Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
• • 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
  • C10G33/00—Dewatering or demulsification of hydrocarbon oils
  • C10G33/06—Dewatering or demulsification of hydrocarbon oils with mechanical means, e.g. by filtration
• • 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
  • C10L2290/08—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
  • C10L2290/24—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
  • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

• the present invention relates to a fuel composition
• a fuel composition comprising a heavy fuel oil and a product derived from biomass.
• Heavy fuel oils are commercial high boiling hydrocarbons, relatively rich in heteroatoms such as sulfur or nitrogen and metals. Heavy fuel oils require, for the most part, to be stored hot so as to avoid any risk of solidification and to facilitate pumping and flow in pipelines. Commercial heavy fuel oils must comply with ASTM D396-98. Usually, heavy fuel oils are formulated by assembling different bases from petroleum refining. In some cases, where commercial specifications are difficult to achieve with the bases usually used for formulation, heavy fuel oil is blended with lighter cuts such as distillates or desulphurized cuts, for example ARDS effluent ("Atmospheric Residue"). DeSulfurization "), which have a greater added value, which the formulator seeks to avoid.
• heavy fuel oils resulting from the assembly of different bases must be sufficiently stable over time.
• the instability can be materialized for example by an increase in the viscosity or by the sedimentation of certain products. It is therefore necessary to carry out stability tests during any new formulation of heavy fuel oil.
• the refining industry tends to decrease the production of heavy fuel oil, due to declining demand. This decrease is related to the shift to alternative energy sources by customers, particularly natural gas, as well as environmental constraints that tend to limit the amount of sulfur present in heavy fuels, sulfur is virtually absent from commercial natural gas. Reducing the amount of sulfur in heavy fuels requires refining investments and running costs that make this purification step often economically unsustainable.
• the heavy fuel oil generally needs to be stored at a temperature of 50 ° C to make it pumpable. A decrease in storage temperature would improve overall energy efficiency.
• the neutralization pastes can advantageously be used, and they essentially comprise base neutralized fatty acids, and come directly from the saponification of a vegetable or animal oil.
• these oils mention may be made of, but not limited to, rapeseed, soya, sunflower, peanut and olive oil.
• the neutralization pastes may contain, depending on their origin and the quality of the saponification, traces of phospholipids or unreacted mono-, di- or tri-glycerides.
• the fatty acids have carbon chains in C 12 -C 24 , preferably C 16 -C 20 or better C 16 -C 18 .
• the implementation of the method also allows the effective removal of solid residues in suspension, such as sludge, heavy metals and others, frequently present in such fuels.
• the centrifugation step has the advantage of simplified implementation, avoiding resorting to complex chemical separation methods, such as distillation, which can be restrictive in terms of unwanted precautions and corrosion, and expensive.
• the final fuel composition which represents the oily organic phase, after centrifugation, can advantageously be used as a fuel in installations referred to under items 2910A and 2910B relating to facilities classified for the protection of the environment (Order of 25 / 07/97 on general requirements for classified environmental protection installations subject to declaration under heading No. 2910: Combustion).
• Item 2910A is for facilities that use commercial fuels with known characteristics, such as gas, coal and biomass.
• Item 2910B refers to fuels not classified as waste and not included in 2910A, which fuels are by-products of the refining or petrochemical industry, such as High Viscosity Fuel (HVC) and oil, with characteristics close to those of commercial fuels, in particular as regards the emissions induced by their combustion.
• HVC High Viscosity Fuel
• the CHV is a solid fuel at room temperature, liquid at the temperature of use, consisting of a mixture of hydrocarbon molecules, similar to those found in heavy fuel oils. Sulfur and metal contents are essentially related to the nature of the crude oils used in their production.
• the heavy fuel can be chosen from the group consisting of FCC slurry (of known terminology), High Viscosity Fuel and heavy fuel oils.
• the heavy fuel may be an oily residue of refining, for example "slops" (recovery products).
• the heavy fuel oil in the context of the invention may be heavy fuel oil comprising a mixture of asphaltenes peptized with resins, such as maltenes, in suspension in an oil.
• asphaltenes are, in general, one of the main sources of carbon unburned production (asphaltene content of 2 to 8%).
• Other parameters of heavy fuel oil also include the possible formation of unburnt carbonaceous: a content of Conradson residue of between 6% and 15%, or an imbalance of the ratio between Conradson carbon and metals.
• Such heavy fuel oils may also be those whose sulfur content is ⁇ 1% by weight (heavy fuel oil STELs: Very Low Sulfur Content) or comprises a sulfur content ⁇ 0.55% by weight (heavy fuel oil TTBTS: Very Very Low Sulfur Content), which may further comprise one or a plurality of additives, such as activators or combustion additives.
• a combustion additive may comprise surfactants. Such compounds are known and commercially available.
• a combustion additive comprising a mixture of Fe, Ca and / or Ce oxide derivatives in a hydrocarbon solvent, such as apolar hydrocarbon solvents, is the most preferred.
• Such an additive is preferably present in a content of between 0.020 and 0.030%.
• An example is the Octapower CA2200 product provided by the Innospec Company.
• heavy fuel oils are those mentioned above and can be very fluid to reduce NOx and dust emissions.
• a preferred example of heavy fuel oil is that comprising 50% -60% by weight of CHV and 50% -40% of FCC slurry.
• the High Viscosity Fuel may be high sulfur ( ⁇ 3.5% by weight - HTS) or SULV.
• the above heavy fuels can be obtained from the Total Refining Marketing Company, and the various physico-chemical properties and the contents of various products of such heavy fuels are readily available, in particular on the said company's website.
• the heavy fuel may be a solid heavy fuel, such as "slop" sludge, residues of dehydrated and polluted soil by hydrocarbons, coke, coal and combustion soot.
• the proportion of the neutralization paste composition in the final fuel composition is not limited, and may preferably be between 10% and 80% by weight, advantageously between 30% and 80% by weight, in particular between 50% by weight. and 75% by weight.
• the advantage of using such a fuel is particularly related to its PCI (Lower Calorific Value) of 7800 kcal / kg, which can vary according to the proportion of water present in said neutralization paste, and its low production cost and exploitation.
• PCI Plant Calorific Value
• the centrifugation step (step b)) may advantageously be a three-phase centrifugation, which provides the best results in terms of water removal.
• the centrifugation step may itself be a combination of steps, in particular comprising a first diphasic type centrifugation step, which makes it possible to separate the suspended matter in the form of sludges containing a minimum of hydrocarbons, coupled in a second three-phase centrifugation step, which separates the recyclable hydrocarbon phase, the purified aqueous phase and the residual suspended solids from the first centrifugation.
• This step can be implemented by any suitable device known and commercially available.
• the centrifugation can be carried out with speeds of 4000 - 6000 rpm.
• the duration of the centrifugation depends on the nature of the species to be separated, their partition coefficient, the difference in density between the aqueous phase, the oily phase and the particles, the particle size, the surface tension of the species to separate, from the temperature, the speed of centrifugation.
• the separation time is therefore adapted to the case by those skilled in the art by conventional means of measurement and control.
• the process may comprise, after step a) and before step b), a heating step up to temperatures advantageously of 60 ° C. and 90 ° C. in order to promote the thermodynamic aspects of the centrifugation, in particular by reducing the the viscosity of the mixture, and to decrease the surface tension.
• the temperature may even be between 100 ° C. and 220 ° C.
• the method may comprise after step b), a filtration step to remove any solid residues in suspension that would not have been removed by the centrifugation step.
• Filtration is usually done on 400 to 600 * m filters.
• the method may further advantageously comprise, prior to step a) of mixing, a step of adding an acid to the neutralization paste composition, followed by a stirring step.
• step b increases the water separation efficiency during the implementation of step b), since the acid promotes the release of water from the water.
• neutralization paste composition to an acidic aqueous phase thus generated, and to improve the physico-chemical properties of said composition, in particular by improving the pumpability of the composition and by reducing the adhesion to the walls.
• the best results are obtained when the acid is present at a content of between 0.2% and 10%, in particular between 3% and 6% by weight relative to the total weight of the neutralization paste composition.
• the acid must be able to ensure its functionality to release water from the organic phase of the neutralization paste.
• the acid is very advantageously an organic or inorganic acid or their mixture of concentration sufficient to perform this operation. It is thus preferable that the acid is a strong inorganic acid, such as sulfuric acid, hydrochloric acid, phosphoric, of concentration greater than or equal to 25%. Sulfuric acid is preferred.
• a stirring step is carried out, which can be carried out by any known means, both during a pilot scale and at an industrial scale.
• the duration of the agitation is variable and generally depends on the nature of the pulp of the neutralization. Stirring is usually carried out for periods of a few minutes, such as 3-10 min, or even longer than 10 min, to reach as needed 10 to 30 min or 30-60 min.
• the increase in the volume of acid present in the reaction medium is in favor of a decrease in the intermediate phase, which increases the weight percentage of the oily phase, and a mass gain of a few percent, advantageously of 1%, is observed. at 5%.
• the process may comprise an acid addition step, as performed above, very advantageously carried out after step a) and before step b), that is to say on the dough mixture neutralization and heavy fuel.
• This embodiment is the most preferred because it allows a better release of water to the aqueous phase, and the presence of water in the final fuel composition is therefore advantageously between 1% and 0.1%, or even better, between 0.8 and 0.1%. Such a residual water content promotes the combustion properties of the final composition.
• the Applicant has observed that the residual water content above is even lower than the mixture from step a) contains more heavy fuel. Without wishing to be bound by any theory, this would be explained by the fact that the increasing proportion of the heavy fuel content in the mixture promotes the lipophilic nature of the mixture and the passage of water from the organic phase to the aqueous phase of the mixture. the final fuel composition.
• the final fuel compositions may be preferably used in various industrial fields, such as in the cement, sugar, glass, paper and heating industry, without being limiting.
• the invention also relates to a fuel composition
• a fuel composition comprising a mixture of a neutralization paste and a heavy fuel, wherein the water content is less than 3% by weight,
• the water content may be less than 1%, in particular between 0.5% and 0.1% by weight.
• the fuel composition contains traces of suspended solid residues, such as sludges, asphaltenes, metals, frequently present in such fuels in variable proportions which correspond substantially to the average of their incorporation from of each of the feedstocks used in the present process modulo the sediments separated during the step of separation of water and sediments and losses.
• Such a final fuel composition can be obtained by carrying out the above process.
• This fuel composition has the advantages as detailed above.
• Heavy fuel oil TBTS has a mass content of sulfur ⁇ 1%. Such heavy fuel oil has been previously described and is available from the Total Refining Marketing Company.
• Example A The mixture thus obtained is heated to a temperature of 80 ° C., followed by centrifugation for 20 minutes at 5000 rpm and filtration on 500 ⁇ m filters. An amount of this mixture is taken for analysis (Sample A).
• sample B A sample of heavy fuel SIDS (Sample B) and a sample of neutralization paste composition (Sample C) undergo the same analyzes after centrifugation.
• the heavy fuel oil TBTS is that described in Example 1.
• Example D A sample is taken (Sample D) and different analyzes are performed to characterize it (Table 3).
• Table 3 ⁇ u> Table 3 ⁇ / u> Analyzes (Sample D) Viscosity at 20 ° C (mm 2 / s) 2528 Viscosity at 100 ° C (mm 2 / s) 23.93 Sulfur content (% by weight) 0.87 Insoluble content (% by mass) 0.08 Ash content (% by weight) > 0.18 Water content (% by mass) 0.20
• the fuel is pumped into a charging tank and sent into a loop with a return to the charging tank, and passes into a heater to bring it to the injection temperature in the burner. There is no problem with the combustion. The flame is stable in all cases.
• the sample C is considered for acidification with an increasing content of concentrated sulfuric acid (50%).
• sample C 97 ml of sample C are mixed with 3 ml of sulfuric acid (Sample E) and 95 ml of sample C with 5 ml of sulfuric acid (Sample F). After mixing, three-phase centrifugation is carried out for 10 minutes, and the following is observed.
• Sample A is considered for acidification with an increasing content of 95% concentrated sulfuric acid.
• sample C 97 ml of sample C are mixed with 3 ml of sulfuric acid (Sample G) and 87 ml of sample C with 3 ml of sulfuric acid and 10 ml of water (Sample H). After mixing, three-phase centrifugation is carried out for 10 minutes, and the following is observed.

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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)
• Mechanical Engineering (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 2012
  • 2012-12-27 FR FR1262841A patent/FR3000498B1/fr not_active Expired - Fee Related
• 2013
  • 2013-12-20 PT PT138208426T patent/PT2938709T/pt unknown
  • 2013-12-20 EP EP13820842.6A patent/EP2938709B1/fr not_active Not-in-force
  • 2013-12-20 WO PCT/FR2013/053211 patent/WO2014102492A1/fr active Application Filing
  • 2013-12-20 ES ES13820842.6T patent/ES2618962T3/es active Active

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