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    • 专利摘要:
    The present invention relates to a fuel composition derived from biomass, in particular liquid biomass, and a process for preparing this fuel composition. The fuel composition comprises: an acidic oil resulting from the acidification of a neutralization paste obtained by a refining process, in particular a saponification process, of one or more oils chosen from a vegetable oil and an animal oil, and a composition based on tall oil pitch. This combustible composition is particularly suitable for being burned in industrial combustion plants.
    公开号:FR3053048A1
    申请号:FR1656029
    申请日:2016-06-28
    公开日:2017-12-29
    发明作者:Patrick Havil；Laurent Julien
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    COMBUSTIBLE COMPOSITION FROM BIOMASS AND PROCESS FOR PREPARING THE SAME
    TECHNICAL AREA
    The present invention relates to a fuel composition derived from biomass, in particular liquid biomass, and a process for preparing this fuel composition.
    Combustible combustion includes an acidic oil and tall oil.
    The fuel composition of the present invention is more particularly adapted for use in combustion plants consuming exclusively, alone or as a mixture, natural gas, liquefied petroleum gases, domestic fuel oil, coal, heavy fuel oil, biomass. It is not a fuel.
    In particular, the fuel composition of the present invention can be used in combustion plants classified in item 2910 A (and a fortiori 2910 B and 2910 C) of the nomenclature of classified installations for the protection of the environment (ICPE nomenclature). defined in Decree No. 2013-814 of 11 September 2013, published in the Official Journal of the French Republic of 13 September 2013.
    PRIOR ART The petroleum refining industry, at least in Europe. the west, tends to decrease the production of heavy fuel oil, due to the decline in demand. This decline is related to the switch to alternative sources of energy by customers, including natural gas, as well as environmental constraints that tend to limit the amount of NOx, SO2 and dust emitted into the atmosphere. In order to comply with the most stringent regulatory requirements, high-power combustion plants should use oil that is free from nitrogen, sulfur and ash or smoke treatment techniques, which is not economically viable. compared to other energies, such as natural gas for example.
    In addition, the heavy fuel oil generally needs to be stored at a temperature of 50 ° C to make it pumpable and to be sprayed at a temperature between 85 and 130 ° C according to burner technology, in connection with the viscosity of the product. These heating steps represent a significant energy consumption.
    In addition, the flash point of heavy fuel oil (typically between 70 and 120 ° C) close to its implementation temperature, may cause additional constraints in terms of safety (explosive atmospheres).
    There is therefore a need for a fuel substitute for heavy fuel which is less restrictive when it is implemented and which makes it possible to meet the higher and higher requirements relating to atmospheric emissions resulting from its combustion.
    There are fuel compositions based on heavy fuel oil and products made from biomass, such as, for example, the fuel compositions prepared by the applicant and described in documents WO2013 / 098524 and WO2014 / 102492. The fuel compositions described in WO2013 / 098524 are a mixture of heavy fuel oil and of tall oil or of a neutralization oil (composition of acid acids neutralized with a base and then acidified), tall oil and oil. of neutralization for stabilizing the fuel composition. The compositions described in WO2014 / 102492 are mixtures of a neutralization paste and a heavy fuel of petroleum origin. These different fuel compositions are however not entirely derived from biomass.
    There is a need for a fuel substitute for heavy fuel oil which is less restrictive during its implementation, which makes it possible to meet the higher and higher requirements relating to atmospheric emissions resulting from its combustion and which is entirely derived from the biomass.
    BRIEF SUMMARY OF THE INVENTION
    The Applicant proposes a composition, in particular liquid, used as fuel. This composition can be substituted for a fuel oil, in particular for being burned in an industrial boiler or an industrial furnace in place of a fuel oil. The Applicant proposes, in particular, a combustible composition, in particular liquid, directly from biomass and can replace a fuel oil, in particular to be burned in an industrial boiler or an industrial furnace instead of a fuel oil. "Direct from biomass" means that it does not contain fossil fuel. This does not exclude the fact that this composition may contain other products, for example additives, not derived from biomass.
    A first subject of the invention thus relates to a fuel composition, in particular a liquid composition, comprising a composition based on tall oil pitch and an acidic oil, in particular resulting from the acidification of a neutralization paste obtained by a process. refining process, preferably a chemical refining process, in particular a saponification process, of one or more oils chosen from a vegetable oil and / or an animal oil.
    Such a composition has the advantage of being derived solely from biomass: it does not include fossil fuel components. It also has the advantage of emitting during its combustion low emissions, meeting high environmental constraints.
    The fuel composition according to the invention may comprise: at least 30% by weight of acidic oil, preferably at least 50% by weight, or even at least 60% by mass, at most 70% by weight of the composition based on oil pitch tall, preferably at most 50% by weight, or even at most 40% by mass, preferably at most 30% by mass.
    Advantageously, the fuel composition may comprise: from 30 to 90% by weight of acidic oil, advantageously from 50 to 85% by weight, preferably from 60 to 80% by weight, and from 10 to 70% by weight of the pitch composition. tall oil, advantageously from 15 to 50% by weight, preferably from 20 to 40% by weight, more preferably from 20 to 30% by weight.
    The fuel composition according to the invention may further comprise one or more additives, preferably chosen from: a combustion additive having the effect of reducing dust emissions; these are generally additives containing metal salts (iron and / or calcium and / or cerium) solubilized in a matrix of fatty acids and hydrocarbons, an additive having the effect of improving the stability; these additives generally contain dispersing agents solubilized in a matrix of fatty acids and hydrocarbons.
    The total additive content of the fuel composition may be from 0.05 to 0.5% by weight, preferably from 0.1 to 0.3% by weight. The acidic oil present in the fuel composition may advantageously have a water content of less than or equal to 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight. This may make it possible to improve the combustion efficiency of the composition.
    Alternatively or in combination, the acidic oil present in the fuel composition may advantageously have an ash content of less than or equal to. 0.1% by weight, ideally less than 0.05% by weight, sulfur less than or equal to 150 mg / kg, preferably less than 100 mg / kg, calcium less than or equal to 5 mg / kg, preferably less than 1 mg / kg, • phosphorus less than or equal to 150 mg / kg, • sodium less than or equal to 10 mg / kg, preferably less than 1 mg / kg.
    According to advantageous forms, the ash content may be less than or equal to 0.04% by weight.
    Advantageously, the acidic oil may further comprise an alkali metal content other than sodium less than or equal to 1 mg / kg.
    The tall oil pitch composition used in the present composition may comprise from 50 to 90% by weight of tall oil pitch, preferably from 60 to 80% by weight, and the balance of 100% by weight. or several solvents, optionally selected from a light pine oil, turpentine, and generally products derived from the distillation of crude tall oil. Light pine oil can be defined as a light fraction recovered at the top of the column during the distillation of crude tall oil. Its flash point is between 40 and 70 ° C (limits included).
    The pitch of tall oil is the product recovered at the bottom of the column during the fractionation of the crude tall oil by distillation.
    The fuel composition according to the invention may comprise at least one of the following characteristics: a flash point greater than or equal to 100 ° C., preferably greater than or equal to 110 ° C., an acid number of less than or equal to 70 mg KOH / g, preferably less than or equal to 60mgKOH / g, preferably less than or equal to 50mgKOH / g, an ash content less than or equal to 0.1% by weight, preferably less than or equal to 0.05% by weight, a lower sulfur content or equal to 0.5% by weight, preferably less than or equal to 0.1% by weight, a nitrogen content of less than or equal to 0.1% by weight, preferably less than or equal to 0.05% by weight, a content of water less than or equal to 0.5% by weight, preferably less than or equal to 0.2% by weight.
    According to a particular embodiment, the fuel composition consists solely of the acidic oil and the composition based on tall oil pitch as described above and optionally of one or more additives as described above.
    The combustible composition of the present invention is obtainable by the method of preparation described hereinafter.
    Another subject of the invention is a process for preparing a fuel composition, in particular a liquid composition, derived from biomass comprising: a) a step of supplying an acidic oil resulting from the acidification of a neutralization paste obtained by a refining process, preferably a chemical refining process, in particular a saponification process, of one or more oils selected from a vegetable oil and / or an animal oil, b) a step of providing a composition based on tall oil pitch, c) a step of mixing the acidic oil obtained in step a) with the composition obtained in step b), d) at least one treatment step comprising a or a number of steps chosen from filtration, centrifugation and decantation, in which a substance chosen from the acidic oil obtained in step a) is treated before the mixing step c), the composition based on pitch of tal oil l obtained in step b) before step c) of mixing and the mixture obtained in step c). The treatment can be done either on a component of the mixture, or both, but also on the mixture. The treatment step may in particular allow to reduce the water content and / or ash, sulfur, and other elements such as alkali metals, phosphorus, sodium of the treated substance.
    Another subject of the invention relates to a method of combustion of a fuel composition in a combustion plant, in particular of type 2910A or 2910B or 2910C according to the ICPE nomenclature, in which the combustible composition is burned as fuel. invention or directly obtained by the process according to the invention. The composition according to the invention can burn in compliance with regulatory constraints on the issue without requiring recourse to expensive smoke treatments. DETAILED DESCRIPTION OF THE INVENTION Step a) supplying an acidic oil The acidic oil supplied in step a) is obtained by refining one or more oils chosen from a vegetable oil and / or an oil animal.
    It is in particular an oil resulting from the acidification of a neutralization paste, this neutralization paste being derived from the refining, in particular the chemical refining, of one or more oils chosen from a vegetable oil and or an animal oil. More particularly, the neutralization paste is preferably derived, especially directly from a saponification process of one or more oils.
    An acidic oil can be defined as base-fed fatty acid compositions and then acidified.
    The fatty acids advantageously come from the saponification of a vegetable and / or animal oil, such that, without being limiting, a sunflower oil, soya, rapeseed, palm, coconut, peanut, olive, a fish oil, and typically comprising in the great majority saturated or unsaturated C 6 -C 18 carbon chains, of which, for example, unsaturated carbon chains of C 1 -C 6. Vegetable oils usually include palmitic, oleic, linoleic acid and other acids in smaller amounts. The base neutralized fatty acid compositions are typically neutralization pastes.
    Typically, an acidic oil contains from 20 to 70% by weight of fatty acids. Step a) may include the provision of an acidic oil having a water content of less than or equal to 3% by weight. The step a) of supplying an acidic oil may advantageously comprise: a) a step of extracting the fatty acids present in a neutralization paste resulting from the refining, preferably chemical refining, in particular the saponification, of a or a plurality of oils chosen from a vegetable oil and / or an animal oil, this extraction step being carried out under acidic conditions under conditions that are effective for forming an aqueous phase and an organic phase comprising said fatty acids, a2) a step separating said organic phase previously formed and recovered.
    The organic phase recovered in step a2) constitutes an acidic oil. This acidic oil generally has a water content of less than or equal to 3% by weight. Neutralization paste used in step a1)
    The neutralization paste treated in step a1) may be a mixture of neutralization pastes obtained from the refining of different oils or may be a neutralization paste resulting from the refining of a single oil. Preferably, the refining of the neutralization paste (s) is a chemical refining.
    Such neutralization pastes come, in particular directly from the saponification of a vegetable oil and / or an animal oil. In general, this saponification is carried out by adding a base, usually sodium hydroxide, and eliminates the free fatty acids present in the oil, which are found in the soapstock. form of alkaline salts of fatty acids. Before this saponification, the vegetable and / or animal oil may undergo a degumming or degumming operation to eliminate phospholipids, lecithins, sugar complexes and other impurities. The separation of the oil and the neutralization paste resulting from the saponification can be carried out by centrifugation.
    The neutralization pastes thus essentially comprise base neutralized fatty acids. They typically comprise from 20 to 70% by weight of fatty acids.
    In addition to the base-neutralized fatty acids, the neutralization pastes may contain, depending on their origin and the quality of the saponification, unreacted phospholipids or mono-, di- or tri-glycerides. Usually, the fatty acids have carbon chains C12-C24, preferably C16-C20 or better C16-C18.
    A neutralization paste is therefore a product derived from biomass. Advantages associated with such neutralization pastes lie, on the one hand, in their low cost of implementation, and, on the other hand, in the absence of undesirable toxic substances, such as pesticides, aflatoxins, heavy metals, precursors of dioxins and furans, PCBs and nitrites.
    However, the neutralization pastes may contain significant proportions of water from the saponification reaction or addition of water for the fluidification in the industrial process. The aqueous phase may represent more than 50% of the mass of the neutralization paste. Another difficulty is related to the fact that it is emulsion cases, which should be treated specifically. The use as a fuel therefore requires the implementation of methods of removing this water and other unwanted solids or viscous liquid residues.
    Extraction step (a) Extraction step a1) of the process according to the invention has the function of extracting the fatty acids contained in the neutralization paste. This extraction is carried out in an acidic medium under conditions that are effective for forming an aqueous phase and an organic phase comprising the fatty acids initially contained in the neutralization paste.
    This organic phase comprising the fatty acids is generally called "acid oil" or "neutralizing oil". The acid used to extract the fatty acids present in the neutralization paste in the form of salts is generally an inorganic acid, such as, for example, sulfuric acid, phosphoric acid or hydrochloric acid. Sulfuric acid is however preferred because it allows better extraction of fatty acids at a favorable economic cost. The extraction is generally carried out under heating, at a temperature between 70 and 100 ° C (inclusive), preferably between 80 and 90 ° C (inclusive).
    In order to obtain a good extraction of the fatty acids, an acidic pH is preferably maintained during the reaction time, for example a pH of less than or equal to 6, preferably less than or equal to 4.
    The reaction time is chosen to allow extraction of all the fatty acids. It is for example from 1 hour to 24 hours, depending on the geometry of the reactor, the nature and the composition of the charge to be treated. The extraction is preferably carried out with stirring.
    The formation of an aqueous phase and an organic phase containing the fatty acids are thus obtained.
    Step a2) of separation
    During this step, the organic phase formed during step a1) of the aqueous phase is separated off. In other words, the acidic oil which will subsequently be subjected to step c) of the process according to the invention is isolated, optionally after a centrifugation step when its water content is greater than 1% but less than or equal to 3%.
    This separation can be carried out by distillation, decantation or even centrifugation. This step can be implemented by any suitable device known and commercially available.
    Advantageously, this separation is carried out by decantation, followed by removal of the aqueous phase. Decantation depends on the difference in density of the liquids and their viscosity, parameters which can be modified in a manner known to those skilled in the art to promote separation if necessary.
    Advantageously, it is possible to carry out a filtration at 150 μιη of the acidic oil before any subsequent step.
    Step b) of supplying a composition based on tall oil pitch Tall oil, or otherwise known as tall oil or tall oil, is a liquid by-product of the Kraft process of wood processing which allows to isolate on one side the wood pulp useful for the paper industry, and on the other the black liquor containing the crude tall oil. Tall oil is mainly obtained when using conifers in the Kraft process. Products derived from the distillation of crude tall oil are generally used as bases in the chemical industry and for the manufacture of glues and adhesives.
    In the Kraft process, wood chips are usually heated in the presence of aqueous sodium sulfide. This treatment is generally at a temperature of 130 to 180 ° C, under pressure for 2 to 5 hours depending on the species of wood. A black liquor is obtained, and, after decantation, the formation of an alkaline upper layer called soap ("tall oil soap"), which can be isolated. This tall oil soap is then acidified, for example with sulfuric acid, to produce crude tall oil. Crude tall oil consists mainly of resin acids, fatty acids and non-saponifiable compounds.
    Insufficient acidification can lead to a crude tall oil containing metal salts, usually sodium. This characteristic is related to the fact that tall oil mainly comprises hydrocarbon compounds functionalized with organic acids, essentially carboxylic acids, sometimes phenols. Tall oil also includes non-saponifiable sterols, fatty alcohols, and other alkylated hydrocarbon derivatives.
    A medium tall oil has an acid number (TAN: total acid number, in mg of KOH per g of product) of between 100 and 200, more generally between 125 and 165.
    When heated, crude tall oil can be separated (by distillation) into a light phase, essentially comprising fatty acids and resins and a heavy phase or residue, which can not be distilled, called oil pitch Tall oil tall oil pitch. Tall oil pitch contains a small amount of fatty acids and resin acids and a significant amount of unsaponifiables. Step b) may thus comprise: bl) a step of supplying tall oil pitch, in particular by fractionation of at least one crude tall oil obtained by conversion of coniferous wood according to the Kraft process, b2) a step of mixing the tall oil pitch obtained in step b1) with at least one solvent, for example selected from light pine oil and turpentine. This mixture makes the pitch of tall oil more easily handled and transportable.
    The mixture recovered in step b2) constitutes a composition based on tall oil pitch.
    In particular, the tall oil pitch corresponds to the undistilled fraction of the crude tall oil.
    Advantageously, the composition based on tall oil pitch provided in step b) comprises: from 50 to 90% by weight of pitch of tall oil, preferably from 60 to 80% by weight, and the complement 100% of one or more solvents, optionally selected from a light pine oil and turpentine.
    Mix step
    During this step, the acid oil obtained in step a) and the tall oil pitch composition obtained in step b) are mixed.
    Advantageously, in order to improve the homogeneity of the mixture obtained, this step is carried out with stirring, for example mechanical and / or by recirculation.
    In particular, the mixing can be carried out in a stirred reactor by simultaneous injection of the acid oil obtained in step a), optionally after at least one treatment step d), and the composition based on oil pitch tall obtained in step b), optionally after at least one treatment step d).
    In order to facilitate the mixing and to improve its homogeneity, the components of the mixture may be heated prior to mixing. This heating may be carried out after one or more optional treatment steps d) of one or more of the components of the mixture. The acidic oil can thus be heated to a temperature of 40 to 70 ° C and the tall oil pitch composition can be heated to a temperature of 40 to 70 ° C, preferably 50 to 60 ° C. .
    During this step c) of mixing, the acidic oil obtained in step a) is mixed, optionally after at least one treatment step d), and the composition based on tall oil pitch obtained at least once. step b), optionally after at least one treatment step d), in the following proportions: at least 30% by weight of acid oil, at most 70% by weight of the composition based on tall oil pitch.
    Step d) treatment
    This step may comprise one or more steps selected from filtration, centrifugation and decantation.
    The process according to the invention may comprise at least one treatment step d) of each component of the mixture (before the mixing step) and of the mixture obtained in step c).
    Alternatively, the method according to the invention may comprise one or more of the following steps: a step of treatment d) of the acidic oil obtained in step a) before step c) of mixing, a step of treatment d) of the composition based on tall oil pitch obtained in step b) before step c) of mixing, - a step of treatment d) of the mixture obtained in step c).
    The method according to the invention can thus comprise at least one treatment step d) which comprises: dl) a treatment step in which the acidic oil obtained in step a) is treated before the mixing step c) in effective conditions for obtaining an acidic oil having a water content of less than or equal to 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight.
    This step d1) may comprise at least one centrifugation step. The centrifugation may advantageously be carried out on an acidic oil obtained in step a2) previously described.
    This centrifugation operation makes it possible to obtain an acidic oil having very advantageously a water content of less than or equal to 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight. % in weight.
    In addition to removing water, recovered in an aqueous phase, centrifugation also allows the removal of a portion of the solid residues in suspension. 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 centrifugation step may advantageously be a triphasic centrifugation.
    However, 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 solids in the form of sludge, coupled with a second centrifugation step. triphasic, which separates the organic phase, the purified aqueous phase and the residual suspended solids from the first centrifugation. This step can be implemented by any appropriate device known and commercially available.
    Conventionally, centrifugation can be implemented 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 organic phase and the particles, the particle size, the surface tension of the particles. species to be separated, temperature, centrifugation rate. The separation time (called residence time) is therefore adapted case by case by those skilled in the art by conventional means of measurement and control. The treatment step d) may further comprise a step d2) of reducing the content of ash, sulfur, phosphorus, calcium, sodium and optionally of alkali metals other than sodium. This step d2) is advantageously carried out on the acidic oil obtained in step d1), but could possibly be carried out on an acid oil which has not undergone step d1).
    During this step d2), the ash, sulfur, calcium, phosphorus, sodium, and possibly alkali metal other than sodium content of the acidic oil is reduced by means of one or more filtration sub-steps. and / or precipitation.
    This step d2) can be implemented by any appropriate device known and commercially available.
    Filtration can thus be carried out by means of a filter press, or a filter cartridge, or a filter membrane or be an ultra filtration, nano filtration or reverse osmosis filtration. Step d2) may advantageously comprise at least one filtration step carried out using at least one passage through a cellulose filter. Such a cellulose filter can improve the efficiency of filtration by avoiding clogging. The precipitation step can advantageously be carried out under conditions that are effective for precipitating the sulphates present in the acidic oil. These sulphates may come from the saponification of the oil and / or the acid extraction of the fatty acids.
    Without wishing to be bound by theory, the precipitation of sulphates from an acidic oil seems to be associated with the precipitation of calcium, phosphorus, sodium, and possibly alkali metals other than sodium, which has the effect of reducing ash content of the product.
    In general, the conditions for carrying out the precipitation will be determined by those skilled in the art by conventional means depending on the species to be precipitated.
    The precipitation of the sulphates may in particular be carried out by addition of Ca 2+ ions, for example in the form of CaCl 2 (calcium chloride).
    The choice and the number of these substeps can be easily determined by those skilled in the art by controlling the content of ash, sulfur, calcium, phosphorus and sodium of the final organic phase, constituting the acidic oil.
    In one embodiment, step d2) may comprise at least two successive filtration steps with increasingly weak mesh filters. By way of example, the filtrations can be carried out by means of a first filter of 100 to 50 μιη and a second filter of 10 to 25 μπι. These filtrations are preferably carried out hot: from 40 to 60 ° C. for the acid oils, from 50 to 80 ° C. for the composition based on tall oil pitch, from 50 to 80 ° C. for the mixed.
    In another embodiment, step d2) may comprise a filtration step followed by a precipitation step, in particular sulphates.
    Optionally, these filtration and precipitation steps may be preceded or followed by one or more other filtration steps, or even one or more precipitation steps. Advantageously, the last step may be a filtration step.
    The method may comprise a succession of filtrations by means of decreasing mesh filters to reach the final target, for example from 200 μπι up to 25 μπι. Advantageously, the last filtration step is then performed by means of a filter having a filtration threshold of 10 to 25 μπι.
    With this step d2), it is possible to obtain an acidic oil having very advantageously levels of: • ash less than or equal to 0.1% by weight, ideally less than 0.05% by weight, • sulfur less than or equal to 150 mg / kg, preferably less than 100 mg / kg, • calcium less than or equal to 5 mg / kg, preferably less than 1 mg / kg, • phosphorus less than or equal to 150 mg / kg, • sodium less than or equal to at 10 mg / kg, preferably less than 1 mg / kg, and optionally an alkali metal content other than sodium less than or equal to 1 mg / kg.
    The calcium content can be measured according to standard NF T 60106.
    The phosphorus content can be measured according to standard NF T 60106.
    The sodium content may be measured according to standard NF T 60106.
    The alkali metal content other than sodium may be measured according to standard NF T 60106.
    It will be noted that the steps d1) and d2) can make it possible to obtain acid oils whose contents in ash, sulfur, calcium, phosphorus, sodium and possibly in alkali metals other than sodium are well below the aforementioned thresholds, or even thousands or almost nil and undetectable by the usual means of quantification.
    In addition, the acidic oil then obtained in step d2) advantageously has a water content less than or equal to 1%, or even less than or equal to 0.8%, in particular from 0.1% to 0.7% in weight.
    The method according to the invention may also comprise, as a variant or in combination, at least one treatment step d) chosen from: a step of 1) treating the composition obtained in step b) before the step c) mixing and - a step d3) of treatment of the mixture obtained in step c).
    These steps of 1) and d3) may comprise one or more steps selected from filtration, centrifugation and decantation. These steps may be similar to steps d1) and d2) previously described. In particular, each of the steps of 1) and d3) can comprise, or consist of one or more filtrations, decantations, precipitations, in particular under conditions similar to those described for the acidic oil, possibly at different temperatures, such as those mentioned above for filtration. EXAMPLES Example 1
    Table 1 summarizes some physicochemical characteristics of a sample of tall oil pitch.
    Table 2 shows the same physicochemical characteristics for the following products: - Product A: composition based on tall oil pitch, the characteristics of which are shown in Table 1, - Product B: acid oil, - Product C: fuel oil STEL (very low sulfur content), not additive, - product D: combustible composition according to the invention consisting of 26% by weight of product A and 74% by weight of product B.
    Table 1
    (*) Measurement carried out according to the method of the Union Française des Industries Pétrolière (UFIP) and the Association Technique Energie Environnement (ATEE).
    Product A comprises 60% by weight of tall oil and 40% by weight of solvent, namely: 10% by weight of pine oil and 30% by weight of turpentine. Product A is stored at a temperature of 40 to 70 ° C. The acidic oil used here is an acidic oil resulting from the acidification of a neutralization paste obtained by saponification of a rapeseed oil. The neutralization paste was subjected to the following treatment: (a) injection of 120% of 97% sulfuric acid into a reactor containing 4000 kg of neutralization paste, where the temperature is 80 to 90 ° C. The reaction time is 24 hours, under continuous control of the pH to maintain the pH at a value below 4, a2) decantation of the aqueous phase and the organic phase formed during step a1) and elimination of the aqueous phase.
    An acidic oil is obtained which is subjected to successive hot filtrations (50 ° C.) by means of decreasing mesh filters (200, 100, 50 and 25 μm). Product B is obtained, which is stored at a temperature of 5 to 40 ° C.
    Product D is a mixture of products A and B. It is carried out as follows: 24 hours before mixing, product B is heated to between 50 and 60 ° C. and stirred (mechanical stirring and recirculation at a rate greater than Stored product / 5) m3 / h). The mixture is produced by simultaneous injection of 74% by weight of product B (acidic oil) and 26% by weight of product A (based on tall oil pitch). The product D is obtained. After the operation, the product D is stirred (mechanical stirring and recirculation at a flow rate greater than (stored product / 5) m 3 / h) for 24 hours. The product D is then stored at a temperature facilitating its transfer as a function of the viscosity, preferably greater than 20 ° C.
    Table 2
    (*): specifications imposed by the CSR 500 for a heavy fuel oil. These specifications are established by the Chambre Syndicale du Raffinage in France.
    The standards used for the measurements of the different products are specified in Table 1 only.
    Example 2: Pilot Test of Combustion
    Each fuel is burned separately in a 1 MW flue gas boiler, 1 unattended mechanical spray burner. The atmospheric emissions are continuously analyzed by means of analyzers placed in the flue gas outlet, at the outlet of the fireplace.
    Table 3
    m3 (n): normal cubic meters, measured at P = 101.3kPa and T = 273K
    The following products were tested: - Product A: composition based on pitch of tall oil, - Product B: acid oil, - Product C: Sulfur oil without additives, - Product D: Composition according to the invention consisting of 26 % by weight of the composition based on tall oil pitch and 74% by weight of the acidic oil,
    The characteristics of these products are those presented in Table 2.
    Table 3 above summarizes the combustion conditions of this test as well as the combustion efficiency and the measured emissions. The combustion of the composition according to the invention (D) has a yield similar to that of heavy fuel oil (A) and slightly higher than each constituent of the composition taken separately (A and B).
    The atmospheric emissions of the composition according to the invention (D) are in the same orders of magnitude as for the acidic oil alone (B) and make it possible to comply with the newly introduced ELVs (Emission Limit Values), which this is not the case for the tall oil pitch composition (A) and the heavy oil SIDS (C). It is noted that the NOx and dust emissions of the composition according to the invention are lower than the emissions of the other products, a consequent decrease being observed for NOx.
    Example 3: Stability test Generally, the use of a fuel in combustion plants involves prior storage tank. The storage period can vary from several days to several months. Stability tests were performed to verify the homogeneity of a composition according to the invention over time.
    The combustible composition (product D) of Examples 1 and 2 was stored at 20 ° C under daylight for 5 months. Table 4 summarizes the observed results.
    It is found that the fuel composition according to the invention has constant physical properties over time. The fuel composition remains homogeneous, even after several months.
    Table 4
    The fuel composition according to the invention thus has the following advantages:
    Environmental: the fuel composition according to the invention contains little nitrogen, sulfur and ash with respect to a heavy fuel oil, which makes it possible to greatly reduce the emissions of NOx, SO2 and dust to the atmosphere and thus to respect the VLE (Limit Values άΈππββίοη), whether for small, medium or large combustion plants, without recourse to a post-flue gas treatment. It should be noted that a composition based on Tall oil pitch can not be used either without implementation of a post-flue gas treatment in compliance with the emission VLEs (mainly for SO2 and dust). ).
    Implementation: the fuel composition according to the invention requires less heating than a heavy fuel oil: 20 ° C storage, rotary cup burner 55 ° C, mechanical burner 85 ° C (respectively 55 ° C, 85 ° C and 130 ° C for a heavy fuel oil), it results in an economic gain.
    Storage: the fuel composition according to the invention has an acid number lower than that of an acid oil alone and a reduced water content. The conjunction of these two elements favors storage conditions. Due to the less water, the accumulation of water in the bottom of the storage tank will be reduced accordingly. As this water is less acidic, the potential corrosion phenomena will be attenuated / slowed down. In addition, the vapors potentially formed in the gaseous sky will be less corrosive than those of the acid oil alone. Finally, the fuel composition according to the invention has a flash point higher than that of a composition based on tall oil pitch alone. The implementation of the mixture, storage to the burner, is thus at a temperature below the flash point. As a result, no ATEX (Explosive Atmosphere) is induced by this fuel as well as an economic gain.
    Burning: the composition according to the invention has a density and a PCI higher than the acid oil alone. As a result, through a specific type of equipment (pump), it will pass a larger mass of product. Since the heating value of the mixture is greater than that of the acid oil alone, the power delivered by the combustion plant is increased. As an indication, in relation to the fuel analyzes (see Table 2), for a given combustion plant, the thermal power delivered by the mixture will be greater than that of the acid-only oil of 5%. the fuel composition according to the invention no longer has the characteristic and strong odor of the pitch of tall oil.
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    A fuel composition, in particular a liquid composition, comprising: an acidic oil resulting from the acidification of a neutralization paste obtained by a refining process, in particular a saponification process, from one or more oils chosen from a vegetable oil and a animal oil, and a composition based on tall oil pitch.
    [2" id="c-fr-0002]
    2. Combustible composition according to claim 1, comprising at least 30% by weight of acid oil, at most 70% by weight of the composition based on tall oil pitch, optionally one or more additives.
    [3" id="c-fr-0003]
    3. Combustible composition according to claim 1 or 2, wherein the acidic oil comprises a water content less than or equal to 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0%. , 7% by weight.
    [4" id="c-fr-0004]
    4. A fuel composition according to any one of claims 1 to 3, wherein the acidic oil comprises an ash content less than or equal to 0.1% by weight, sulfur less than or equal to 150 mg / kg, calcium less than or equal to 5 mg / kg, • phosphorus less than or equal to 150 mg / kg, • sodium less than or equal to 10 mg / kg.
    [5" id="c-fr-0005]
    The fuel composition according to any of claims 1 to 4, wherein the tall oil pitch composition comprises from 50 to 90 wt% tall oil pitch, and the 100 wt. one or more solvents, optionally selected from a light pine oil and turpentine.
    [6" id="c-fr-0006]
    6. Combustible composition according to any one of claims 1 to 5 comprising at least one of the following characteristics: a flash point greater than or equal to 100 ° C, preferably greater than or equal to 110 ° C, a lower acid number or equal to 70mgKOH / g, preferably less than or equal to 60mgKOH / g, preferably less than or equal to 50mgKOH / g, an ash content less than or equal to 0.1% by weight, preferably less than or equal to 0.05% by weight , a sulfur content less than or equal to 0.5% by weight, preferably less than or equal to 0.1% by weight, a nitrogen content of less than or equal to 0.1% by weight, preferably less than or equal to 0.05; % weight, a water content less than or equal to 0.5% by weight, preferably less than or equal to 0.2% by weight.
    [7" id="c-fr-0007]
    7. Process for the preparation of a fuel composition derived from biomass comprising: a) a step of supplying an acidic oil resulting from the acidification of a neutralization paste obtained by a refining process, in particular a saponification process , one or more oils selected from a vegetable oil and an animal oil, b) a step of supplying a composition based on tall oil pitch, c) a step of mixing the acid oil obtained with step a) with the composition obtained in step b), d) at least one treatment step comprising one or more steps selected from filtration, centrifugation and decantation, in which a chosen substance is treated from the acid oil obtained in step a) before the mixing step c), the tall oil pitch composition obtained in step b) before the mixing step c) and the mixing obtained in step c).
    [8" id="c-fr-0008]
    8. Preparation process according to claim 7, characterized in that it comprises at least one treatment step d) which comprises: dl) a treatment step treats the acidic oil obtained in step a) before the step c) mixing under conditions effective to obtain an acidic oil having a water content less than or equal to 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight; weight. d2) Optionally, a step of reducing the ash, sulfur, phosphorus, calcium and sodium content of the acidic oil obtained in step d1), this reduction step comprising one or more sub-steps selected from one of filtration and precipitation, carried out under conditions effective to obtain a fuel acid oil comprising an ash content of less than or equal to 0.1% by weight, ideally less than 0.05% by weight, • sulfur less than or equal to 150 mg / kg, preferably less than 100 mg / kg, • calcium less than or equal to 5 mg / kg, preferably less than 1 mg / kg, • phosphorus less than or equal to 150 mg / kg, • sodium less than or equal to at 10 mg / kg, preferably below 1 mg / kg,
    [9" id="c-fr-0009]
    9. Preparation process according to any one of claims 7 or 8, characterized in that it comprises at least one treatment step d) of the composition obtained in step b) before step c) of mixing.
    [10" id="c-fr-0010]
    10. Preparation process according to any one of claims 7 to 9, characterized in that it comprises at least one treatment step d) of the mixture obtained in step c).
    [11" id="c-fr-0011]
    11. Preparation process according to any one of claims 7 to 10, characterized in that, prior to the mixing step, the acidic oil obtained in step a), optionally after at least one treatment step d ), is heated to a temperature of 40 to 70 ° C, and the tall oil pitch composition obtained in step b), optionally after at least one treatment step d), is heated to a temperature of from 40 to 70 ° C, preferably from 50 to 60 ° C.
    [12" id="c-fr-0012]
    12. Preparation process according to any one of claims 7 to 11, characterized in that, during the mixing step c), mixing is performed in a stirred reactor by simultaneous injection of the acid oil obtained. in step a), optionally after at least one treatment step d), and the tall oil pitch composition obtained in step b), optionally after at least one treatment step d).
    [13" id="c-fr-0013]
    13. Preparation process according to any one of claims 7 to 12, characterized in that during step c) of mixing, the acidic oil obtained in step a) is mixed, optionally after at least one treatment step d), and the tall oil pitch composition obtained in step b), optionally after at least one treatment step d), in the following proportions: at least 30% by weight of oil acid, at most 70% by weight of the composition based on tall oil pitch.
    [14" id="c-fr-0014]
    The preparation method according to any one of claims 7 to 13, wherein the step a) of supplying an acidic oil comprises: a) a step of extracting the fatty acids present in a neutralization paste resulting from refining one or more oils chosen from a vegetable oil and / or an animal oil, this extraction step being carried out under acidic conditions under conditions that are effective for forming an aqueous phase and an organic phase comprising said fatty acids, a2) a separation step during which said previously formed organic phase is separated and recovered, the organic phase recovered in step a2) constituting the acidic oil.
    [15" id="c-fr-0015]
    The preparation method according to any one of claims 7 to 14, wherein the step b) of providing a tall oil pitch composition comprises: a) a pitch supplying step; tall oil, b2) a step of mixing the pitch of tall oil obtained in step b1) with at least one solvent.
    [16" id="c-fr-0016]
    16. A method of burning a fuel in a combustion plant, in which a fuel composition according to any one of claims 1 to 6 is burned or a fuel directly obtained by the process according to any one of claims 7 to 15. .
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    同族专利:
    公开号 | 公开日
    EP3263675A1|2018-01-03|
    FR3053048B1|2019-08-23|
    ES2784707T3|2020-09-30|
    EP3263675B1|2020-03-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4326854A|1979-03-09|1982-04-27|Tanner John D|Synthetic firelog|
    EP0542616A1|1991-11-12|1993-05-19|Elf Antar France|Fuel for controlling frost and fog|
    US20060021276A1|2004-07-28|2006-02-02|Sonnier William E|Environmentally friendly fire logs|
    WO2008076456A1|2006-12-19|2008-06-26|Duraflame, Inc.|Artificial firelog using non-petroleum waxes|
    WO2009106696A1|2008-02-29|2009-09-03|Raisio Nutrition Ltd|Process for separating sterols and acids from tall oil pitch|
    WO2013098524A1|2011-12-28|2013-07-04|Total Raffinage Marketing|Fuel composition comprising a heavy fuel oil and a biomass product|
    FR3000498B1|2012-12-27|2015-03-13|Total Raffinage Marketing|COMBUSTIBLE COMPOSITION COMPRISING A HEAVY FUEL AND A PRODUCT FROM THE BIOMASS.|FR3075812B1|2017-12-21|2020-06-05|Total Marketing Services|FUEL COMPOSITION FROM BIOMASS, USE OF A COMPOSITION FROM BIOMASS AS A FUEL, AND PROCESS FOR PREPARING SAME.|
    FR3085685A1|2018-09-10|2020-03-13|Total Marketing Services|PROCESS FOR TREATING TALL OIL PIX, FUEL COMPOSITION FROM BIOMASS, USE OF COMPOSITION FROM BIOMASS AS FUEL, AND PREPARATION METHOD|
    FI128827B|2018-12-14|2021-01-15|Upm Kymmene Corp|Process for purifying renewable feedstock comprising fatty acids|
    法律状态:
    2017-05-22| PLFP| Fee payment|Year of fee payment: 2 |
    2017-12-29| PLSC| Search report ready|Effective date: 20171229 |
    2018-10-23| PLFP| Fee payment|Year of fee payment: 3 |
    2019-05-22| PLFP| Fee payment|Year of fee payment: 4 |
    2020-05-20| PLFP| Fee payment|Year of fee payment: 5 |
    2021-06-22| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1656029|2016-06-28|
    FR1656029A|FR3053048B1|2016-06-28|2016-06-28|COMBUSTIBLE COMPOSITION FROM BIOMASS AND PROCESS FOR PREPARING THE SAME|FR1656029A| FR3053048B1|2016-06-28|2016-06-28|COMBUSTIBLE COMPOSITION FROM BIOMASS AND PROCESS FOR PREPARING THE SAME|
    EP17177472.2A| EP3263675B1|2016-06-28|2017-06-22|Biomass fuel composition andmethod for preparing and combusting the same|
    ES17177472T| ES2784707T3|2016-06-28|2017-06-22|Fuel composition from biomass, its preparation and combustion procedure|
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