kerosene distillate that may be used as a component of aviation turbine fuel, in which little or no atypical amines are present such that aviation turbine fuels including this component do not exhibit undesirable thermal instability as discussed above.
  • the composition of the third aspect of the invention overcomes the observed thermal stability issues associated with atypical amines being present in aviation turbine fuels.
  • composition of the third aspect of the invention may comprise further additional components.
  • additional components are typical crude oil additives arising from for example drilling, fracturing, completion, production, storage and transport. Such additives are known to those skilled in the art.
  • a fourth aspect of the present invention provides a distillate fuel component boiling in the kerosene range obtainable by (or obtained by) a method according to the second aspect of the present invention.
  • the distillate fuel component of the fourth aspect of the present invention is particularly suitable for use as a component of an aviation turbine fuel composition, as discussed herein.
  • a fifth aspect of the present invention provides the use of a distillate fuel component boiling in the kerosene range according to the fourth aspect of the present invention in an aviation turbine fuel composition.
  • a sixth aspect of the present invention provides an aviation turbine fuel composition comprising a distillate fuel component boiling in the kerosene range according to the fourth aspect of the present invention.
  • R 1 may represent a methyl group or a 5C alkyl group, more particularly R 1 may represent a 5C alkyl group.
  • Figure 1 shows the amine content found in distillation fractions treated with Scavenger C in Example 1 , with % w/w of the Scavenger C on the y axis and the distillation fraction (in °C) on the x axis;
  • Figure 2 shows the amine content found in distillation fractions treated with tert-octylamine in Example 1 , with % w/w of the tert-octylamine on the y axis and the distillation fraction (in °C) on the x axis;
  • Figure 3 shows the amine content found in distillation fractions treated with Scavenger A in Example 1 , with % w/w of the Scavenger A on the y axis and the distillation fraction (in °C) on the x axis;
  • Figure 4 shows the amine content found in distillation fractions treated with Primene 81 R Amine in Example 1 , with % w/w of the Primene 81 R on the y axis and the distillation fraction (in °C) on the x axis;
  • Figure 5 shows hydrogen sulfide scavenging efficiency for Scavenger C according to Example
  • Figure 6 shows hydrogen sulfide scavenging efficiency for Scavenger C according to Example
  • 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.
  • Example 1 Distillation profile of nitrogen-containing oil additives
  • FIGS 1 and 2 show that Scavenger C and tert-octylamine (the potential nitrogen-containing constituents present when treating oil-products with Scavenger C) are found solely in the low temperature (i.e. ⁇ 200 °C) distillation fractions. Consequently, only a small amount of these materials would be expected within higher temperature cuts.
  • Scavenger A and Primene 81 R Amine the potential nitrogen-containing constituents present when treating oil- products with Scavenger A
  • Figures 3 and 4 See Figures 3 and 4. Amines from Scavenger A and Primene 81 R Amine would therefore be considerably more likely to be present within higher temperature cuts, including those corresponding to aviation turbine fuel.
  • Example 2 Hydrogen sulfide scavenging efficiency
  • Figure 5 shows that Scavenger C reduces the amount of hydrogen sulfide in the system.
  • Example 3 Hydrogen sulfide scavenging efficiency
  • Figure 6 shows that Scavenger C reduces the amount of hydrogen sulfide in the system.
  • Example 4 Hydrogen sulfide scavenging efficiency
  • 2ml of a stock solution containing 0.6 mg/ml of Na 2 S in MeOH was added to 8 ml of Caromax and the vessel sealed.
  • Hydrogen sulfide was generated in situ by injecting 0.07 ml of 0.5M HCI (2 molar equivalents).
  • the solution contained approximately 50 mg/L of hydrogen sulfide.
  • Scavenger C was then injected in an amount as shown in Table 1 . The mixture was heated to 75°C for 30 minutes and then allowed to cool.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé d'élimination ou d'abaissement de quantités de sulfure d'hydrogène dans une huile brute, le procédé comprenant l'ajout à l'huile brute d'un composé imine représenté par la formule R1-C(CH3)2-N=CH2, où R1 représente un groupe (1-5C) alkyle.
PCT/GB2019/051535 2018-06-05 2019-06-03 Procédé et composition pour le piégeage du h2s comprenant une imine WO2019234404A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201862680695P 2018-06-05 2018-06-05
US62/680,695 2018-06-05

Publications (1)

Publication Number Publication Date
WO2019234404A1 true WO2019234404A1 (fr) 2019-12-12

Family

ID=66857939

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2019/051535 WO2019234404A1 (fr) 2018-06-05 2019-06-03 Procédé et composition pour le piégeage du h2s comprenant une imine

Country Status (2)

Country Link
US (1) US20190367819A1 (fr)
WO (1) WO2019234404A1 (fr)

Citations (7)

* 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
US5266185A (en) * 1990-09-10 1993-11-30 Petrolite Corporation Method of suppression of hydrogen sulfide with heterocyclic-amine aldehyde reaction products
US5567213A (en) * 1995-04-27 1996-10-22 Petrolite Corporation Use of olefinic imines to scavenge sulfur species
US20120329930A1 (en) * 2011-06-21 2012-12-27 Baker Hughes Incorporated Hydrogen sulfide scavenger for use in hydrocarbons

Patent Citations (7)

* 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
US5266185A (en) * 1990-09-10 1993-11-30 Petrolite Corporation Method of suppression of hydrogen sulfide with heterocyclic-amine aldehyde reaction products
US5567213A (en) * 1995-04-27 1996-10-22 Petrolite Corporation Use of olefinic imines to scavenge sulfur species
US20120329930A1 (en) * 2011-06-21 2012-12-27 Baker Hughes Incorporated Hydrogen sulfide scavenger for use in hydrocarbons

Also Published As

Publication number Publication date
US20190367819A1 (en) 2019-12-05

Similar Documents

Publication Publication Date Title
US5169411A (en) Suppression of the evolution of hydrogen sulfide gases from crude oil, petroleum residua and fuels
CA2805404C (fr) Utilisation d'alpha-amino-ethers pour l'elimination de sulfure d'hydrogene d'hydrocarbures
AU673236B2 (en) Removal of H2S from a hydrocarbon liquid
CA2007965C (fr) Elimination du degagement d'hydrogene sulfure gazeux a partir de residus de produits petroliers
CA2491973A1 (fr) Adjuvants monomeres d'une amine encombree steriquement et d'un aldehyde ou d'un donneur comme amines pour pieger le soufre
AU2010281621A1 (en) Processes for removing hydrogen sulfide from refined hydrocarbo streams
EP2465975A1 (fr) Composition pour eliminer des sulfures d'hydrogene
WO2015123329A1 (fr) Procédé de piégeage de sulfure d'hydrogène présent dans un flux de fluide
EP2313481A2 (fr) Procédé de production d'essence sans plomb à indice d'octane élevé, et essences ainsi obtenues
AU2009271069A1 (en) Systems and methods for producing oil and/or gas
US10457817B2 (en) 2-mercaptobenzimidazole derivatives as corrosion inhibitors
US20190367819A1 (en) Methods for reducing hydrogen sulfide in crude oil
EP3562915B1 (fr) Compositions d'additif de piégeage de sulfure d'hydrogène à base d'amine de sels de cuivre, et milieu comprenant lesdites compositions
US20030150153A1 (en) Method
WO2019234403A1 (fr) Procédé et composition de piégeage de h2s comprenant une imine
AU649471B2 (en) Heterocyclic-amine aldehyde reaction products useful for the suppression of hydrogen sulfide
JPH03502819A (ja) 燃料安定化剤組成物
EP4148110A1 (fr) Fixateurs de sulfure d'hydrogène et de mercaptans
IL24848A (en) Sweetening distillates of unsaturated hydrocarbons
US20230365873A1 (en) Nitrogen-free hydrogen sulphide and mercaptans scavengers
US3895925A (en) Motor fuel composition
CN112805248A (zh) 与酸性硫化物物质的清除有关的方法、产品和用途
AU2009270989A1 (en) Systems and methods for producing oil and/or gas

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19730486

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19730486

Country of ref document: EP

Kind code of ref document: A1