EP3441442B1 - Procédé de réduction de la teneur en soufre de carburants - Google Patents

Procédé de réduction de la teneur en soufre de carburants Download PDF

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EP3441442B1
EP3441442B1 EP18175487.0A EP18175487A EP3441442B1 EP 3441442 B1 EP3441442 B1 EP 3441442B1 EP 18175487 A EP18175487 A EP 18175487A EP 3441442 B1 EP3441442 B1 EP 3441442B1
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fuel
sulphur
carried out
water
liquid
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EP3441442A1 (fr
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Jorge Manuel Gomes Antunes
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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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/14—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with ozone-containing gases
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/10—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for with the aid of centrifugal force
    • 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
    • C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
    • 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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1275—Inorganic compounds sulfur, tellurium, selenium containing compounds
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    • 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
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    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/04—Catalyst added to fuel stream to improve a reaction
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    • 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
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    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect
    • C—CHEMISTRY; METALLURGY
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    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/08—Drying or removing water
    • 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
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    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
    • C10L2290/141—Injection, e.g. in a reactor or a fuel stream during fuel production of additive or catalyst
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    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
    • C10L2290/146—Injection, e.g. in a reactor or a fuel stream during fuel production of water
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    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/24—Mixing, stirring of fuel components
    • 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
    • C10L2290/34—Applying ultrasonic energy
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    • 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
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    • 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
    • C10L2290/544—Extraction for separating fractions, components or impurities during preparation or upgrading of a fuel
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    • 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
    • C10L2290/545—Washing, scrubbing, stripping, scavenging for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • the present invention resides in the field of hydrocarbons desulphurisation.
  • it relates to a process for the reduction of the sulphur content of petroleum products and liquid petroleum-based fuels, in particular fuels used in the maritime industry.
  • Sulphur in any of its forms reacts with oxygen in the combustion air (spontaneously or during combustion), producing sulphur oxides SO and SO2, called SO x , of which sulphur dioxide (SO 2 ) is the most abundant, that in the presence of combustion moisture leads to (H 2 SO 4 ) or sulphuric acid, responsible for the phenomenon called acid rain.
  • SO x sulphur dioxide
  • SO 2 sulphur dioxide
  • H 2 SO 4 sulphuric acid
  • Sulphur is also responsible for the emission of particulate matter (known as soot) PM2.5 being particularly important, since it is related to cancer. Sulphur compounds, given their effects, tend to threaten various ecosystems, causing irreversible damage to their quality of life. In response to these concerns various regulations have been ratified and tight requirements have been imposed to reduce the sulphur content released to the atmosphere of the fuels.
  • the hydrodesulphurisation process has certain limitations, including the ability to carry out the conversion of only few organic sulphur compounds present in the fuel (such as mercaptans, thioethers and disulphides).
  • Other compounds such as aromatics, condensed cyclic and multicyclic compounds (e.g., benzothiophenes (BT) or dibenzothiophenes (DBT)) will be difficult to remove by this technique.
  • VOC's volatile organic sulphur compounds
  • U.S. Patent 8,926,825 B2 describes the use of the Hydrodesulphurisation (HDS) technique as a way of removing sulphur compounds in hydrocarbons (more specifically in diesel samples).
  • HDS Hydrodesulphurisation
  • the process like any HDS method, uses high temperatures and pressures, which makes the method expensive and potentially dangerous.
  • the method also describes a subsequent fractionation step in a distillation column of a more loaded undercurrent in sulphur species resistant to Hydrodesulphurisation.
  • the chain is subject to an oxidation process in the presence of an oxidising agent (hydrogen peroxide in percentages of around 2.5 wt%) and exposed to an ultrasound system (power consuming 1Kw min/litre processed).
  • Oxidative Desulphurisation Another technique used more recently in the removal of sulphur compounds in heavy fuels is called Oxidative Desulphurisation (ODS). This process is based on the use of a chemical reactant with high oxidation potential, in particular 50% hydrogen peroxide (H 2 O 2 ) which causes the oxidation of free sulphur and molecular sulphur (originating sulphur oxides such as sulphones and sulphoxides). Sulphur compounds are known to be slightly more polar than hydrocarbons, however, oxides of sulphur compounds such as sulphones or sulphoxides are substantially more polar than sulphides.
  • Oxidating sulphides and sulphoxides or sulphones is usually easy and quick.
  • the conversion of slightly polar sulphides into more polar sulphones or sulphoxides allows the sulphur compounds to be extracted more easily from the fuels into an aqueous phase.
  • the ODS process has the advantage of allowing refractory sulphur compound to be removed, something that by HDS could't be achieved. These species are readily converted by oxidation and subsequently removed. The applicability of oxidative desulphurisation depends on the kinetics and selectivity of organic sulphide oxidation.
  • the oxidant is a product that, although it is not pollutant or harmful to the environment, is expensive and also potentially dangerous.
  • This technique has the advantage of not requiring as much thermal energy as hydrodesulphurisation, nor high hydrogen pressures, being likewise compatible with smaller processing units in terms of processing capacity. It allows a safer operation as it is carried in more reasonable operatory conditions (reacting at low temperatures and pressures) and makes it easier to detect and remove sulphur species resistant to HDS.
  • Another advantage of ODS over HDS is that it does not require hydrogen in the process (equally expensive). This technique presents, however, the inherent difficulty in the cost of the liquid oxidising agent, as well as the inherent danger of its handling.
  • CN 101381625 discloses a method for reducing the sulfur content of heavy fuel oil (HFO) comprising a step of blending the HFO with a liquid catalyst, adding an oxidation agent, applying sonication and using an extraction solvent to remove oxidized sulfur compounds.
  • HFO heavy fuel oil
  • Ultrasonic-Assisted Oxidative Desulphurisation is performed by combining the fuel with the oxidising agent (hydroperoxide) in the presence of an aqueous fluid (for example water), and submitting the mixture to an ultrasonification process to increase the reactivity of the species in the blend.
  • the UAOD process operates at ambient temperature and atmospheric pressure allowing the selective removal of sulphur compounds from hydrocarbons.
  • US 6,402,939 B1 discloses a method of treating Diesel Oil where the sulphur is removed from the fuel with a yield of 13.40 to 44.70%.
  • the method comprises two steps.
  • an oxidant (2 wt% hydrogen peroxide) is added to the fuel, compatibilised in an aqueous phase (water) in the presence of a solid catalyst (Tungstate: CuSO 4 or Fe(II), in a concentration of 10 mM to 100 mM) to regulate the activity of the OH radical and a phase transfer agent (PTA), more specifically dodecyltrimethylammonium fluoride or dodecyltrimethylammonium bromide) to accelerate the conversion of sulphides to sulphones.
  • a solid catalyst Tungstate: CuSO 4 or Fe(II)
  • PTA phase transfer agent
  • PTA phase transfer agent
  • the mixture is sonicated for an optimum time of 7.5 minutes and kept in an ice bath (-5 to 20 ° C), in order to avoid overheating resulting from the sonication process.
  • the second stage of the treatment consists of liquid-liquid extraction (3 successive extractions with polar solvent such as Acetonitrile, Dimethylformamide (DMF) or N-Methylpyrrolidone (NMP)) or solid-liquid (using silica gel, zeolites or polymer resin).
  • U.S. Patent No. 8,197,763 B2 describes a method similar to the above (UAOD, for Diesel fuel treatment) with the following process differences.
  • a phosphotungstic acid catalyst and a higher amount of oxidant (2 to 4% wt of hydrogen peroxide) are used.
  • the exposure time to the ultrasound system is also higher (20 minutes) and the catalyst and solvents used in the process can be recovered.
  • the yield rate of sulphur removal is from 90.30 to 97.53%.
  • US 7,758,745 B2 may also be mentioned. It corresponds to a method of Ultrasound-Assisted Oxidative Desulphurisation (UAOD), presenting, nevertheless, some differences.
  • oxidant Hydrogen Peroxide
  • two catalysts the first used in a first stage of the treatment (Desulphurisation of OSCs), consisting of a mixture of acetic acid and trifluoroacetic acid (20:80), and a microporous solid catalyst to be used in a second desulphurisation treatment of thiophenes in a fluidised bed reactor.
  • a Lewis acid type at ambient temperature ionic liquid for example trimethylammonium chloroaluminate
  • a mixture of two phase transfer agents (Acetonitrile and tetraoctylammonium fluoride) are also used.
  • This method despite having a considerably high sulphur removal rate (in the order of 99.90%), presents very high operating costs due to the fact that the operation is performed in different stages (one phase of Desulphurisation to remove OScs and another for the thiophenes), for considering metal catalysts that are difficult to synthesise, for using several reactive compounds that are toxic and expensive (ionic liquid, two phase transfer agents, two catalysts, and high amount of peroxide) and the high frequencies and intensities of the sonication process (50 kHz and 50 W/cm 2 ).
  • the use of a high amount of oxidant may also lead to a loss of the calorific value of the fuel.
  • the technique has limited results, being a specific technique for the removal of only certain sulphur species (as a case of dibenzothiophenes) and demonstrating high yields only in cases where the concentration and sulphur in the oils was relatively low (300 to 800 ppm).
  • sulphur reductions in fuels such as the HFO (Heavy Fuel Oil).
  • this type of fuel is generally purchased with sulphur concentrations of the order of 3.5%.
  • the present invention contemplates a continuous Ultrasonic-Assisted Oxidative Desulphurisation (UAOD) process to which an ozone generator is coupled to promote a more efficient oxidation of the sulphur compounds (such as sulphides, disulphides, mercaptans, thiols, thiophenes, benzothiophenes and dibenzothiophenes) present in liquid fuels, more specifically Fuel Heavy Oil, for its application in the maritime industry, or Diesel. It can also be used in other applications such as power generation industry.
  • UOD Ultrasonic-Assisted Oxidative Desulphurisation
  • Ozone has an oxidising potential higher than oxygen or other oxidising species, such as hydrogen peroxide.
  • Their formation in the process of the invention will, together with the effect of the ultrasound system, enable the sulphur compounds to be more efficiently converted to oxides and peroxides, easing their removal.
  • the process of the invention aims to obtain low-sulphur fuel, and as a consequence emissions resulting from the combustion of those fuels are less harmful to health and the environment.
  • the present invention seeks to ensure extensive and selective oxidation, while reducing the incorporation of new elements external to the system (lower peroxide addition), and the respective production and operation costs.
  • ozone allows not only the oxidation of sulphur species present in the fuel but also the conversion of the water present in the fuel composition to hydrogen peroxide, thereby increasing its oxidising potential.
  • the ozone is produced in a generator suitable for that purpose.
  • Peroxides as well as the ozone added, give rise to sulphur oxides which are easier to remove than in their initial state.
  • the peroxides formed in the ozone addition step are members of the peroxide group of hydrogen and water-soluble hydroperoxide.
  • the present invention contemplates a method for reducing the sulphur content in liquid fossil fuels comprising:
  • the fuel obtained in the method of the present invention in step h) is subjected to an additional centrifugation step (6) to remove excess water.
  • the fuel obtained as the final product has a substantially reduced sulphur content, with a minimum yield of 50% per cycle compared to the initial sulphur value (starting with sulphur fuel in the order of 3.5% by weight).
  • Ozone reagent (O 3 ) has a high oxidising potential, potential even higher than that of hydrogen peroxide (H 2 O 2 ) (2.07 V and 1.77 V respectively).
  • this oxidant can be prepared by a continuous process adjusted to the sulphur content and fuel flow being treated. This gives rise to an economic and operational safety advantage compared to the addition of other types of oxidants, not least of all because the present process does not require significant amounts of energy (low cost of production), does not take up too much space, and is fast, safe and efficient.
  • ozone in the system also adds operational advantages.
  • the oxidising agent, ozone (O 3 ) is prepared in situ through an ozone generator coupled to the process (no consumables required - outside air supplied), allows saturation of water (existing in the fuel and / or added) that will serve as a cavitation agent in ultrasonic cavitation chambers, allowing minimal use of reactants (leads to the formation of peroxides that will oxidise sulphur compounds present in the fuel).
  • the developed method thus allows the formation of oxidising species resulting from the thermionic decomposition of water in the sonication process and from the generation of ozone.
  • the oxidising species which allow the conversion of sulphur into sulphur oxides are removed at a later stage by a liquid-liquid extraction process with a polar aprotic solvent, preferably Acetonitrile (D), implying a number of passages of solvent suitable to the desired yield.
  • Acetonitrile acts as a Phase Transfer Agent (PTA), leading to the transfer of the sulphones to the aqueous phase (formed by an aqueous solution of solvent, catalyst and sulphones), maintaining the organic phase formed by the treated fuel (with lower sulphur content).
  • PTA Phase Transfer Agent
  • the extraction process preferably involves three solvent passages (not being completely required) to ensure a more efficient separation between the aqueous phase and the organic phase.
  • the transfer agent should be added in equal proportion in volume to that of the fuel to be processed. Ozone concentration can also be controlled by using sensors that accurately measure the quantity from ppm (parts per million) to ppb (parts per billion).
  • Another advantage of the invention is the use of a commercially available liquid catalyst (advantage over other previously described methods) and the possibility of recovering the extraction solvent in a high yield by fractional vacuum distillation, as well as catalyst and water added in the process, with a high recovery rate at the end of the treatment.
  • the amount of extraction solvent used can also be lower than that tested by other references - in the case of the patent CN102703111A ), which is considered a significant saving for an equally superior yield.
  • the recovery will be done as a function of the different boiling points of the different components among themselves and in relation to the sulphones
  • the process developed presents no danger in terms of storage and handling since the oxidising agent is prepared on demand and exists only in saturated aqueous solution. It is a clean oxidant because it only oxidises and does not form undesirable side products.
  • the present invention has also an advantage from an environmental point of view compared to other processes described above, since it is a process compatible with the desulphurisation of relatively modest flow rates and can therefore be implemented on board ships, allowing them to burn with the appropriate Sulphur content (S).
  • S Sulphur content
  • By-products sulphones and sulphoxides
  • By-products can be treated as oily wastes by using existing dedicated systems used on board and disposed of in the usual way (17).
  • the process of the present invention enables sulphur compounds to be removed with high yield from the fuel, based on a process which has a low energy consumption and which is adaptable to different production capacities.
  • the process does not require high temperatures nor pressures, and is safer than conventional desulphurisation processes.
  • the present invention allows the treatment of heavy fuel oils with significantly higher sulphur content (3.5% by weight), making use of liquid catalysts that are easier to obtain, using smaller amounts of extraction solvent (considerable savings), and requiring less energy and respective costs in using ultrasound technology (20 kHz compared to 40 kHz). Also, the present invention contemplates the recovery of reactants, and by-product segregation for disposal.
  • the sulphur present in the fuel consists of a wide variety of compounds which correspond to hydrocarbons containing one or more sulphur atoms covalently linked to the reminiscent molecular structure.
  • compounds are thiols, thioethers, sulphides, disulphides, mercaptans, among others.
  • Some of the more refractory compounds correspond to aromatic or nonaromatic heterocycles, which may range from thiophenes to benzothiophenes or dibenzothiophenes.
  • the present invention is intended to promote the oxidation of said species (making them easier to eliminate) to obtain a cleaner final product, while possessing a high calorific value for the intended applications.
  • the invention describes a continuous process for removing sulphur species from hydrocarbons, which is revolutionary in comparison to other identified techniques.
  • FIG. 1 shows a diagram of an embodiment of the process, in which the following steps are carried out:
  • the water will work in these situations as aqueous fluid, allowing a better compatibility between the formed peroxides and the fuel.
  • the addition of the catalyst to the system aims to increase the reactivity of the process.
  • the addition of this component should be in a ratio of 1-10% (V/V) (preferably 9% (V/V)).
  • the reaction mixture is subsequently introduced into a cavitation chamber (3) within which a titanium sonotrode (4) resonating at about 20 kHz and amplitude between 50-100% is fitted.
  • Preferred sonication conditions will be 20 kHz and 100% amplitude.
  • thermionic decomposition of the water in its various peroxides, as well as the intimate contact of those and the ozone with the free and molecular sulphur (guaranteeing complete homogeneity and stability of the emulsion) react.
  • the sonication process should be maintained for a period of time between 10 and 30 minutes (the tests performed demonstrate that the optimal sonication time depends on the fuel flow rate).
  • the mixture comprising fuel, ozone saturated water (O 3 ) and catalyst enters the cavitation chamber (3) in a continuous flow exiting the chamber as a function of the time, temperature and ultrasound energy required for the optimisation of the process.
  • an intimate admixture comprising ozone (O 3 ) and oxidising agents and peroxides resulting from the thermionic decomposition of water (EQ.1) resulting from cavitation by ultrasonication.
  • the mixture of these oxidising agents with the free sulphur and with the molecular sulphur contained in the fuel results in the formation of sulphoxides and sulphones.
  • the method is based on the joint use of two effects, oxidation of free and molecular sulphur with ozone (O 3 ) and oxidation by peroxides.
  • the product exiting the cavitation chamber is then mixed in a static mixer (5), with polar solvent (Acetonitrile-phase separation agent, PTA- (D)), in a volumetric ratio equivalent to that of the fuel to be processed (1:1).
  • polar solvent Alcohol-phase separation agent, PTA- (D)
  • the solvent being added has low affinity with the fuel and high polarity, so that it can make the sulphones, sulphides and sulphoxides separate from the liquid fuel in the centrifuge (6), going along with the aqueous phase.
  • Various passages of the polar solvent acetonitrile (D) can be made in order to ensure a more efficient separation between the aqueous and the organic phase. According to the laboratory tests, it has been found that more than one wash in order to achieve a more efficient removal of the sulphur compounds.
  • the solution consisting of acetonitrile, distilled water, acetic acid (catalyst), sulphoxides and sulphones, is then subjected to a unitary operation (fractional distillation- (8)) to recover the extraction solvent, catalyst and added water in the process (with high recovery rate due to differences in boiling points compared to the sulphones ( ⁇ 200°C)).
  • the recovery process consists of a vacuum fractional distillation with three condensers, shell and tube heat exchangers (8), the fuel being preheated in the heat exchanger (7).
  • the recovered compounds (depending on their boiling temperatures) are then condensed in the heat-exchangers (9, 10, 11 and 12 and 11) to be re-incorporated into the process (continuous process) after being recovered.
  • Acetonitrile, distilled water and acetic acid are stored in the tanks 14, 15 and 16.
  • the boiling temperature of the different compounds to be recovered will be: 82 °C for the extraction solvent, 100° C for water and 118 °C for acetic acid.
  • the sulphones and sulphoxides which are by-products of the process which are stored in the tank (17) for further treatment.
  • any other vapours (F) released in the distillation step may be extracted by means of an exhaust line placed in the process (18).
  • the initial value of the sulphur content of the fuel (A) as well as the value after treatment (13) can be determined using an X-Ray Fluorescence (FRX) technique, which follows ASTM D4294 standard.

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  • 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)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Claims (11)

  1. Procédé de réduction de la teneur en soufre élevée dans des combustibles fossiles liquides dénommés fuel lourd (HFO), comprenant :
    a) une étape de chauffage et de mélange du combustible avec de l'eau (1) ;
    b) une étape d'ozonation (2) à laquelle, tout en maintenant l'agitation, de l'ozone est ajouté en tant qu'agent oxydant au combustible à la température atteinte en a) ;
    c) une étape de mélange du combustible obtenu en b) avec un catalyseur liquide (C) et, facultativement, de l'eau (B), à la température atteinte en a), par un mélangeur statique ;
    d) une étape de sonication (3, 4) par application d'ultrasons au mélange obtenu en c) pour l'oxydation des composés soufrés et l'émulsion du combustible ;
    e) une étape d'extraction des composés soufrés oxydés obtenus en d) au moyen d'un solvant polaire aprotique et d'une différence de densité ;
    f) une étape de récupération du catalyseur liquide, du solvant d'extraction et, facultativement, de l'eau utilisés dans le processus, et au moyen d'une centrifugation ;
    g) une étape d'obtention du combustible ayant une teneur en soufre réduite.
  2. Procédé selon la revendication 1, caractérisé en ce qu'il comprend une étape de chauffage a) qui est réalisée à une température comprise entre 30 et 90 °C.
  3. Procédé selon la revendication 1 et 2, caractérisé en ce qu'il comprend une étape d'ozonation b) qui est réalisée pendant 30 à 60 minutes.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend une étape de mélange c) qui est réalisée pendant 5 à 30 minutes, et en ce que le catalyseur liquide est un acide carboxylique, ou en particulier l'acide acétique, en un rapport de 1 et 10 % du volume du mélange.
  5. Procédé selon la revendication 4, caractérisé par l'ajout d'eau en une proportion de 0 à 30 % en volume du mélange.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend une étape de sonication, l'étape de sonication d) étant réalisée pendant une durée comprise entre 10 et 30 minutes, à une fréquence comprise entre 20 et 50 kHz et dans une plage de 50 et 100 %.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend une étape d'extraction e) qui est réalisée au moyen d'un processus de séparation liquide-liquide, où le solvant polaire aprotique est l'acétonitrile en une proportion volumique égale au combustible à traiter.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend une étape de récupération f) qui est réalisée sur la base de différences entre les points d'ébullition des différents composés à récupérer par rapport aux sulfones.
  9. Procédé selon la revendication 8, caractérisé en ce qu'il comprend une étape de récupération f) qui est réalisée au moyen d'une distillation fractionnée sous vide.
  10. Procédé selon la revendication 8, caractérisé en ce qu'il comprend un renvoi des composants récupérés vers le système, représentant un processus continu.
  11. Procédé selon l'une quelconque des revendications précédentes, caractérisé par le fait que le combustible obtenu en (g) est soumis à une étape de centrifugation supplémentaire pour éliminer l'eau en excès.
EP18175487.0A 2017-08-10 2018-06-01 Procédé de réduction de la teneur en soufre de carburants Active EP3441442B1 (fr)

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US11352578B2 (en) 2020-02-19 2022-06-07 Marathon Petroleum Company Lp Low sulfur fuel oil blends for stabtility enhancement and associated methods
US11905468B2 (en) 2021-02-25 2024-02-20 Marathon Petroleum Company Lp Assemblies and methods for enhancing control of fluid catalytic cracking (FCC) processes using spectroscopic analyzers
US20220268694A1 (en) 2021-02-25 2022-08-25 Marathon Petroleum Company Lp Methods and assemblies for determining and using standardized spectral responses for calibration of spectroscopic analyzers
US11898109B2 (en) 2021-02-25 2024-02-13 Marathon Petroleum Company Lp Assemblies and methods for enhancing control of hydrotreating and fluid catalytic cracking (FCC) processes using spectroscopic analyzers
US11692141B2 (en) 2021-10-10 2023-07-04 Marathon Petroleum Company Lp Methods and systems for enhancing processing of hydrocarbons in a fluid catalytic cracking unit using a renewable additive
CA3188122A1 (fr) 2022-01-31 2023-07-31 Marathon Petroleum Company Lp Systemes et methodes de reduction des points d'ecoulement de gras fondus

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