EP2798046A1 - Fuel composition comprising a heavy fuel oil and a biomass product - Google Patents

Fuel composition comprising a heavy fuel oil and a biomass product

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Publication number
EP2798046A1
EP2798046A1 EP12824698.0A EP12824698A EP2798046A1 EP 2798046 A1 EP2798046 A1 EP 2798046A1 EP 12824698 A EP12824698 A EP 12824698A EP 2798046 A1 EP2798046 A1 EP 2798046A1
Authority
EP
European Patent Office
Prior art keywords
oil
fuel
mixture
weight
heavy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12824698.0A
Other languages
German (de)
French (fr)
Inventor
Anne Christine BARBIER
Bernard Manon
Barbara HEYBERGER
Vincent BAPTISTE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Marketing Services SA
Original Assignee
Total Raffinage Marketing SA
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
Priority claimed from FR1162487A external-priority patent/FR2985266B1/en
Priority claimed from FR1162488A external-priority patent/FR2985267B1/en
Application filed by Total Raffinage Marketing SA filed Critical Total Raffinage Marketing SA
Publication of EP2798046A1 publication Critical patent/EP2798046A1/en
Withdrawn legal-status Critical Current

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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
    • 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1888—Carboxylic acids; metal salts thereof tall oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the 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

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.
  • heavy fuel oils are formulated by assembling different bases from petroleum refining.
  • heavy fuel oil is blended with lighter cuts such as distillates or desulphurized cuts, for example an ARDS residue ("Atmospheric Residue").
  • ARDS residue an ARDS 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.
  • Tall oil or otherwise known as tall oil or tall oil, is a liquid by-product of the Kraft wood-processing process that isolates one side of the wood pulp useful for the paper industry, and the other tall oil.
  • Tall oil is mainly obtained when using conifers in the Kraft process. After treatment of the wood chips with sodium sulphide in aqueous solution, the isolated tall oil is alkaline. The latter is then acidified with sulfuric acid to produce crude tall oil.
  • tall oil mainly comprises hydrocarbon compounds functionalized with organic acids, essentially carboxylic acids, sometimes phenols.
  • Tall oil also includes unsaponifiable sterols, fatty alcohols and other alkylated hydrocarbon derivatives.
  • An average tall oil has a TAN (total acid number, in mg of KOH per mg of product) between 100 and 200, more generally between 125 and 165.
  • Tall oils are generally used as bases in the chemical industry and for the manufacture of glues and adhesives.
  • neutralization oils are derived from the acidification of neutralization pastes.
  • the neutralization pastes essentially comprise base-neutralized fatty acids, and come directly from the saponification of a vegetable or animal oil.
  • the neutralization oils may contain, depending on their origin and the quality of the saponification, traces of phospholipids or unreacted mono-, di- or tri-glycerides.
  • Neutralization oils are frequently used for animal feed.
  • the refining industry tends to decrease the production of heavy fuel oil, due to declining demand. This decrease is linked to the switch to alternative sources of energy by customers, particularly natural gas, as well as environmental constraints that tend to limit the amount of sulfur present in heavy fuels, sulfur being virtually absent from natural gas. commercial. 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 applicant proposes the use of a liquid fuel derived from biomass as an additive for the stabilization of a fuel composition comprising a heavy fuel oil, the heavy fuel being defined according to the ASTM D396-98 standard.
  • the Applicant has shown that the use of such an additive in a composition comprising heavy fuel oil, made it possible to stabilize the resulting fuel mixture composition or total fuel composition (liquid fuel from the biomass and fuel composition comprising a heavy fuel oil), that is to say to maintain substantially constant storage viscosity, that is to say, whose variation is advantageously at most 10%, of the total fuel composition for storage times greater than 3 months, preferably 3 to 6 months.
  • This provides a significant gain in terms of storage temperature of said mixing composition, which can be reduced, and to limit the need for reheating of such a mixture.
  • the stability gain is measured by the acid number, determined by the “Total Acid Number” (TAN) measurement.
  • TAN Total Acid Number
  • the acid number of the blend composition can be high, the risk of acid corrosion is limited.
  • the stability of the total fuel composition is determined by monitoring the evolution of peptization parameters, measured according to the ASTM D7157 standard, and the homogeneity of the mixture by measuring the sulfur content.
  • the liquid fuel from the biomass is advantageously chosen from the group consisting of a neutralization oil and tall oil.
  • the neutralization oil is defined as base-neutralized fatty acid compositions, which have been acidified, the fatty acids preferably coming directly from the saponification of a vegetable or animal oil, such as, without being limited to, sunflower, soybean, rapeseed and olive, and typically comprising in the great majority saturated or unsaturated C16-C18 carbon chains, including preferably unsaturated C18 carbon chains.
  • Vegetable oils usually include palmitic, oleic and linoleic acid and the like in smaller amounts.
  • the base neutralized fatty acid compositions are typically neutralization pastes.
  • the neutralization oil is advantageously present in the total fuel composition in a proportion ranging from 1 to 80% by weight, preferably from 10 to 50% by weight, more preferably from 20 to 40% by weight relative to the total weight of the total fuel composition, the best results being observed for this last range of proportion (20-40% by weight).
  • the neutralization oil can therefore advantageously be used as a fluxing agent for the preparation of a fuel mixture composition containing a heavy fuel oil.
  • the reduction in the viscosity obtained by adding this neutralization oil is a definite advantage, since the storage temperatures can be significantly reduced.
  • the neutralization oil is advantageously used for the preparation of a fuel mixture composition containing a heavy fuel oil for pour point improvement and / or for reducing the sulfur content of the fuel mixture composition.
  • the neutralization oil is also used as an additive for the preparation of a fuel mixture composition containing a heavy fuel oil, for reducing the storage temperature relative to the storage temperature in the absence of said additive, namely the neutralization oil.
  • the liquid fuel derived from the biomass is advantageously tall oil (tall oil) or possibly one of its by-products or precursors.
  • the tall oil is present in the total fuel composition in a proportion ranging from 1 to 80% by weight, preferably from 5 to 50% by weight, more preferably from 10 to 30% by weight relative to the total weight of the composition of the composition. fuel mixture, the best results being observed for this last range of proportion (10-30% by weight).
  • Tall oil is advantageously used as an additive for the preparation of a total fuel composition containing a heavy fuel oil to reduce the storage temperature relative to the storage temperature in the absence of said additive, namely tall oil.
  • the total fuel composition advantageously comprises a combustion promoter.
  • a combustion promoter is not limited and may be chosen from the group constituted by a combustion catalyst, such as based on noble metals, organic derivatives of noble and non-noble metals. metal, in a broad sense, a combustion additive comprising 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.
  • the fuel derived from the biomass used as an additive advantageously comprises proportionally less sulfur than the heavy fuel oil.
  • the fuel mixture composition according to the invention may advantageously be used for feeding an oven or a boiler.
  • Another object of the present invention is the use of a total fuel composition comprising a liquid fuel derived from biomass and a fuel composition comprising a heavy fuel oil, the heavy fuel being defined according to the ASTM standard D396-98, such as previously defined, for feeding an oven or boiler.
  • FIGS. 1 and 2 show graphically the evolution of the viscosity and the TAN of the oil / neutralization oil mixture during storage, for example 1, hereinafter.
  • FIG. 3 shows the evolution of storage viscosity at 80 ° C, for a tall oil alone or mixed with a fuel oil, compared to fuel oil alone.
  • FIG. 4 represents the evolution of the S-value during storage for the products identified in FIG. 3.
  • FIGS. 3 and 4 are related to example 2.
  • Figure 5 shows the diagram of the homogenization circuit of a tall oil / heavy fuel oil mixture 30/70 (weight / weight) for combustion tests (Example 3).
  • FIG. 6 shows the diagram of the storage circuit up to the burners, including the homogenization circuit of FIG. 5.
  • FIG. 7 represents the evolution of the temperature of the fumes as a function of the oxygen supply in the context of Example 3.
  • the neutralizing oil is much less viscous than a heavy fuel oil or a tall oil. Its acid number is much higher; in general, the TAN of the tall oils is of the order of 50 to 60mgKOH.g -1 while that of the neutralization oil characterized in this study is 120mgKOH.g -1 .
  • PCI is a little weaker than the tall oils (averaging 1 .5MJ.kg- 1 ).
  • Table II shows the evolution of the TAN and the viscosity during storage in an oven at 80 ° C., open bottles.
  • Viscosities at t 0, 1 and 4 days could not be measured due to the evaporation of a fraction of the sample in the viscometer; these values are given for information only.
  • Table II Evolution of the TAN and the viscosity @ 100 ° C. of the mixture during storage at 80 ° C.
  • Figures 1 and 2 graphically show the evolution of the viscosity and the TAN of the oil / neutralization oil mixture during storage.
  • the viscosity of the heavy fuel oil / neutralization oil mixture changes little during storage.
  • evaporation of the light fraction is observed during viscosity measurements at the beginning of the storage which prevents the measurement of viscosity. After 6 days this phenomenon disappears, the viscosity measurement becomes possible but no noticeable increase in viscosity is observed as in the case of the heavy oil / tall oil HLC mixture.
  • the acid number of the heavy fuel oil / neutralization oil mixture is quite high (of the order of 35 mgKOH / g of fuel oil) and corresponds to the value calculated from the mixing law.
  • the evolution during storage seems significantly different than in the case of mixing with tall oil HLC. Indeed, if one observes, just as with the tall oil HLC a slight increase followed by a decrease in the TAN at the beginning of storage, it increases again in the case of the mixture with the neutralization oil.
  • the TAN after the 30 days of storage is of the same order of magnitude as the calculated TAN of the mixture.
  • the corrosion test (copper blade test) shows a lack of corrosive action of the mixture (rating of the blade: 1 a).
  • the neutralization oil is a potentially useful ex-biomass fuel to be incorporated into the heavy fuel oil. Its good fluxing power leads to a significant decrease in the viscosity of the mixture which would reduce the temperature of storage and reheating of such fuel.
  • the mixture is storage stable, especially since, given the low viscosity of the mixture, the storage temperature can be considerably reduced.
  • the rate of incorporation of tall oil to heavy fuel oil has been targeted at 10% by volume, for a storage period of one month.
  • the storage temperature is of the order of 65 ° C.
  • the purpose of these measurements is to verify the stability of the mixture by monitoring the evolution of the viscosity and peptisation parameters, and the homogeneity of the mixture by measuring the sulfur content at two sampling points (top and low) in the bottle.
  • the heavy fuel oil used for the tests is a SIDS oil.
  • the incorporation rate of tall oil is 10% by volume.
  • Peptide parameters are measured according to ASTM D7157: A precise amount of sample is added with a quantity precise toluene. To this mixture is then added a quantity of heptane until the onset of asphaltene flocculation.
  • Sa indicates the aromatic character of asphaltenes.
  • S0 indicates the aromatic character of the matrix.
  • a fuel oil is stable if its S-value is greater than 1 .4 (or 1 .45).
  • the viscosity of the mixture follows the evolution of the viscosity of the heavy fuel oil. Considering the severity of the test conditions and the difference between the viscosity of the fuel oil and the mixture, it seems that the risk of instability of the mixture is limited under the conditions of implementation on site.
  • FIG. 4 which represents the evolution of the S-value during storage, shows that the S-value of the mixture is greater than 1 .7. Thus, even if one observes variations of the S-value over time, the mixture can be regarded as stable (S> 1 .4).
  • the homogeneity of the mixture is therefore evaluated by measuring the sulfur content at two sampling points.
  • the mixture can be considered homogeneous.
  • the standard NF EN ISO 2160 - Corrosive action on copper - prescribes a test method for determining the corrosive action of petroleum products on copper.
  • This test involves immersing a polished copper strip in a sample of product at a temperature and for a time specific to the class of product studied (3 hours at 100 ° C for fuels). At the end of the heating period, the blade is removed, rinsed and the color compared to the corrosion standards.
  • Tall oil has a high ash content.
  • the incorporation of 10% of tall oil with heavy fuel oil leads to an increase of about a factor of 2 in the ash content of the mixture.
  • the storage stability of the tall oil / heavy fuel oil mixture was evaluated by monitoring the viscosity and the peptization parameters of the products and the mixture during the aging of the samples placed in an oven at 80 ° C. , open bottles.
  • the results show an evolution of the viscosity of heavy fuel oil and to a lesser extent of tall oil.
  • the viscosity of the mixture follows the evolution of the viscosity of the heavy fuel oil.
  • the peptization parameters are relatively stable. Given the severity of the aging conditions and the analysis of the peptization parameters, the mixture does not seem to present any risk of instability under the storage conditions under consideration.
  • Example 3 Combustion of a Tall Oil / Heavy Fuel Oil Mixture
  • the tall oil HLC denotes the mixture of pitch and head compounds derived from the distillation of crude tall oil from paper mills.
  • the tests were carried out on the 1 MW TOTALTUB flue gas boiler equipped with a two-stage mechanical spray Cuenod burner (spray pressure 26 bar), without preheating combustion air.
  • the stress on this installation is the viscosity at the nose of the burner which must be of the order of 17cSt, or about 130 ° C for a heavy fuel oil.
  • the mixing tank with a capacity of 500L, makes it possible to homogenize the fuel, whether during its additivation or the preparation of mixtures, by recirculation of the product on the tank. This tank is maintained at 55 ° C in order to guarantee the mixture a sufficient viscosity, allowing a correct homogenization.
  • Figure 5 shows the diagram of the homogenization circuit of the mixture.
  • A, B, C, D, E manual valves
  • FIG. 6 shows the diagram of the storage circuit up to the burners, including the homogenization circuit of FIG. 5.
  • the additive or combustion enhancer is the Octapower CA2200 supplied by Innospec. It is a trimetallic additive, Fe / Ca / Ce, whose recommended additive rate is 1/4000.
  • the temperature of the mixing tank was maintained at 52/53 ° C.
  • the tests with the reference fuel were carried out under normal conditions, ie a fuel preheating temperature of 140 ° C and an injection pressure of 27.5 bar.
  • the preheating temperature was 120 ° C. and the injection pressure of 28bars. At 135 ° C, there was a blockage of the HP filter and then only a hard point on the filter passing at 130 ° C. Then the combustion becomes unstable when the temperature decreases to become pulsatory towards 96 ° C.
  • the preheating temperature was 130 ° C. and the injection pressure 26 bars.
  • a problem of instability of the flame was observed during the tests with 4.5% of O2 with tendency to recess.
  • the mixtures comprising a combustion promoter have made it possible to obtain a significant decrease in the carbon deposits, which are observed mainly on the filters connected to the exhaust stacks of the combustion gases.
  • tall oil HLC as a fuel preferably requires the installation of a suitable after-treatment system for fumes (bag filters or electro-filters) in order to limit atmospheric emissions.
  • SO x and NO x emissions are related to the sulfur and nitrogen content of the fuel. It is also noted, during the combustion of the oil / tall oil mixture, the presence in a significant amount of sulfates on the filters.

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  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

The invention relates to the use of a liquid fuel from biomass as an additive for stabilising a fuel composition comprising a heavy fuel oil which is defined according to standard ASTM D396-98.

Description

COMPOSITION COMBUSTIBLE COMPRENANT UN FIOUL LOURD ET UN PRODUIT ISSU DE LA BIOMASSE  COMBUSTIBLE COMPOSITION COMPRISING A HEAVY FUEL AND A PRODUCT FROM THE BIOMASS
La présente invention concerne une composition combustible comprenant un fioul lourd et un produit issu de la biomasse. The present invention relates to a fuel composition comprising a heavy fuel oil and a product derived from biomass.
Les fiouls lourds sont des hydrocarbures commerciaux à haut point d'ébullition, relativement riches en hétéroatomes comme le soufre ou l'azote et en métaux. Les fiouls lourds nécessitent, pour la plupart d'entre eux, d'être stockés à chaud afin d'éviter tout risque de solidification et afin d'en faciliter le pompage et l'écoulement dans des conduites d'acheminement. Les fiouls lourds commerciaux doivent être conformes à la norme ASTM D396-98.  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.
Habituellement, les fiouls lourds sont formulés par assemblage de différentes bases issues du raffinage de pétrole. Dans certains cas, lorsque les spécifications commerciales sont difficiles à atteindre avec les bases utilisées habituellement pour la formulation, le fioul lourd est mélangé avec des coupes plus légères comme des distillais ou des coupes désulfurées, par exemple un résidu d'ARDS (« Atmospheric Residue DeSulfurization »), qui ont une valeur ajoutée plus importante, ce que le formulateur cherche à éviter. Par ailleurs, les fiouls lourds résultant de l'assemblage de différentes bases doivent être suffisamment stables dans le temps. L'instabilité peut être matérialisée par exemple par une augmentation de la viscosité ou par la sédimentation de certains produits. Il est donc nécessaire d'effectuer des essais de stabilité lors de toute nouvelle formulation de fioul lourd. Le Tall oil, ou autrement dénommé huile de tall ou tallol, est un sous- produit liquide du procédé Kraft de transformation du bois permettant d'isoler d'un côté de la pulpe de bois utile pour l'industrie papetière, et de l'autre du tall oil. Le tall oil est essentiellement obtenu lors de l'utilisation de conifères dans le procédé Kraft. Après traitement des copeaux de bois par du sulfure de sodium en solution aqueuse, le tall oil isolé est alcalin. Ce dernier est ensuite acidifié par de l'acide sulfurique pour produire du tall oil brut.  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 an ARDS residue ("Atmospheric Residue"). DeSulfurization "), which have a greater added value, which the formulator seeks to avoid. In addition, 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. Tall oil, or otherwise known as tall oil or tall oil, is a liquid by-product of the Kraft wood-processing process that isolates one side of the wood pulp useful for the paper industry, and the other tall oil. Tall oil is mainly obtained when using conifers in the Kraft process. After treatment of the wood chips with sodium sulphide in aqueous solution, the isolated tall oil is alkaline. The latter is then acidified with sulfuric acid to produce crude tall oil.
Une acidification insuffisante peut conduire à un tall oil brut contenant des sels métalliques, généralement de sodium. Cette caractéristique est liée au fait que le tall oil comprend majoritairement des composés hydrocarbonés fonctionnalisés par des acides organiques, essentiellement des acides carboxyliques, parfois des phénols. Le tall oil comprend aussi des stérols non saponifiables, des alcools gras et d'autres dérivés d'hydrocarbures alkylés. Un tall oil moyen a un TAN (total acid number, en mg de KOH par mg de produit) compris entre 100 et 200, plus généralement entre 125 et 165. Insufficient acidification can lead to a crude tall oil containing metal salts, usually sodium. This characteristic is related to the fact that the tall oil mainly comprises hydrocarbon compounds functionalized with organic acids, essentially carboxylic acids, sometimes phenols. Tall oil also includes unsaponifiable sterols, fatty alcohols and other alkylated hydrocarbon derivatives. An average tall oil has a TAN (total acid number, in mg of KOH per mg of product) between 100 and 200, more generally between 125 and 165.
Les tall oils sont généralement utilisés comme bases dans l'industrie chimique et pour la fabrication de colles et adhésifs.  Tall oils are generally used as bases in the chemical industry and for the manufacture of glues and adhesives.
Par ailleurs, les huiles de neutralisation sont issues de l'acidification de pâtes de neutralisation. Les pâtes de neutralisation comprennent essentiellement des acides gras neutralisés par une base, et proviennent directement de la saponification d'une huile végétale ou animale. En plus des acides gras ayant leur fonction acide carboxylique libre, les huiles de neutralisation peuvent contenir, selon leur origine et la qualité de la saponification, des traces de phospholipides ou de mono-, di- ou tri-glycérides n'ayant pas réagi. In addition, the neutralization oils are derived from the acidification of neutralization pastes. The neutralization pastes essentially comprise base-neutralized fatty acids, and come directly from the saponification of a vegetable or animal oil. In addition to fatty acids having their free carboxylic acid function, the neutralization oils may contain, depending on their origin and the quality of the saponification, traces of phospholipids or unreacted mono-, di- or tri-glycerides.
Les huiles de neutralisation sont fréquemment utilisées pour l'alimentation animale.  Neutralization oils are frequently used for animal feed.
L'industrie du raffinage, au moins en Europe de l'ouest, a tendance à diminuer la production de fioul lourd, en raison de la baisse de la demande. Cette baisse est liée au passage à des sources d'énergie alternatives par les clients, notamment du gaz naturel, ainsi qu'aux contraintes environnementales qui tendent à limiter la quantité de soufre présent dans les combustibles lourds, le soufre étant quasiment absent du gaz naturel commercial. La diminution de la quantité de soufre présent dans les combustibles lourds nécessite des investissements en raffinage et des frais de fonctionnement qui rendent cette étape de purification souvent non viable économiquement. De plus, le fioul lourd nécessite généralement d'être stocké à une température voisine de 50°C afin de le rendre pompable. Une diminution de la température de stockage permettrait d'améliorer le rendement énergétique global. The refining industry, at least in Western Europe, tends to decrease the production of heavy fuel oil, due to declining demand. This decrease is linked to the switch to alternative sources of energy by customers, particularly natural gas, as well as environmental constraints that tend to limit the amount of sulfur present in heavy fuels, sulfur being virtually absent from natural gas. commercial. Reducing the amount of sulfur in heavy fuels requires refining investments and running costs that make this purification step often economically unsustainable. In addition, 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.
Il existe donc un besoin pour obtenir des fiouls lourds mieux adaptés aux contraintes environnementales.  There is therefore a need to obtain heavy fuel oils better adapted to environmental constraints.
A cette fin, la demanderesse propose une utilisation d'un combustible liquide issu de la biomasse comme additif pour la stabilisation d'une composition combustible comprenant un fioul lourd, le fioul lourd étant défini selon le standard ASTM D396-98.  To this end, the applicant proposes the use of a liquid fuel derived from biomass as an additive for the stabilization of a fuel composition comprising a heavy fuel oil, the heavy fuel being defined according to the ASTM D396-98 standard.
Ainsi, la Demanderesse a montré que l'utilisation d'un tel additif dans une composition comprenant du fioul lourd, permettait de stabiliser la composition de mélange combustible résultante ou composition combustible totale (combustible liquide issu de la biomasse et composition combustible comprenant un fioul lourd), c'est-à-dire de maintenir pratiquement constante la viscosité au stockage, c'est-à-dire dont la variation est avantageusement d'au plus 10%, de la composition combustible totale pour des durées de stockage supérieures à 3 mois, de préférence de 3 à 6 mois. Ceci procure un gain sensible en termes de température de stockage de ladite composition de mélange, qui peut donc être diminuée, et de limiter le besoin de réchauffage d'un tel mélange. Egalement, le gain en stabilité est mesuré par l'indice d'acidité, déterminé par la mesure de « TAN » (« Total Acid Number »). Même si selon des modes de réalisation, l'indice d'acide de la composition de mélange peut être élevé, le risque de corrosion acide est limité. Thus, the Applicant has shown that the use of such an additive in a composition comprising heavy fuel oil, made it possible to stabilize the resulting fuel mixture composition or total fuel composition (liquid fuel from the biomass and fuel composition comprising a heavy fuel oil), that is to say to maintain substantially constant storage viscosity, that is to say, whose variation is advantageously at most 10%, of the total fuel composition for storage times greater than 3 months, preferably 3 to 6 months. This provides a significant gain in terms of storage temperature of said mixing composition, which can be reduced, and to limit the need for reheating of such a mixture. Also, the stability gain is measured by the acid number, determined by the "Total Acid Number" (TAN) measurement. Although according to embodiments, the acid number of the blend composition can be high, the risk of acid corrosion is limited.
En outre, la stabilité de la composition combustible totale est déterminée par le suivi de l'évolution des paramètres de peptisation, mesuré selon le standard ASTM D7157, et de l'homogénéité du mélange par mesure de la teneur en soufre.  In addition, the stability of the total fuel composition is determined by monitoring the evolution of peptization parameters, measured according to the ASTM D7157 standard, and the homogeneity of the mixture by measuring the sulfur content.
Le combustible liquide issu de la biomasse est avantageusement choisi dans le groupe constitué par une huile de neutralisation et le tallol. The liquid fuel from the biomass is advantageously chosen from the group consisting of a neutralization oil and tall oil.
La Demanderesse a observé que le choix de ces deux combustibles liquides issus de la biomasse répondait de façon particulièrement avantageuse aux objectifs recherchés. L'huile de neutralisation est définie comme étant des compositions d'acides gras neutralisés par une base, lesquels ont été acidifiés, les acides gras provenant avantageusement directement de la saponification d'une huile végétale ou animale, telle que, sans être limitatif, de tournesol, de soja, de colza et d'olive, et comprenant classiquement en très grande majorité des chaînes carbonées en C16-C18, saturées ou insaturées, parmi lesquelles de préférence des chaînes carbonées insaturées en C18. Les huiles végétales comprennent habituellement de l'acide palmitique, oléique et linoléique et autres en plus faibles quantités. Les compositions d'acides gras neutralisés par une base sont typiquement des pâtes de neutralisation. Dans le cadre de l'invention, il peut également s'agir des sous-produits ou des précurseurs de l'huile de neutralisation. L'huile de neutralisation est avantageusement présente dans la composition combustible totale dans une proportion variant de 1 à 80% en poids, de préférence de 10 à 50% en poids, plus préférentiellement de 20 à 40% en poids par rapport au poids total de la composition combustible totale, les meilleurs résultats étant observés pour cette dernière gamme de proportion (20-40% en poids). The Applicant has observed that the choice of these two liquid fuels from biomass responds particularly advantageously to the desired objectives. The neutralization oil is defined as base-neutralized fatty acid compositions, which have been acidified, the fatty acids preferably coming directly from the saponification of a vegetable or animal oil, such as, without being limited to, sunflower, soybean, rapeseed and olive, and typically comprising in the great majority saturated or unsaturated C16-C18 carbon chains, including preferably unsaturated C18 carbon chains. Vegetable oils usually include palmitic, oleic and linoleic acid and the like in smaller amounts. The base neutralized fatty acid compositions are typically neutralization pastes. In the context of the invention, it may also be by-products or precursors of the neutralization oil. The neutralization oil is advantageously present in the total fuel composition in a proportion ranging from 1 to 80% by weight, preferably from 10 to 50% by weight, more preferably from 20 to 40% by weight relative to the total weight of the total fuel composition, the best results being observed for this last range of proportion (20-40% by weight).
L'huile de neutralisation peut donc avantageusement être utilisée comme fluxant pour la préparation d'une composition de mélange combustible contenant un fioul lourd. En effet, la diminution de la viscosité obtenue par ajout de cette huile de neutralisation est un avantage certain, car les températures de stockage peuvent être significativement réduites.  The neutralization oil can therefore advantageously be used as a fluxing agent for the preparation of a fuel mixture composition containing a heavy fuel oil. In fact, the reduction in the viscosity obtained by adding this neutralization oil is a definite advantage, since the storage temperatures can be significantly reduced.
L'huile de neutralisation est avantageusement utilisée pour la préparation d'une composition de mélange combustible contenant un fioul lourd pour l'amélioration du point d'écoulement et/ou pour diminuer la teneur en soufre de la composition de mélange combustible.  The neutralization oil is advantageously used for the preparation of a fuel mixture composition containing a heavy fuel oil for pour point improvement and / or for reducing the sulfur content of the fuel mixture composition.
L'huile de neutralisation est également utilisée en tant qu'additif pour la préparation d'une composition de mélange combustible contenant un fioul lourd, pour diminuer la température de stockage par rapport à la température de stockage en l'absence dudit additif, à savoir l'huile de neutralisation.  The neutralization oil is also used as an additive for the preparation of a fuel mixture composition containing a heavy fuel oil, for reducing the storage temperature relative to the storage temperature in the absence of said additive, namely the neutralization oil.
Selon d'autres modes de réalisation, le combustible liquide issu de la biomasse est avantageusement du tall oil (tallol) ou éventuellement un de ses sous-produits ou précurseurs. According to other embodiments, the liquid fuel derived from the biomass is advantageously tall oil (tall oil) or possibly one of its by-products or precursors.
Le tall oil est présent dans la composition combustible totale dans une proportion variant de 1 à 80% en poids, de préférence de 5 à 50% en poids, plus préférentiellement de 10 à 30% en poids par rapport au poids total de la composition de mélange combustible, les meilleurs résultats étant observés pour cette dernière gamme de proportion (10-30% en poids).  The tall oil is present in the total fuel composition in a proportion ranging from 1 to 80% by weight, preferably from 5 to 50% by weight, more preferably from 10 to 30% by weight relative to the total weight of the composition of the composition. fuel mixture, the best results being observed for this last range of proportion (10-30% by weight).
Le tall oil est avantageusement utilisé en tant qu'additif pour la préparation d'une composition combustible totale contenant un fioul lourd pour diminuer la température de stockage par rapport à la température de stockage en l'absence dudit additif, à savoir le tallol.  Tall oil is advantageously used as an additive for the preparation of a total fuel composition containing a heavy fuel oil to reduce the storage temperature relative to the storage temperature in the absence of said additive, namely tall oil.
La composition combustible totale comprend avantageusement un activateur de combustion. Un tel activateur de combustion n'est pas limité et peut être choisi dans le groupe constitué par un catalyseur de combustion, tels qu'à base de métaux nobles, dérivés organiques de métaux nobles et non métalliques, dans un sens large, un additif de combustion comprenant des tensio-actifs. De tels composés sont connus et disponibles dans le commerce. Un additif de combustion comprenant un mélange de dérivés d'oxydes de Fe, Ca et/ou Ce dans un solvant hydrocarboné, tels que des solvants à base d'hydrocarbures apolaires, est le plus préféré. Un tel additif est de préférence présent en une teneur comprise entre 0,020 et 0,030%. Un exemple est le produit Octapower CA2200 fourni par la Société Innospec. The total fuel composition advantageously comprises a combustion promoter. Such a combustion promoter is not limited and may be chosen from the group constituted by a combustion catalyst, such as based on noble metals, organic derivatives of noble and non-noble metals. metal, in a broad sense, a combustion additive comprising 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.
Le combustible issu de la biomasse utilisé comme additif comprend avantageusement proportionnellement moins de soufre que le fioul lourd.  The fuel derived from the biomass used as an additive advantageously comprises proportionally less sulfur than the heavy fuel oil.
La composition de mélange combustible selon l'invention peut être avantageusement utilisée pour l'alimentation d'un four ou d'une chaudière.  The fuel mixture composition according to the invention may advantageously be used for feeding an oven or a boiler.
Ainsi, un autre objet de la présente invention est l'utilisation d'une composition combustible totale comprenant un combustible liquide issu de la biomasse et une composition combustible comprenant un fioul lourd, le fioul lourd étant défini selon le standard ASTM D396-98, telles définies précédemment, pour l'alimentation d'un four ou d'une chaudière. Thus, another object of the present invention is the use of a total fuel composition comprising a liquid fuel derived from biomass and a fuel composition comprising a heavy fuel oil, the heavy fuel being defined according to the ASTM standard D396-98, such as previously defined, for feeding an oven or boiler.
Description des figures Description of figures
Les figures 1 et 2 représentent graphiquement l'évolution de la viscosité et du TAN du mélange fioul/huile de neutralisation au cours du stockage, pour l'exemple 1 , ci-après.  FIGS. 1 and 2 show graphically the evolution of the viscosity and the TAN of the oil / neutralization oil mixture during storage, for example 1, hereinafter.
La figure 3 représente l'évolution de la viscosité au stockage à 80°C, pour un tall oil seul ou en mélange avec un fioul, comparé au fioul seul. La figure 4 représente l'évolution de la S-value au stockage pour les produits identifiés à la figure 3. Les figures 3 et 4 sont liées à l'exemple 2.  Figure 3 shows the evolution of storage viscosity at 80 ° C, for a tall oil alone or mixed with a fuel oil, compared to fuel oil alone. FIG. 4 represents the evolution of the S-value during storage for the products identified in FIG. 3. FIGS. 3 and 4 are related to example 2.
La figure 5 présente le schéma du circuit d'homogénéisation d'un mélange tall-oil/fioul lourd 30/70 (poids/poids) en vue d'essais de combustion (exemple 3).  Figure 5 shows the diagram of the homogenization circuit of a tall oil / heavy fuel oil mixture 30/70 (weight / weight) for combustion tests (Example 3).
La figure 6 présente le schéma du circuit de stockage jusqu'aux brûleurs, incluant le circuit d'homogénéisation de la figure 5.  FIG. 6 shows the diagram of the storage circuit up to the burners, including the homogenization circuit of FIG. 5.
La figure 7 représente l'évolution de la température des fumées en fonction de l'apport en oxygène dans le cadre de l'exemple 3.  FIG. 7 represents the evolution of the temperature of the fumes as a function of the oxygen supply in the context of Example 3.
EXEMPLES EXAMPLES
Exemple 1 : Huile de neutralisation  Example 1: Neutralization Oil
Caractéristiques physico-chimiques des produits et du mélange Caractérisation du fioul et de l'huile Physico-chemical characteristics of the products and the mixture Characterization of oil and oil
Les caractéristiques des produits et du mélange sont présentées dans le tableau I.  The characteristics of the products and the mixture are presented in Table I.
L'huile de neutralisation est beaucoup moins visqueuse qu'un fioul lourd ou un tall oil. Son indice d'acide quant à lui est beaucoup plus élevé ; de manière générale, le TAN des tall oils est de l'ordre de 50 à 60mgKOH.g"1 alors que celui de l'huile de neutralisation caractérisée dans cette étude est de 120mgKOH.g"1. The neutralizing oil is much less viscous than a heavy fuel oil or a tall oil. Its acid number is much higher; in general, the TAN of the tall oils is of the order of 50 to 60mgKOH.g -1 while that of the neutralization oil characterized in this study is 120mgKOH.g -1 .
Ses faibles teneurs en soufre et en azote lui confèrent des propriétés intéressantes en termes de polluants réglementés.  Its low levels of sulfur and nitrogen give it interesting properties in terms of regulated pollutants.
Son PCI est un peu plus faible que les tall oils (de 1 .5MJ.kg"1 en moyenne). Its PCI is a little weaker than the tall oils (averaging 1 .5MJ.kg- 1 ).
Les viscosités à 50 et 100°C ainsi que la densité ont été calculées à partir des lois de mélange et sont données dans le tableau I à titre indicatif.  The viscosities at 50 and 100 ° C and the density were calculated from the mixing laws and are given in Table I for information.
La viscosité à 100°C du mélange n'a pu être mesurée car l'échantillon s'évapore dans le tube du viscosimètre. La valeur est donnée à titre indicatif, cependant elle est proche de la viscosité théorique obtenue par application de la loi de mélange en viscosité. The viscosity at 100 ° C. of the mixture could not be measured because the sample evaporated in the viscometer tube. The value is given as an indication, however it is close to the theoretical viscosity obtained by applying the law of mixing in viscosity.
Tableau I : Caractéristi ues des roduits et des mélan es Table I: Characteristics of products and mixtures
"Valeur calculée à partir de la loi de variation de la viscosité avec la température.  "Value calculated from the law of variation of viscosity with temperature.
**valeur calculée d'après la relation entre PE Luchaire et PE Pensky Martens (cf. FD T 60-145) Caractérisation du mélange ** value calculated from the relationship between PE Luchaire and PE Pensky Martens (see FD T 60-145) Characterization of the mixture
Cette étude a consisté à suivre l'évolution dans le temps d'un mélange 70% fioul lourd/30% huile de neutralisation porté à 80°C en termes de viscosité et d'indice d'acide (TAN - Total Acid Number).  This study consisted in following the evolution over time of a mixture 70% heavy fuel oil / 30% neutralization oil brought to 80 ° C in terms of viscosity and acid number (TAN - Total Acid Number).
Le tableau II présente l'évolution du TAN et de la viscosité lors du stockage dans une étuve à 80°C, flacons ouverts.  Table II shows the evolution of the TAN and the viscosity during storage in an oven at 80 ° C., open bottles.
Les viscosités à t=0, 1 et 4 jours n'ont pu être mesurées en raison de l'évaporation d'une fraction de l'échantillon dans le viscosimètre ; ces valeurs sont données à titre indicatif.  Viscosities at t = 0, 1 and 4 days could not be measured due to the evaporation of a fraction of the sample in the viscometer; these values are given for information only.
Tableau II : Evolution du TAN et de la viscosité@100°C du mélange lors du stockage à 80°C Table II: Evolution of the TAN and the viscosity @ 100 ° C. of the mixture during storage at 80 ° C.
Les figures 1 et 2 représentent graphiquement l'évolution de la viscosité et du TAN du mélange fioul/huile de neutralisation au cours du stockage. Figures 1 and 2 graphically show the evolution of the viscosity and the TAN of the oil / neutralization oil mixture during storage.
A titre de comparaison des comportements des mélanges fioul/biomasse, les résultats obtenus avec le mélange fioul/tall oil ont également été portés sur ces graphes. Le fioul lourd utilisé est le même.  As a comparison of the behavior of the oil / biomass mixtures, the results obtained with the oil / tall oil mixture were also plotted on these graphs. The heavy fuel oil used is the same.
La viscosité du mélange fioul lourd/huile de neutralisation évolue peu au cours du stockage. Par contre, on observe une évaporation de la fraction légère lors des mesures de viscosité au début du stockage qui empêche la mesure de viscosité. Au bout de 6 jours ce phénomène disparaît, la mesure de viscosité devient possible mais on n'observe pas d'augmentation notable de la viscosité comme dans le cas du mélange fioul lourd/tall oil HLC.  The viscosity of the heavy fuel oil / neutralization oil mixture changes little during storage. On the other hand, evaporation of the light fraction is observed during viscosity measurements at the beginning of the storage which prevents the measurement of viscosity. After 6 days this phenomenon disappears, the viscosity measurement becomes possible but no noticeable increase in viscosity is observed as in the case of the heavy oil / tall oil HLC mixture.
L'indice d'acide du mélange fioul lourd/huile de neutralisation est assez élevé (de l'ordre de 35 mgKOH/g de fioul) et correspond à la valeur calculée à partir de la loi de mélange. Par contre l'évolution au cours du stockage semble sensiblement différente que dans le cas du mélange avec du tall oil HLC. En effet, si on observe, tout comme avec le tall oil HLC une légère augmentation suivie d'une diminution du TAN au début du stockage celui-ci augmente à nouveau dans le cas du mélange avec l'huile de neutralisation. Cependant, le TAN après les 30 jours de stockage est du même ordre de grandeur que le TAN calculé du mélange. The acid number of the heavy fuel oil / neutralization oil mixture is quite high (of the order of 35 mgKOH / g of fuel oil) and corresponds to the value calculated from the mixing law. On the other hand, the evolution during storage seems significantly different than in the case of mixing with tall oil HLC. Indeed, if one observes, just as with the tall oil HLC a slight increase followed by a decrease in the TAN at the beginning of storage, it increases again in the case of the mixture with the neutralization oil. However, the TAN after the 30 days of storage is of the same order of magnitude as the calculated TAN of the mixture.
D'autre part le test de corrosion (essai à la lame de cuivre) montre une absence d'action corrosive du mélange (cotation de la lame : 1 a). En résumé et de façon non limitative, bien que présentant un indice d'acide élevé et un PCI inférieur à un fioul lourd ou un tall oil, l'huile de neutralisation est un combustible ex-biomasse potentiellement intéressant à incorporer dans le fioul lourd. Son bon pouvoir fluxant conduit à une diminution importante de la viscosité du mélange ce qui permettrait de diminuer la température de stockage et de réchauffage d'un tel combustible.  On the other hand the corrosion test (copper blade test) shows a lack of corrosive action of the mixture (rating of the blade: 1 a). In summary and in a nonlimiting manner, although having a high acid number and a lower ICP than a heavy fuel oil or a tall oil, the neutralization oil is a potentially useful ex-biomass fuel to be incorporated into the heavy fuel oil. Its good fluxing power leads to a significant decrease in the viscosity of the mixture which would reduce the temperature of storage and reheating of such fuel.
Le mélange est stable au stockage, d'autant plus que, compte tenue de la faible viscosité du mélange, la température de stockage pourra être considérablement diminuée.  The mixture is storage stable, especially since, given the low viscosity of the mixture, the storage temperature can be considerably reduced.
En cas d'utilisation d'un tel produit des précautions particulières devront être prises en raison du fort indice d'acide ; toutefois, le risque de corrosion acide est très faible d'après les résultats de l'essai à la lame de cuivre.  When using such a product, special precautions should be taken because of the high acid number; however, the risk of acid corrosion is very low based on the results of the copper blade test.
Exemple 2 : Tall oil Example 2: Tall oil
Evaluation de la stabilité du mélange  Evaluation of the stability of the mixture
Conditions de mise en œuvre  Conditions of implementation
Le taux d'incorporation de tall oil au fioul lourd a été ciblé à 10% en volume, pour une durée de stockage d'un mois. La température de stockage est de l'ordre de 65°C.  The rate of incorporation of tall oil to heavy fuel oil has been targeted at 10% by volume, for a storage period of one month. The storage temperature is of the order of 65 ° C.
Programme d'analyses  Program of analyzes
L'objectif de ces mesures est de vérifier la stabilité du mélange par le suivi de l'évolution de la viscosité et des paramètres de peptisation, et de l'homogénéité du mélange par mesure de la teneur en soufre en deux points de prélèvement (haut et bas) dans le flacon.  The purpose of these measurements is to verify the stability of the mixture by monitoring the evolution of the viscosity and peptisation parameters, and the homogeneity of the mixture by measuring the sulfur content at two sampling points (top and low) in the bottle.
Le fioul lourd utilisé pour les essais est un fioul TBTS. Le taux d'incorporation de tall oil est de 10% volumique.  The heavy fuel oil used for the tests is a SIDS oil. The incorporation rate of tall oil is 10% by volume.
Les paramètres de peptisation sont mesurés selon la norme ASTM D7157 : Une quantité précise d'échantillon est additionnée d'une quantité précise de toluène. A ce mélange est ensuite ajoutée une quantité d'heptane jusqu'à l'apparition de la floculation des asphaltènes. Peptide parameters are measured according to ASTM D7157: A precise amount of sample is added with a quantity precise toluene. To this mixture is then added a quantity of heptane until the onset of asphaltene flocculation.
Trois essais à différents volumes de solvant sont réalisés et permettent de calculer les indices suivants :  Three tests with different volumes of solvent are carried out and make it possible to calculate the following indices:
S : indique la stabilité intrinsèque du produit.  S: indicates the intrinsic stability of the product.
Sa : indique le caractère aromatique des asphaltènes.  Sa: indicates the aromatic character of asphaltenes.
S0 : indique le caractère aromatique de la matrice.  S0: indicates the aromatic character of the matrix.
Généralement, on considère qu'un fioul est stable si sa S-value est supérieure à 1 .4 (ou 1 .45).  Generally, it is considered that a fuel oil is stable if its S-value is greater than 1 .4 (or 1 .45).
Stabilité au stockage Storage stability
Afin d'étudier le vieillissement du produit dans des conditions de stockage relativement sévères, les échantillons ont été placés dans une étuve à 80°C, flacons ouverts. Les mesures de viscosité à 100°C et des paramètres de peptisation ont été réalisées à t=0, 1 , 3, 7, 15 et 30 jours.  In order to study the aging of the product under relatively severe storage conditions, the samples were placed in an oven at 80 ° C., open flasks. Viscosity measurements at 100 ° C and peptization parameters were performed at t = 0, 1, 3, 7, 15 and 30 days.
Les résultats sont présentés dans le tableau ci-après.  The results are shown in the table below.
L'évolution des paramètres de peptisation du fioul lourd et du mélange sont présentés dans le tableau ci-après. Les paramètres de peptisation du tall oil n'ont pu être mesurés en raison de l'absence d'asphaltènes. The evolution of the peptization parameters of heavy fuel oil and of the mixture are presented in the table below. The tall oil pepting parameters could not be measured due to the absence of asphaltenes.
Tableau IV : Evolution lors du stockage à 80°C des paramètres de peptisation (S-value) Fioul Donges Mélange (10% Tall Oil/90% fioul) t (jours) FOL 270 FOL 271 Table IV: Evolution during storage at 80 ° C of the peptization parameters (S-value) Oil Donges Blend (10% Tall Oil / 90% Oil) t (days) FOL 270 FOL 271
S So Sa S So Sa S So Sa S So Sa
0 1 ,80 0,93 0,48 1 ,89 1 ,00 0,470 1, 80 0.93 0.48 1, 89 1, 00 0.47
1 1 ,73 0,91 0,47 1 ,89 0,99 0,481 1, 73 0.91 0.47 1, 89 0.99 0.48
3 1 ,68 0,90 0,46 1 ,97 1 ,09 0,453 1, 68 0.90 0.46 1, 97 1, 09 0.45
7 1 ,65 0,91 0,45 1 ,76 0,94 0,477 1, 65 0.91 0.45 1, 76 0.94 0.47
15 1 ,75 1 ,03 0,41 1 ,95 1 ,1 1 0,431, 75 1, 03 0.41 1, 95 1, 1 1 0.43
30 1 ,64 0,96 0,42 1 ,71 0,94 0,45 30 1, 64 0.96 0.42 1, 71 0.94 0.45
Sur la figure 3, qui représente l'évolution de la viscosité au stockage@80°C, le tall oil n'évolue que très peu contrairement au fioul lourd. L'évolution du fioul lourd n'est cependant pas surprenante compte tenu des conditions d'essai particulièrement sévères (80°C, flacons ouverts). In Figure 3, which shows the evolution of storage viscosity @ 80 ° C, tall oil evolves very little unlike heavy fuel oil. The evolution of heavy fuel oil is however not surprising given the particularly severe test conditions (80 ° C, open flasks).
La viscosité du mélange suit l'évolution de la viscosité du fioul lourd. Si on considère la sévérité des conditions d'essais et l'écart entre la viscosité du fioul et du mélange, il semblerait que risque d'instabilité du mélange soit limité dans les conditions de mise en œuvre sur site.  The viscosity of the mixture follows the evolution of the viscosity of the heavy fuel oil. Considering the severity of the test conditions and the difference between the viscosity of the fuel oil and the mixture, it seems that the risk of instability of the mixture is limited under the conditions of implementation on site.
La figure 4 qui représente l'évolution de la S-value au stockage, montre que la S-value du mélange est supérieure à 1 .7. Ainsi, même si on observe des variations de la S-value au cours du temps, le mélange peut être considéré comme stable (S > 1 .4). FIG. 4, which represents the evolution of the S-value during storage, shows that the S-value of the mixture is greater than 1 .7. Thus, even if one observes variations of the S-value over time, the mixture can be regarded as stable (S> 1 .4).
Homogénéité du mélange Homogeneity of the mixture
La différence, en termes de caractéristique physicochimique, la plus significative entre les deux produits est la teneur en soufre.  The difference, in terms of physicochemical characteristic, the most significant between the two products is the sulfur content.
L'homogénéité du mélange est donc évaluée par mesure de la teneur en soufre en deux points de prélèvement.  The homogeneity of the mixture is therefore evaluated by measuring the sulfur content at two sampling points.
Les résultats sont présentés dans le tableau ci-dessous. Tableau V : Evolution lors du si tockage à 80°C de la viscosité @100°C (mm2/s)The results are shown in the table below. Table V: Evolution at 80 ° C viscosity @ 100 ° C (mm 2 / s)
Tall oil Fioul Donges Mélange (10% Tall Oil / 90% fioul) Tall Oil Oil Donges Blend (10% Tall Oil / 90% Fuel Oil)
Référence FOL 267 FOL 270 FOL 271  Reference FOL 267 FOL 270 FOL 271
échantillon Prélèvement Prélèvement haut bas Sample Sampling High Low Sampling
Teneur en <0,2 0,941 0,910 0,906 soufre Content in <0,2 0,941 0,910 0,906 sulfur
Compte tenu de l'incertitude sur la mesure de la teneur en soufre, les teneurs en soufre mesurées au point haut et au point bas sont comparables. Le mélange peut être considéré comme homogène. Given the uncertainty in the measurement of sulfur content, the sulfur contents measured at the high and low points are comparable. The mixture can be considered homogeneous.
Autres caractéristiques du tall oil et/ou du mélange Other characteristics of tall oil and / or mixture
Afin de s'assurer de l'innocuité de ce produit vis-à-vis du matériel (cuve, circuit, pompe...) mais également de son intérêt environnemental outre l'aspect incorporation de combustible ex-biomasse, un certain nombre de caractéristiques ont été mesurées telles que : corrosion, teneur en eau, teneur cendres. To ensure the safety of this product vis-à-vis the equipment (tank, circuit, pump ...) but also its environmental interest in addition to the incorporation of fuel ex-biomass, a number of characteristics were measured such as: corrosion, water content, ash content.
Tableau VI : Evolution lors du stockage à 80°C de la viscosité @100°C Table VI: Evolution during storage at 80 ° C. of the viscosity @ 100 ° C.
*calculé Corrosion * calculated Corrosion
La norme NF EN ISO 2160 - Action corrosive sur le cuivre - prescrit une méthode d'essai pour la détermination de l'action corrosive des produits pétroliers sur le cuivre.  The standard NF EN ISO 2160 - Corrosive action on copper - prescribes a test method for determining the corrosive action of petroleum products on copper.
Ce test consiste à immerger une lame de cuivre polie dans un échantillon de produit à une température et pendant un temps spécifiques à la classe du produit étudié (3heures à 100°C pour les combustibles). A la fin de la période de chauffe, la lame est retirée, rincée et la couleur comparée aux étalons de corrosion.  This test involves immersing a polished copper strip in a sample of product at a temperature and for a time specific to the class of product studied (3 hours at 100 ° C for fuels). At the end of the heating period, the blade is removed, rinsed and the color compared to the corrosion standards.
Les résultats (cotation 1 a) montrent que ni le produit, ni le mélange ne présentent de risque de corrosion vis-à-vis du matériel.  The results (rating 1 a) show that neither the product nor the mixture presents a risk of corrosion with respect to the material.
Teneur en cendres  Ash content
Le tall oil présente une teneur en cendres importante. L'incorporation de 10% de tall oil au fioul lourd conduit à une augmentation d'un facteur 2 environ de la teneur en cendres du mélange.  Tall oil has a high ash content. The incorporation of 10% of tall oil with heavy fuel oil leads to an increase of about a factor of 2 in the ash content of the mixture.
Toutefois cette augmentation est sans impact dans la configuration d'utilisation compte-tenu de la présence d'électrofiltres. Par contre si la mise en œuvre d'un tel mélange est envisagée sur une autre installation (chaudière par exemple) l'impact sur les émissions de poussières doit être pris en compte. However this increase has no impact in the configuration of use in view of the presence of electrofilters. On the other hand, if the such a mixture is envisaged on another installation (boiler for example) the impact on dust emissions must be taken into account.
Teneur en azote Nitrogen content
Même si l'incorporation de tall oil conduit à une diminution sensible de la teneur en azote, la principale voie de formation des NOX en four verrier est la voie thermique. Ainsi, la diminution de l'azote constitutif du fioul ne permet pas un gain significatif sur les émissions de NOx.  Although the incorporation of tall oil leads to a significant decrease in the nitrogen content, the main route of NOX formation in glass furnace is the thermal pathway. Thus, the reduction of the constituent nitrogen of the fuel oil does not allow a significant gain on the NOx emissions.
En résumé et de façon non limitative, la stabilité au stockage du mélange tall oil/fioul lourd a été évaluée par suivi de la viscosité et des paramètres de peptisation des produits et du mélange lors du vieillissement des échantillons placés dans une étuve à 80°C, flacons ouverts. Les résultats montrent une évolution de la viscosité du fioul lourd et dans une moindre mesure du tall oil. La viscosité du mélange suit l'évolution de la viscosité du fioul lourd. Par contre les paramètres de peptisation sont relativement stables. Compte tenu de la sévérité des conditions de vieillissement et de l'analyse des paramètres de peptisation, le mélange ne semble pas présenter de risque d'instabilité dans les conditions de stockage considérées. Exemple 3 : Combustion d'un mélange Tall oil/fioul lourd  In summary and in a nonlimiting manner, the storage stability of the tall oil / heavy fuel oil mixture was evaluated by monitoring the viscosity and the peptization parameters of the products and the mixture during the aging of the samples placed in an oven at 80 ° C. , open bottles. The results show an evolution of the viscosity of heavy fuel oil and to a lesser extent of tall oil. The viscosity of the mixture follows the evolution of the viscosity of the heavy fuel oil. On the other hand, the peptization parameters are relatively stable. Given the severity of the aging conditions and the analysis of the peptization parameters, the mixture does not seem to present any risk of instability under the storage conditions under consideration. Example 3 Combustion of a Tall Oil / Heavy Fuel Oil Mixture
Les essais de combustion présentés ici ont été réalisés sur une chaudière 1 MW équipée d'un brûleur à pulvérisation mécanique. La contrainte avec ce type de brûleur est la nécessité d'amener le combustible avec une viscosité de l'ordre de 17mm2/s ce qui correspond pour un fioul lourd classique à une température d'environ 130°C. The combustion tests presented here were carried out on a 1 MW boiler equipped with a mechanical spray burner. The constraint with this type of burner is the need to bring the fuel with a viscosity of the order of 17 mm 2 / s which corresponds for a conventional heavy fuel at a temperature of about 130 ° C.
Compte tenu de la variabilité de la qualité du tall oil HLC, de nouvelles mesures de stabilité ont été effectuées (évaluation de la stabilité du mélange au stockage mais également dans les conditions de mise en œuvre en raison du réchauffage avant brûleur).  Given the variability in the quality of the tall oil HLC, new stability measurements were made (evaluation of the stability of the mixture on storage but also under the conditions of implementation due to reheating before burner).
Evaluation de la combustibilité d'un mélange fioul lourd/tall oil HLC Evaluation of the combustibility of a heavy fuel oil / tall oil HLC mixture
La dénomination tall oil HLC désigne le mélange de pitch et de composés de tête issus de la distillation du tall oil brut en provenance de papeteries. The tall oil HLC denotes the mixture of pitch and head compounds derived from the distillation of crude tall oil from paper mills.
Les caractéristiques du fioul lourd et du tall oil HLC utilisés lors de cette étude ainsi que du mélange fioul lourd/tall oil HLC sont présentées dans le tableau VII. A noter que la teneur en soufre du fioul lourd de RP est de 0.98% masse. Celle du tall oil HLC n'a pas été déterminée. The characteristics of the heavy fuel oil and tall oil HLC used in this study as well as the heavy oil / tall oil mixture HLC are presented in Table VII. It should be noted that the sulfur content of the heavy fuel oil of RP is 0.98% by mass. That of tall oil HLC has not been determined.
L'étude de combustibilité a été réalisée à partir d'un mélange fioul lourd/tall oil HLC 70/30. The combustibility study was carried out using a heavy oil / tall oil mixture HLC 70/30.
Combustibilité Combustibility
Installation de combustion  Combustion plant
Les essais ont été réalisés sur la chaudière à tubes de fumées TOTALTUB de 1 MW équipée d'un brûleur Cuenod à pulvérisation mécanique deux allures (pression d'atomisation 26 bars), sans préchauffage d'air de combustion. La contrainte sur cette installation est la viscosité au nez du brûleur qui doit être de l'ordre de 17cSt, soit environ 130°C pour un fioul lourd. La cuve de mélange, d'une capacité de 500L, permet d'homogénéiser le combustible, que ce soit lors de son additivation ou de la préparation de mélanges, par recirculation du produit sur la cuve. Cette cuve est maintenue à 55°C afin de garantir au mélange une viscosité suffisante, permettant une homogénéisation correcte. The tests were carried out on the 1 MW TOTALTUB flue gas boiler equipped with a two-stage mechanical spray Cuenod burner (spray pressure 26 bar), without preheating combustion air. The stress on this installation is the viscosity at the nose of the burner which must be of the order of 17cSt, or about 130 ° C for a heavy fuel oil. The mixing tank, with a capacity of 500L, makes it possible to homogenize the fuel, whether during its additivation or the preparation of mixtures, by recirculation of the product on the tank. This tank is maintained at 55 ° C in order to guarantee the mixture a sufficient viscosity, allowing a correct homogenization.
La figure 5 présente le schéma du circuit d'homogénéisation du mélange.  Figure 5 shows the diagram of the homogenization circuit of the mixture.
Liste des références visibles sur la figure 5 :  List of references visible in Figure 5:
A, B, C, D, E : vannes manuelles  A, B, C, D, E: manual valves
1 : cuve (500L)  1: tank (500L)
2 : flexible de retour vers la cuve par le dessus  2: hose back to the tank from above
3 : Réchauffeur de cuve  3: Tank heater
4 : manomètre (P = 2 bars)  4: pressure gauge (P = 2 bar)
5 : Pompe de gavage  5: Feeding pump
6 : filtre (filtre 1 mm)  6: filter (1 mm filter)
La figure 6 présente le schéma du circuit de stockage jusqu'aux brûleurs, incluant le circuit d'homogénéisation de la figure 5.  FIG. 6 shows the diagram of the storage circuit up to the burners, including the homogenization circuit of FIG. 5.
Liste des références visibles sur la figure 6 :  List of references visible in Figure 6:
7 : filtre (filtre 250 microns)  7: filter (250 micron filter)
8 : pompe HP  8: HP pump
9 : manomètre (P = 26 bars)  9: pressure gauge (P = 26 bar)
10 : réchauffeur HP  10: HP heater
1 1 : filtre HP (filtre 160 microns)  1 1: HP filter (160 micron filter)
Matériel de mesure Measuring equipment
Le matériel de mesure utilisé pour caractériser les fumées est décrit dans le tableau ci-dessous : The measuring equipment used to characterize the fumes is described in the table below:
Tableau VIII : Matériel et principe de mesure des émissions Table VIII: Equipment and Measurement Principle
Réalisation des essais Performing tests
Lors de chaque série d'essais, les mesures d'émissions ont été réalisées aux 3 excès d'air suivants : 6%, 4.5% et 3%.  During each series of tests, the emission measurements were performed on the following 3 air excesses: 6%, 4.5% and 3%.
Les essais suivants ont été réalisés :  The following tests were carried out:
Mesures de référence sur un fioul lourd TBTS  Reference measurements on a SIDS heavy fuel oil
Mesures sur le mélange Fioul / Tall oil HLC 70/30 (% volume)  Mixture measurements Oil / Tall oil HLC 70/30 (% volume)
Mesures sur le mélange Fioul / Tall oil HLC 70/30 additivé (additif de combustion)  Mixture measurements Oil / Tall oil HLC 70/30 additive (combustion additive)
Mesures de référence sur le fioul lourd TBTS  Reference measurements on SVEV heavy fuel oil
L'additif ou activateur de combustion est l'Octapower CA2200 fourni par Innospec. C'est un additif trimétallique, Fe/Ca/Ce, dont le taux d'additivation recommandé est de 1/4000.  The additive or combustion enhancer is the Octapower CA2200 supplied by Innospec. It is a trimetallic additive, Fe / Ca / Ce, whose recommended additive rate is 1/4000.
Observations lors des tests  Observations during tests
Pendant toute la durée des essais, la température de la cuve de mélange a été maintenue à 52/53°C. Les essais avec le fioul de référence ont été réalisés dans les conditions normales, soit une température de préchauffage du fioul de 140°C et une pression d'injection de 27,5bars.  Throughout the testing, the temperature of the mixing tank was maintained at 52/53 ° C. The tests with the reference fuel were carried out under normal conditions, ie a fuel preheating temperature of 140 ° C and an injection pressure of 27.5 bar.
Lors des essais avec le mélange fioul/tall oil HLC (non additivé), la température de préchauffage était de 120°C et la pression d'injection de 28bars. A 135°C, on a observé un blocage du filtre HP puis uniquement un point dur sur le filtre en passant à 130°C. Puis la combustion devient instable quand la température diminue pour devenir pulsatoire vers 96°C. In tests with the oil / tall oil HLC mixture (not additive), the preheating temperature was 120 ° C. and the injection pressure of 28bars. At 135 ° C, there was a blockage of the HP filter and then only a hard point on the filter passing at 130 ° C. Then the combustion becomes unstable when the temperature decreases to become pulsatory towards 96 ° C.
Enfin, pour les essais avec le mélange fioul/tall oil HLC additivé la température de préchauffage était de 130°C et la pression d'injection de 26bars. Un problème d'instabilité de la flamme a été observé lors des essais à 4,5% d'O2 avec tendance au décrochement. Finally, for the tests with the additive oil / tall oil HLC mixture, the preheating temperature was 130 ° C. and the injection pressure 26 bars. A problem of instability of the flame was observed during the tests with 4.5% of O2 with tendency to recess.
La combustion du tall oil HLC conduit à la formation de dépôts carbonés en quantité relativement importante. Il semblerait que ces essais aient conduits à un encrassement des tubes mis en évidence par l'élévation de la température des fumées (figure 7) d'une dizaine de degrés entre les deux points de référence (essais au fioul lourd avant et après les essais de mélanges).  The combustion of tall oil HLC leads to the formation of relatively large amounts of carbonaceous deposits. It seems that these tests led to a fouling of the tubes evidenced by the rise in the flue gas temperature (Figure 7) of about ten degrees between the two reference points (heavy fuel oil tests before and after the tests mixtures).
Les mélanges comprenant un activateur de combustion ont permis d'obtenir une diminution significative des dépôts carbonés, qui s'observent principalement sur les filtres connectés sur les cheminées d'évacuation des gaz de combustion.  The mixtures comprising a combustion promoter have made it possible to obtain a significant decrease in the carbon deposits, which are observed mainly on the filters connected to the exhaust stacks of the combustion gases.
L'étude d'évaluation de la stabilité du tall oil HLC en mélange a démontré la stabilité du mélange. Par contre l'indice d'acide très élevé du tall oil HLC peut entraîner des problèmes de corrosion acide. Une attention particulière doit être prêtée au stockage et aux tuyauteries. D'autre part la température de mise en oeuvre doit être maîtrisée afin d'éviter certains dysfonctionnements observés, à savoir le blocage des filtres, des phénomènes de combustion pulsatoire...  The stability evaluation study of tall oil HLC as a mixture demonstrated the stability of the mixture. On the other hand, the very high acid number of tall oil HLC can lead to acid corrosion problems. Special attention should be paid to storage and piping. On the other hand the temperature of implementation must be controlled in order to avoid certain observed malfunctions, namely the blocking of filters, pulsating combustion phenomena ...
Les émissions de polluants sont conformes à aux attentes souhaitées. Pollutant emissions are in line with the desired expectations.
On note une forte augmentation des émissions de poussières en raison de la teneur en cendres du tall oil HLC très supérieure à celle d'un fioul lourd. L'utilisation de tall oil HLC comme combustible nécessite de préférence l'installation d'un système de post-traitement des fumées adéquat (filtres à manches ou électro-filtres) afin de limiter les rejets atmosphériques. Les émissions de SOx et de NOx sont liées à la teneur en soufre et azote du combustible. On note également, lors de la combustion du mélange fioul/tall oil, la présence en quantité notable de sulfates sur les filtres. There is a large increase in dust emissions because of the ash content of tall oil HLC much higher than that of a heavy fuel oil. The use of tall oil HLC as a fuel preferably requires the installation of a suitable after-treatment system for fumes (bag filters or electro-filters) in order to limit atmospheric emissions. SO x and NO x emissions are related to the sulfur and nitrogen content of the fuel. It is also noted, during the combustion of the oil / tall oil mixture, the presence in a significant amount of sulfates on the filters.
Les analyses de différents tall oil ont montré une variabilité relativement modérée des principales caractéristiques physico-chimiques.  Analyzes of different tall oils showed relatively moderate variability in the main physicochemical characteristics.

Claims

REVENDICATIONS
1 . Utilisation d'un combustible liquide issu de la biomasse comme additif pour la stabilisation d'une composition combustible comprenant un fioul lourd, le fioul lourd étant défini selon le standard ASTM D396-98. 1. Use of a liquid fuel derived from biomass as an additive for the stabilization of a fuel composition comprising a heavy fuel oil, the heavy fuel oil being defined according to the ASTM D396-98 standard.
2. Utilisation selon la revendication 1 , dans laquelle le combustible liquide issu de la biomasse est choisi dans le groupe constitué par une huile de neutralisation et le tallol. Use according to claim 1, wherein the liquid fuel from the biomass is selected from the group consisting of a neutralizing oil and tall oil.
3. Utilisation selon la revendication 2, dans laquelle l'huile de neutralisation est une composition d'acides gras neutralisés par une base puis acidifiés. Use according to claim 2, wherein the neutralizing oil is a base-neutralized fatty acid composition and then acidified.
4. Utilisation selon la revendication 2 ou 3, dans laquelle l'huile de neutralisation est présente dans la composition combustible totale en une proportion variant de 1 à 80% en poids, de préférence de 10 à 50% en poids, plus préférentiellement de 20 à 40% en poids par rapport au poids total de la composition combustible totale. 4. Use according to claim 2 or 3, wherein the neutralizing oil is present in the total fuel composition in a proportion ranging from 1 to 80% by weight, preferably from 10 to 50% by weight, more preferably from 10 to 50% by weight. 40% by weight relative to the total weight of the total fuel composition.
5. Utilisation selon la revendication 2, dans laquelle le tall oil est présent dans la composition combustible totale dans une proportion variant de 1 à 80% en poids, de préférence de 5 à 50% en poids, plus préférentiellement de 10 à 30% en poids par rapport au poids total de la composition combustible totale. 5. Use according to claim 2, wherein the tall oil is present in the total fuel composition in a proportion ranging from 1 to 80% by weight, preferably from 5 to 50% by weight, more preferably from 10 to 30% by weight. weight relative to the total weight of the total fuel composition.
6. Utilisation selon l'une des revendications 1 à 5, dans laquelle la composition combustible totale comprend en outre un activateur de combustion choisi dans le groupe constitué par un catalyseur de combustion, un additif de combustion comprenant des tensio-actifs et un mélange de dérivés d'oxydes de Fe, Ca et/ou Ce dans un solvant hydrocarboné. The use according to one of claims 1 to 5, wherein the total fuel composition further comprises a combustion promoter selected from the group consisting of a combustion catalyst, a combustion additive comprising surfactants and a mixture of derivatives of Fe, Ca and / or Ce oxides in a hydrocarbon solvent.
7. Utilisation d'une composition combustible totale comprenant un combustible liquide issu de la biomasse et une composition combustible comprenant un fioul lourd, le fioul lourd étant défini selon le standard ASTM D396-98, telles définies selon l'une des revendications 1 à 6, pour l'alimentation d'un four ou d'une chaudière. 7. Use of a total fuel composition comprising a liquid fuel derived from biomass and a fuel composition comprising a heavy fuel oil, the heavy fuel oil being defined according to ASTM standard D396-98, as defined according to one of claims 1 to 6. , for feeding an oven or boiler.
EP12824698.0A 2011-12-28 2012-12-26 Fuel composition comprising a heavy fuel oil and a biomass product Withdrawn EP2798046A1 (en)

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FR3040709B1 (en) * 2015-09-03 2019-06-28 Total Marketing Services LUBRICATION ADDITIVE FOR FUEL WITH LOW SULFUR CONTENT.
FR3053048B1 (en) * 2016-06-28 2019-08-23 Total Marketing Services COMBUSTIBLE COMPOSITION FROM BIOMASS AND PROCESS FOR PREPARING THE SAME
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