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    • 专利摘要:
    Use of an alkylamine-aldehyde resin modified with at least one alkylamine in a crude oil composition or in a product derived from a crude oil composition as a dispersant additive for aphaltenes. Process for the treatment of a crude oil composition or a by-product, which makes it possible to prevent the precipitation of asphaltenes, in particular in crude oils and products derived therefrom by refining processes and / or extraction. Bituminous compositions comprising an alkylphenol-aldehyde resin modified with at least one alkylamine.
    公开号:FR3034778A1
    申请号:FR1553102
    申请日:2015-04-10
    公开日:2016-10-14
    发明作者:Frederic Tort；Nicolas Passade-Boupat；Marianna Rondon；Carlos QUINTERO
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to the use of a modified alkyl phenol aldehyde resin in a crude oil composition or in a product derived from a crude oil composition. as a dispersant additive for the aphaltenes. It also relates to a process for treating a crude oil composition or a by-product, which makes it possible to prevent the precipitation of asphaltenes, in particular in the crude oils and products derived therefrom by refining processes and / or extraction. The invention relates in particular to the additivation of a bituminous binder by a modified alkylphenol-aldehyde resin, which makes it possible to reduce the temperatures of manufacture, of implementation, of compaction of the mixes and to reduce the temperatures of manufacture and application. asphalts. The invention relates to a process for the preparation of asphalt and asphalt at low temperature, as well as the asphalt and asphalt obtained from said process. The invention also relates to the bituminous compositions additive using a modified alkylphenol-aldehyde resin. The invention finally relates to the use of these bituminous binders, coated or asphalt for the manufacture of coatings. STATE OF THE PRIOR ART A crude oil mainly comprises two classes of products: maltenes and asphaltenes, maltenes whose main constituents are: oils (saturated hydrocarbon compounds and aromatics) and resins. Asphaltenes include very polar species that tend to associate to form agglomerates. They are the heaviest component of crude oil. Asphaltenes are composed of molecules containing polycyclic, polyaromatic fragments, short aliphatic chains, heteroatoms such as N, O, S and metals (eg Ni, V, Fe). They are insoluble in alkanes such as n-pentane or n-heptane, but they are soluble in aromatic solvents such as toluene or xylene. The interaction of asphaltenes with their environment is a complex phenomenon, difficult to control. Asphaltene precipitation can occur in production wells, pipelines and surface facilities. Asphaltenes present in crude oils or in heavy residues from refining operations can precipitate and lead to clogging of filters or clogging of pipes. This phenomenon leads to a loss of productivity and a reduction in the transport stream's ICG70042 Text deposition 3034778. Without treatment to avoid this phenomenon, it is necessary to dismantle the crude refining and transportation facilities and the frequency of maintenance operations of the production sites and transport facilities represents a significant economic burden.
    [0002] The main factors that favor the precipitation of asphaltenes are: a rise in pressure, a rise in temperature, variations in composition, in particular due to an injection of material into the crude or the by-product, for example the arrival of a drilling mud in the tank, a mixture of crudes or an injection of gas or other fluid.
    [0003] The composition of the crude or the by-product also influences the phenomenon of asphaltene precipitation: light oils with a low asphaltene content are rich in alkanes in which the asphaltenes are poorly soluble, and these tend to precipitate. in this place. Heavy oils, rich in asphaltenes, include high amounts of intermediate compounds, such as resins, which are good solvents for asphaltenes, and retard or prevent their precipitation. However, in crudes, precipitation of asphaltenes often results in co-precipitation of other components such as resins or waxes. In subterranean formations, the injection of fluids and the application of high pressures cause the adsorption of residues on the rock and a drop in permeability which can cause blockage of the reservoir. During refining operations, the temperature rise applied to the crudes causes coking and fouling problems in distillation columns and heat exchangers, as well as deactivation of the catalysts. During the transportation of petroleum products (crude and refined), the pressure applied to the fluid can cause the pipes to be plugged. These phenomena are largely attributable to the precipitation of asphaltenes. The resulting production losses and remediation operations represent significant costs. The problem which the invention proposes to solve is to provide a new additive which is effective for dispersing the asphaltenes responsible for the operating difficulties described above, on the production sites and in the transport and refining facilities of the plants. raw or heavy residues. Additives are known and used today to limit the precipitation of asphaltenes. In particular ungrafted alkylphenol resins have been described for this use in Energy & Fuels 2009, 23, 1575-1582, and US Pat. No. 5,0214,981. Polyethylenepolyamine-formaldehyde alkylphenol resins have been described in US Pat. No. 5,494,607 for the same application. The effectiveness of existing additives depends on the quality of the oils and the chemical structure of the asphaltenes. These additives are specific to the type of oil to be treated and are not effective on a wide range of crudes and derived products. Moreover, depending on the quality of the oils, their effectiveness is limited. In particular, the crudes can be more or less difficult to treat depending on their asphaltene content. Some additives are ineffective or must be implemented with a treatment rate too high which represents a low or no economic interest. The modified alkylphenol-aldehyde resins, obtained by Mannich reaction of an alkylphenol-aldehyde condensation resin with at least one aldehyde and at least one hydrocarbon compound having at least one alkylamine group, are known for their use in fuel compositions. as anti-sedimentation additives WASA (WO2012 / 085865), for resistance to low temperatures (WO2013 / 189868) and as an antioxidant (WO2014 / 173844). In WO2012 / 085865 and WO2013 / 189868, the disclosed technical effect is to prevent formation and precipitation, or sedimentation, of paraffin crystals, particularly at low temperatures. The document WO2014 / 173844 teaches that these compounds prevent the oxidation of unstable molecules sensitive to oxidation which are mainly molecules containing unsaturations, for example olefins in gasolines, methyl or ethyl esters of fatty acids (EMAG). and EEAG), animal fat esters or other sources of triglycerides in Biodiesels or partially hydrogenated olefins and aromatics in distillate cuts from catalytic or thermal cracking of petroleum refining products. However, these applications concern the stabilization of molecules (paraffins, fatty esters, olefins) whose structure is very different from that of asphaltenes and which precipitate under the effect of very different physicochemical factors, even opposed, from those which provoke the precipitation of asphaltenes. In particular, in the case of paraffins, precipitation is observed at low temperatures, while that of asphaltenes is observed at high temperatures.
    [0004] In addition, additives with outstanding effectiveness as paraffin dispersants, such as polyacrylates and succinic anhydride polyisobutylenes, have limited effectiveness as asphaltene dispersants, particularly when used in crude oils or in derivatives. Thus, none of the documents of the prior art mentions or suggests that modified alkylphenol aldehyde resins obtainable by Mannich reaction of an alkyl phenol aldehyde condensation resin with at least one aldehyde and at least one a hydrocarbon compound having at least one alkylamine moiety, are capable of improving dispersion and preventing precipitation of asphaltenes. The additivation of bituminous binder compositions, asphalt mixes or asphalt compositions with dispersant additives is known from the prior art.
    [0005] The preparation of hot mixes or asphalts comprises several steps. The first step is to mix the bituminous binder with aggregates (for asphalt mix) or with fillers (for asphalts) at a temperature called manufacturing temperature or coating temperature. The bituminous binder / aggregate mixture or the bituminous binder / filler mixture is then spread (for asphalt mixes) or cast (for asphalts) at a so-called processing temperature. For bituminous mixes, there is then a compaction step at a so-called compaction temperature. After compacting asphalt or pouring asphalt, asphalt or asphalt is cooled to room temperature. The different temperatures used in the preparation of traditional asphalt and asphalt are very high. Thus, for bituminous mixes, the manufacturing temperature (or coating temperature) and processing are between 160 ° C and 180 ° C, the compacting temperature is between 120 ° C and 150 ° C. For asphalts these temperatures are even higher, the manufacturing temperatures (or coating temperature) and processing are between 200 ° C and 250 ° C. These relatively high temperatures induce high energy costs, greenhouse gas emissions and volatile organic compounds and make working conditions difficult due to radiation and gaseous emissions.
    [0006] "Cold" techniques have been proposed. These techniques are based on the use of bitumen emulsions, dispersions of bitumen in water. But the mechanical performance obtained via these so-called "cold" techniques are generally behind, compared to so-called "hot" techniques. Another way of lowering the preparation temperatures of hot mixes and asphalts is based on so-called "lukewarm" intermediate techniques, based on the additivation of the bituminous binder. Various solutions based on the additivation of the bituminous binder have already been proposed: hydrocarbon waxes having a melting point greater than 85 ° C. (EP0690102), a combination of a hydrocarbon wax whose point melting point is greater than 85 ° C and a fatty acid ester wax of synthetic, plant or plant origin with a melting point of less than 85 ° C (W02004108830), ICG70042 Texte dépôt 3034778 A combination of a macromolecular compound chosen from natural resins of vegetable origin or hydrocarbon waxes, with a fatty acid derivative chosen from the group consisting of fatty acid diesters and acid ethers; fatty acid (WO2007135097), 5 - a fatty acid triglyceride (EP2192158), - a combination of additives comprising a surfactant and rheology modifier comprising a wax and a resin (WO2009062925), - at least 10% by weight of glycerol (EP2062941) in a binder bituminous. However, there is still a need for alternative compounds to presently existing additives, making it possible to reduce the temperatures for manufacturing, processing and compaction of the mixes and the temperatures for manufacturing and using the asphalts. The invention is based on the fact that by involving a bituminous binder additive with at least one modified alkyl phenol aldehyde resin, the preparation of asphalt or asphalt could be carried out at lower temperatures. SUMMARY OF THE INVENTION The invention firstly relates to the use of at least one modified alkyl phenol aldehyde resin in a crude oil composition or in a product derived from a crude oil composition and comprising asphaltenes, for dispersing the asphaltenes and / or preventing and / or delaying and / or preventing and / or reducing the precipitation of asphaltenes, said modified alkylphenol-aldehyde resin being obtainable by Mannich reaction of an alkylphenol-aldehyde condensation resin With at least one aldehyde and / or ketone having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms; and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms, preferably from 4 to 30 carbon atoms, said alkylphenol-aldehyde condensation resin being itself capable of being obtained by condensation - of at least one alkylphenol substituted with at least one linear or branched alkyl group having from 1 to 30 carbon atoms, preferably a monoalkylphenol, with at least one aldehyde and / or a ketone having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. The subject of the invention is also the use of a modified alkylphenol-aldehyde resin as defined above in a crude oil composition or in a product derived from a crude oil composition, as a dispersant additive for the aphaltenes.
    [0007] The invention also relates to a composition comprising asphaltenes, chosen from: bitumen compositions, bituminous binders, bituminous mixes and asphalts, said composition comprising at least one modified alkylphenol-aldehyde resin as defined above .
    [0008] The invention further relates to a process for treating a crude oil composition or a product derived from a crude oil composition and comprising asphaltenes, which process comprises at least: (i) introducing at least one modified alkyl phenol aldehyde resin as defined above into the crude oil composition or the product derived from a crude oil composition and including asphaltenes, (ii) a treatment step selected from: a pressure rise, a temperature rise, a mixture with at least one other fluid, According to a preferred embodiment of the invention, this is carried out in a crude oil composition or in a a product derived from a crude oil composition and comprising asphaltenes subjected to one or more of the following conditions: - a pressure rise, - a temperature rise, - a mixture with at least one other fluid. According to a preferred embodiment of the invention, the modified alkylphenolaldehyde resin can be obtained from p-nonylphenol, formaldehyde and at least one hydrocarbon compound having at least one alkylmonoamine or alkylpolyamine group. According to a preferred embodiment of the invention, the modified alkyl phenol aldehyde resin is used in diluted form in a solvent, preferably in an aromatic solvent, or in an oil. According to a preferred embodiment of the invention, the modified alkylphenolaldehyde resin is used in a crude oil composition or in a hydrocarbon fraction of crude oils comprising asphaltenes.
    [0009] According to a preferred embodiment, the invention is implemented in equipment chosen from: a tank, a refining plant, a pipeline, a wellbore, a storage tank, a transport equipment, a filter. According to a preferred embodiment of the invention, the modified alkyl phenol aldehyde resin is used in a product derived from a crude oil composition chosen from: bituminous binders, bituminous mixes and asphalts. According to a preferred embodiment of the invention, the modified alkylphenol-aldehyde resin is used to reduce the preparation temperature and / or the implementation temperature of the bituminous binder, and / or to reduce the manufacturing temperatures. , implementation and / or compaction during the preparation of a bituminous mix, and / or to reduce the manufacturing and / or implementation temperatures during the preparation of an asphalt.
    [0010] According to a preferred embodiment, the composition is a bituminous binder comprising from 0.1 to 5% by weight of modified alkylphenol aldehyde resin relative to the total mass of binder.
    [0011] According to a preferred embodiment, the composition is an asphalt mixture comprising from 1 to 10% by weight of bituminous binder and from 90 to 99% by weight of aggregates, relative to the total weight of the bituminous mix. According to a preferred embodiment, the composition is an asphalt comprising from 1 to 20% by weight of bituminous binder and from 80 to 99% by weight, based on the total weight of the asphalt. According to a preferred embodiment, the composition chosen from bituminous binders, asphalt mixes and asphalts is used for the manufacture of pavements of roads, pavements, sidewalks, roads, urban developments, soils, waterproofing of buildings or structures, in particular for the manufacture of ICG70042 Text deposition 3034778 8 road applications, foundation layers, base courses, foundation layers, surface layers such as tie layers and / or the wearing courses. According to a preferred embodiment of the method of the invention, steps (i) and (ii) are carried out successively. According to a preferred embodiment of the process of the invention, step (ii) is chosen from: extraction of a crude oil from a reservoir, a step of refining a crude oil or a by-product , transporting a crude oil or a by-product, filtering a crude oil or a by-product, injecting gas into a crude oil or a by-product, a crude oil mixture or derived products, a mixture of a crude oil or a by-product with a solvent. According to a preferred embodiment, the method of the invention is implemented in equipment chosen from: a reservoir, a wellbore, a refinery plant, a pipeline, a storage tank, a transport equipment, a filtered. According to a preferred embodiment, the process of the invention is carried out for the preparation of a bituminous binder, and comprises a step (ii) of mixing the bitumen and the modified alkylphenol aldehyde resin in which the temperature at which is achieved this mixture is between 100 ° C and 170 ° C. According to a preferred embodiment, the process of the invention is carried out for the preparation of a mix, and comprises a step (ii) of coating the bituminous binder and aggregates, the embedding temperature being included between 100 ° C and 150 ° C. According to a preferred embodiment, the process of the invention is carried out for the preparation of an asphalt, and comprises a step (ii) of mixing the bituminous binder and fillers, the mixing temperature being between 140.degree. ° C and 180 ° C. These additives, modified alkylphenol-aldehyde resin type of the invention have the function of maintaining asphaltenes dispersed in the hydrocarbon matrix and avoid or delay the phenomena of agglomeration and precipitation of asphaltenes.
    [0012] The additives of the invention have many advantages, and in particular: they are more effective than additives based on alkylphenol-aldehyde resins already known in the treatment of asphaltenes; they are effective on a wide variety of crudes, of varied compositions; they are effective in small quantities. These additives make it possible to significantly reduce the manufacturing, processing and compacting temperatures of the processes for preparing the mixes and the manufacturing and implementation temperatures of the asphalt preparation processes. The preparation process according to the invention is an anhydrous type process that does not involve the supply of external water, only the additivation of the binder makes it possible to reduce the manufacturing temperatures. The additives of the invention are inexpensive to implement because, more effective, they are added in small amounts and are therefore more economical. The additives of the invention allow the preparation of asphalt mixes and asphalts cast at lower temperatures, the properties of the additive binder being little or no change compared to the non-additive base bitumen. The process for the preparation of asphalt and asphalt cast at lower temperatures makes it possible to ensure good adhesiveness between the bituminous binder additive and the aggregates and makes it possible to obtain a mix having good resistance to stripping, a good resistance at rutting, a good modulus of rigidity. It makes it possible to obtain an asphalt manufactured at a lower temperature, having the required values of indentation and shrinkage.
    [0013] The process for preparing asphalt and asphalt cast at lower temperatures according to the invention is an anhydrous process. DETAILED DESCRIPTION The modified alkylphenol-aldehyde resin: The modified alkylphenol-aldehyde resin is obtainable by Mannich reaction of an alkylphenol-aldehyde condensation resin with at least one aldehyde and / or ketone having from 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms; and at least one hydrocarbon compound having at least one alkylmonoamine or alkylpolyamine (alkylamine) group, having between 1 and 30 carbon atoms, preferably between 4 and 30 carbon atoms, said alkylphenol-aldehyde condensation resin being itself obtainable by condensation - of at least one alkylphenol substituted with at least one linear or branched alkyl group having from 1 to 30 carbon atoms, preferably a monoalkylphenol, ICG70042 Texte dépôt 3034778 10 - with at least an aldehyde and / or a ketone having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. The alkylphenol-aldehyde condensation resin may be chosen from any resin of this type already known and in particular those described in the documents EP-S 311542, EP-857776 and EP-1584673. The modified alkylphenol-aldehyde resin according to the invention is advantageously obtained from at least one para-substituted alkylphenol. Nonylphenol is preferably used. The average number of phenol nuclei per molecule of nonylphenol-aldehyde resin is preferably greater than 6 and less than or equal to 25 and more preferably between 8 and 17, and even more preferably between 9 and 16, phenolic rings per molecule. The number of phenolic nuclei can be determined by nuclear magnetic resonance (NMR) or gel permeation chromatography (GPC).
    [0014] Advantageously, the modified alkylphenol-aldehyde resin is obtained by using the same aldehyde or the same ketone at the two stages of its preparation. According to a preferred embodiment, the modified alkylphenol-aldehyde resin can be obtained from at least one aldehyde and / or a ketone selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethyl- hexanal, benzaldehyde, acetone. Preferably, the modified alkylphenol-aldehyde resin can be obtained from at least formaldehyde. According to a particular embodiment, the modified alkylphenol-aldehyde resin is obtained from at least one alkylamine having at least one primary and / or secondary amine group. In particular, the alkylamine is advantageously chosen from primary or secondary amines substituted with, respectively, one or two alkyl groups preferably comprising from 12 to 24 carbon atoms, more preferably from 12 to 22 carbon atoms. According to a preferred variant, the modified alkylphenol-aldehyde resin is obtained from at least one alkylamine having at least one primary amine group. In particular, the modified alkylphenol-aldehyde resin may advantageously be obtained from at least one alkylamine or at least one alkylpolyamine all of whose amine groups are primary amines. The alkylamine is preferably an alkylamine or fatty alkylpolyamine having 12 to 24 carbon atoms, preferably 12 to 22 carbon atoms. According to another preferred variant, the modified alkylphenol-aldehyde resin is obtained from at least one alkylamine or an alkylpolyamine having at least one primary amine group and comprising a fatty chain having from 12 to 24 carbon atoms. preferably from 12 to 22 carbon atoms.
    [0015] Commercial alkylamines are generally not pure compounds but mixtures. Among the marketed alkyl amines which are suitable, there may be mentioned the fatty-chain alkyl amines sold under the names Norame, Trinorame, Duomeene, Dinoram, Triameene, Armeene, Polyram, Lilamine and Hemulcate.
    [0016] As a preferred example, Trinoram® S, which is a dipropylenetriamine of tallow, also known under the name N (Tallowalkyl) dipropylenetriamine. Crude oils and derived products: The invention relates to the treatment of a crude oil composition or a by-product comprising asphaltenes. Bitumens may represent a particular case of crude oil compositions, characterized by their high viscosity. By product derived from a crude oil composition is meant both a fraction derived from a crude oil composition by a fractionation method, such as, for example, refining, extraction, but also any product derived therefrom by mixing with other components, such as an additive bituminous composition. According to a first embodiment, the medium to be treated may be any crude oil composition comprising asphaltenes, and in particular, a composition located in an underground reservoir, a crude oil composition extracted from the soil, a composition of bitumen, or any hydrocarbon fraction derived from a crude oil composition by a fractionation method, such as, for example, refining, extraction. According to the invention, bitumens include: bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or tar sands. The invention also relates to bitumens derived from the refining of crude oil, in particular atmospheric and / or vacuum distillation of petroleum. These bitumens can be optionally blown, visbroken and / or deasphalted and / or mixed. Derivatives include crude oil compositions, bituminous binders.
    [0017] By bituminous binder is meant binders obtained directly from natural crude oils or from the processing of natural crude oils. These binders ICG70042 Text deposit 3034778 12 bituminous can be obtained by different crude oil refining processes (atmospheric distillation, vacuum distillation). The invention aims to avoid, prevent, delay or reduce the precipitation of asphaltenes. This phenomenon may involve compositions having very varied asphaltene contents, since the phenomenon of precipitation of asphaltenes is due to the presence of these compounds, but also to the presence or absence of other components. For example, in crude oils the alkanes promote the precipitation of asphaltenes and the resins contribute to their solubilization. The mixture of crude oils of different compositions can lead to precipitation of heavier compounds such as asphaltenes. According to a second embodiment, the medium to be treated may be an asphalt composition, or bituminous mix or a bituminous binder for its implementation in an asphalt composition, or bituminous mix. By asphalt is meant a mixture of bituminous binder with mineral fillers. The mineral fillers consist of fines (particles smaller than 0.063 mm), sand (particles with dimensions of between 0.063 mm and 2 mm) and possibly chippings (particles with dimensions larger than 2 mm, preferably between 2 mm and 4 mm). Bituminous mix means a mixture of bituminous binder with granulates and optionally mineral fillers. The aggregates are inorganic and / or synthetic aggregates, in particular recycling costs, of dimensions greater than 2 mm, preferably of between 2 mm and 14 mm. Asphalt is mainly used to make and cover sidewalks, while asphalt is used to make roads. In contrast to asphalt, asphalts are not compacted with the roller when they are put in place. Additive composition comprising the modified alkylphenol-aldehyde resin Depending on the embodiment of the invention, suitable compositions based on modified alkylphenol-aldehyde resin are formulated. Additive composition for crude oils and hydrocarbon fractions from crude oils: According to a first preferred embodiment, the modified alkyl phenol aldehyde resin is used in a diluted form in a solvent or dispersant. This embodiment relates to the additivation of the crude oil compositions and the hydrocarbon fractions which are derived therefrom.
    [0018] By way of example, the solvent or dispersant is chosen from aliphatic and / or aromatic hydrocarbons and hydrocarbon mixtures, for example the gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ICG70042 Text deposition 3034778 13 ethylbenzene, commercial solvent mixtures such as Solvarex 10 ®, Solvarex 10 LN ®, Solvent Naphta ®, Shellsol AB ®, Shellsol D ®, Solvesso 150 ®, Solvesso 150 ND ®, Solvesso 200 ® , Exxsol ®, ISOPAR ®. The solvent or dispersant is preferably aromatic.
    [0019] The composition may also contain, in addition to the solvent, a polar dissolution aid, such as 2-ethylhexanol, decanol, isodecanol and / or isotridecanol. The mass concentration of the modified alkylphenol-aldehyde resin diluted in the solvent or the dispersant can advantageously vary from 1 to 99.5%, preferably from 5 to 95%, more preferably from 10 to 90% and even more preferentially. from 30 to 90%. The viscosity of the modified alkylphenol-aldehyde condensation resin, diluted with 30% by weight of aromatic solvent measured at 50 ° C. using a dynamic rheometer with a shear rate of 100 s -1, is preferably between 1000 and 10000 mPa.s, preferably between 1500 and 6000 mPa.s, and advantageously between 2500 and 5000 mPa.s. The modified alkylphenol-aldehyde resin can also be used in a composition in combination with one or more additional additives. Additional additives which may be used in combination with the modified alkyl phenol aldehyde resin include: dispersants / detergents, metal passivators, antioxidants, corrosion inhibitors, biocides, demulsifiers, anti-foams, paraffin deposit inhibitors; pour point depressants, anti-sedimentation additives for paraffins; H2S scavengers, organic deposit inhibitors such as naphthenic acids, inorganic deposit inhibitors, markers, thermal stabilizers, emulsifiers, friction reducing agents, surfactants, deodorants, and mixtures thereof. Among the other additional additives, mention may be made especially of: a) anti-foam additives, in particular (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils; b) detergent and / or anti-corrosion additives, in particular (but not limited to) selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines and polyetheramines; imidazolines; c) lubricity additives or anti-wear agent, in particular (but not limited to) selected from the group consisting of fatty acids and their ester derivatives ICG70042 Text deposition 3034778 14 or amide, especially glycerol monooleate, and derivatives thereof mono- and polycyclic carboxylic acids; (d) crystallization modifying additives, paraffin deposition inhibiting additives, pour point depressant additives; low temperature rheology modifiers such as ethylene / vinyl acetate (EVA) and / or ethylene / vinyl propionate (EVP) copolymers, ethylene / vinyl acetate / vinyl versatate terpolymers (EA / AA / EOVA); ethylene / vinyl acetate / alkyl acrylate terpolymers; graft-modified EVA copolymers; polyacrylates; acrylate / vinyl acetate / maleic anhydride terpolymers; the amidic anhydride / alkyl (meth) acrylate copolymers obtainable by reaction of a maleic anhydride / alkyl (meth) acrylate copolymer and an alkyl amines or polyalkyl amines having a hydrocarbon chain of 4 and 30 carbon atoms, preferably from 12 to 24 carbon atoms; amidated alpha-olefin / maleic anhydride copolymers obtainable by reaction of an alpha-olefin / maleic anhydride copolymer and an alkylamine or polyalkylamine, the alpha-olefin being selectable from alpha C 10 -C 50 olefin, preferably C 16 -C 20, and the alkylamine or polyalkylamine having, advantageously, a hydrocarbon chain of 4 and 30 carbon atoms, preferably 12 to 24 carbon atoms. Exemplary terpolymers include those described in EP01692196, WO2009 / 106743, WO2009 / 106744, US4758365 and US4178951. e) antioxidants, for example of hindered phenolic or amine type of paraphenylene diamine alkyls; f) metal passivators; (g) acid neutralizers. Additive composition for products derived from bitumens: According to a second preferred embodiment, the invention relates to products derived from bitumens, such as bituminous mixes and asphalts. The modified alkylphenol-aldehyde resin additive is advantageously introduced into the bitumen in pure form (that is to say as such) or diluted in an oil. This oil can be synthetic or of mineral or vegetable origin or a combination of all three. This oil does not evaporate and its presence does not modify the properties of the final bituminous binder. The percentage of oil may be between 0 and 50% by weight of the oil mixture plus additive, and preferably between 20 and 50% by weight. In addition to the additives a) to g) described above, the additive composition for the products derived from bitumens may also comprise one or more additives chosen from: ICG70042 Texte dépôt 3034778 15 h) additives allowing to lower the temperature of asphalt mixtures and mixes, those for improving the adhesion of bituminous binders to fillers and aggregates, such as, for example, polyisobutylene succinimides Process for treating crude oils and derived products: The invention also relates to a process process for treating a crude oil composition or a product derived from a crude oil composition and comprising asphaltenes, which process comprises at least: (i) introducing at least one alkylphenol-aldehyde resin modified in the crude oil composition or in the product derived from a crude oil composition and comprising asphaltenes, (ii) a treatment step selected from: elevation of pressure, a rise in temperature, a mixture with at least one other fluid. According to the invention, the two steps can be implemented simultaneously or successively. Preferentially step (ii) is implemented after step (i).
    [0020] When the two steps are implemented successively, it is possible to provide one or more intermediate steps after step (i) and before step (ii). Use in crude oil compositions and hydrocarbon fractions: In the case of crude oils and hydrocarbon fractions derived therefrom, for example by refining or extraction, the treatment can be carried out at any stage since the recovery of crude oils in a tank, including the refining and the use of hydrocarbon fractions, including the transportation of these different products. The aim of the invention is to maintain asphaltenes in dispersion in the medium so as to improve the recovery of the crude oils, to prevent, prevent, reduce, delay the precipitation of asphaltenes, the formation of asphaltene deposits, the fouling, in tanks, treatment and transportation facilities such as extraction, refining equipment, pipelines, pipelines of all types, filters, storage tanks. Advantageously, the crude oil composition or the crude oil hydrocarbon fraction is additivated with a quantity of modified alkylphenol-aldehyde resin of between 1 and 5000 mass ppm, preferably between 10 and 2000 ppm, more preferably between 50 and 1500. ppm, more preferably between 100 and 1200 ppm. Step (ii) may, without limitation, correspond to pressurization, for example in a pipeline or any type of pipeline, or through a filter; it may comprise heating in a refining plant, a gas injection or a mixture with another variety of crude oil or with another quality of heavy oil resulting from the refining. Conventionally, such treatment steps lead to precipitation of asphaltenes and fouling and / or clogging of the installations. The modified alkylphenol-aldehyde resin additives of the invention allow asphaltenes to be maintained in dispersion during these processing steps and improve the compatibility of the asphaltenes with the non-asphaltenic part of the oil. These additives thus make it possible to avoid or limit the phenomena of agglomeration or flocculation of asphaltenes. 10 - Implementation in bituminous compositions: The bituminous compositions, such as bituminous binder, asphalt, asphalt, are characterized by hot mixing steps, for which the introduction of the modified alkylphenol-aldehyde resin additive presents the the advantage of allowing efficient mixing at a lower temperature compared to previous compositions, without degrading the properties of use of these compositions. The invention also relates to a process for the preparation of a bituminous binder as defined above, comprising mixing the bitumen and the modified alkylphenol aldehyde resin. Other components, usual additives for bituminous binders, described below, may also be present in this mixture. Preferably, in this process, the temperature at which this mixture is produced is between 100 ° C. and 170 ° C., preferably between 110 ° C. and 150 ° C., more preferably between 120 ° C. and 130 ° C. The mixing time is between 10 minutes and 4 hours, preferably between 30 minutes and 3 hours, more preferably between 1 hour and 2 hours. The invention also relates to the use of a modified alkylphenol-aldehyde resin in a bituminous binder comprising at least one bitumen, to reduce the preparation temperature of the bituminous binder. The invention relates to a process for the preparation of a bituminous mix comprising mixing or coating a bituminous binder with aggregates, the bituminous binder comprising at least one bitumen and at least one a modified alkylphenol-aldehyde resin of the invention. Preferably in this process, the bituminous binder comprises from 0.1 to 5% by weight of modified alkylphenol aldehyde resin, based on the total weight of bituminous binder, preferably from 0.5 to 3% by weight, more preferably from 0.5 to 2% by weight. Advantageously, the coating temperature of the bituminous binder and aggregates is between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C., more preferably between 120 ° C. and 130 ° C. Preferably, the bituminous binder and the aggregates are both at a temperature of between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C, when coating. When coating, the aggregates and the bituminous binder additive are either both at the same temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C. C., or the bituminous binder additive 10 is at a temperature around 160 ° C and the aggregates are at a temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C C and 130 ° C. Due to the large amount of aggregates with respect to the bituminous binder additive (approximately 95% by weight of aggregates with respect to 5% by weight of bituminous binder additive), it is the temperature of the aggregates which dictates the overall temperature. coating which will therefore be between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C. It is preferred to use the aggregates at the temperature between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C., more preferably between 120 ° C. and 130 ° C. and the bituminous binder additive at the same temperature between 100 ° C. C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C. Since the additivation of the bituminous binder by the modified alkylphenol aldehyde resin does not affect the viscosity of the bituminous binder and does not reduce it, when the viscosity of the bituminous binder is too great to allow the pumping of the bituminous binder, It is then preferred to use the additivated bituminous binder at about 160 ° C. and the aggregates at a temperature between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C., more preferably between 120 ° C. and 130 ° C. overall coating temperature being still between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C. In this case, the additive bituminous binder is preferably at a temperature between 120 ° C and 180 ° C, preferably between 140 ° C and 160 ° C and the aggregates at a temperature between 100 ° C and 150 ° C preferably between 110 ° C. and 140 ° C., more preferably between 120 ° C. and 130 ° C., the overall coating temperature always being between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C. C, more preferably between 120 ° C and 130 ° C.
    [0021] Although the coating temperature is lower in the process according to the invention, the coating is of good quality and the coating time is not increased compared to a conventional higher temperature process. Thus the coating time of the process according to the invention is between 2 seconds and 30 minutes, preferably between 5 seconds and 20 minutes, more preferably between 10 seconds and 10 minutes, even more preferably between 20 seconds. and 5 minutes, even more preferably between 30 seconds and 1 minute. It is preferred that the mixing time or coating time be as short as possible to avoid fines formation and changing the distribution of aggregates. In any case, it is not necessary to have longer coating times in the present invention and it is even sought that they be as short as possible. Once the aggregates are coated, the additive bituminous binder / aggregate mixture is spread. The operating temperature during spreading of the bituminous binder / granulate mixture is between 80 ° C. and 130 ° C., preferably between 90 ° C. and 120 ° C., more preferably between 100 ° C. and 110 ° C. The whole is then compacted and the compaction temperature of the spilled mixture is between 70 ° C. and 120 ° C., preferably between 80 ° C. and 110 ° C., more preferably between 90 ° C. and 100 ° C.
    [0022] The whole is then cooled to room temperature. The invention also relates to a bituminous mix obtainable by the process as defined above. Asphalt mixes include bituminous binder, aggregates and possibly fillers. The bituminous mix comprises from 1 to 10% by weight of bituminous binder additive, relative to the total mass of the mix, preferably from 4 to 8% by weight. The invention also relates to the use of a modified alkylphenol aldehyde resin as described above in a bituminous binder comprising at least one bitumen, for reducing the manufacturing, processing and / or compaction temperatures during the preparing a bituminous mix. The method of preparing an asphalt in which a bituminous binder is mixed with fillers, the bituminous binder comprising at least one bitumen and at least one alkylphenol-aldehyde resin. modified form of the invention. Preferably in this process, the bituminous binder comprises from 0.1 to 5% by weight of modified alkyl phenol aldehyde resin, based on the total weight of bituminous binder, preferably from 0.5 to 3% by weight, more preferably from 0.5 to 2% by weight. Advantageously, the manufacturing temperature is between 140 ° C. and 180 ° C., preferably between 150 ° C. and 170 ° C.
    [0023] Preferably, the bituminous binder and the fillers are both at a temperature between 140 ° C and 180 ° C, preferably between 150 ° C and 170 ° C, when mixed. ICG70042 Filing text 3034778 19 It should be noted that during manufacture, the fillers and the additive bituminous binder are both at the same temperature (between 140 ° C and 180 ° C, preferably between 150 ° C and 170 ° C ). Then, the bituminous binder / additive mixture is poured. The operating temperature during the pouring of the bituminous binder / filler mixture is between 120 ° C and 160 ° C, preferably between 130 ° C and 150 ° C. The whole is then cooled to room temperature. The invention also relates to an asphalt that can be obtained by the process as defined above. Asphalts include bituminous binder and mineral fillers. Advantageously, the asphalt comprises from 1 to 20% by weight of bituminous binder additive, relative to the total mass of the asphalt, preferably from 5 to 10% by weight. The invention also relates to the use of a modified alkylphenol aldehyde resin as described above in a bituminous binder comprising at least one bitumen, to reduce the manufacturing and / or implementation temperatures during the preparation of an asphalt. Bituminous compositions: The invention also relates to a composition comprising asphaltenes, said composition being chosen from bituminous binders, bituminous mixes and asphalts, said composition comprising at least one modified alkylphenol-aldehyde resin which has been described above. above. Preferably, the bituminous binder comprises from 0.1 to 5% by weight of modified alkylphenol-aldehyde resin, relative to the total weight of bituminous binder, preferably from 0.5 to 3% by weight, more preferably from 0, 5 to 2% by weight. It is preferred to use as little additive amount as possible, for economic as well as technical reasons. Indeed, if the additive is present in a large quantity in the bituminous binder, the properties of the bituminous binder such as penetrability, ball and ring temperature, viscosity, adhesiveness, complex modulus and properties of the bituminous mix. obtained from said bituminous binder such as Duriez resistance, rut resistance and modulus may be affected and become too far from those of the non-additive binder and the coating obtained from the non-additive binder. Among the bitumens that can be used in the compositions according to the invention, mention may be made first of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or oil sands. Bitumens according to the invention are also bitumens derived from the refining of crude oil. Bitumens come from the atmospheric and / or vacuum distillation of oil. These bitumens can be optionally blown, vis-reduced and / or deasphalted. The various bitumen obtained by the refining processes can be combined with one another to obtain the best technical compromise. Bitumen can also be a recycling bitumen. The bitumens may be hard grade or soft grade bitumens. The bitumens according to the invention have a penetrability, measured at 25 ° C according to EN 5 1426, of between 5 and 200 1/10 mm, preferably between 10 and 100 1/10 mm, more preferably between 20 and 60 1 / 10 mm, even more preferably between 30 and 50 1/10 mm. Preferably, the bituminous binder further comprises a polymer. The polymers used are elastomers or plastomers. For example, thermoplastic elastomers such as styrene and butadiene random or block copolymers, linear or star (SBR, SBS) or styrene and isoprene (SIS) copolymers, may be mentioned, for example, in a non-limiting manner. copolymers of ethylene and vinyl acetate, copolymers of ethylene and propene, ethylene / propene / diene terpolymers (EPDM), acrylonitrile / butadiene / styrene terpolymers (ABS), olefinic homopolymers and copolymers of ethylene (or propylene, or butylene), polyisobutylenes, polybutadienes, polyisoprenes, polyvinylchlorides, rubber crumbs, butyl rubbers, polychloroprenes, polynorbornenes, polybutenes, polyisobutenes, polyethylenes or still any polymer used for the modification of bitumens as well as mixtures thereof. Preferred polymers are copolymers of styrene and butadiene. The styrene-butadiene copolymer advantageously has a weight content of styrene ranging from 5% to 50% by weight, based on the weight of the copolymer, preferably from 20% to 40%.
    [0024] The styrene-butadiene copolymer advantageously has a weight content of butadiene, ranging from 50% to 95% by weight, based on the weight of the copolymer, preferably from 60% to 80%. Among the butadiene units, the 1-4-double-butadiene units derived from butadiene and the 1-2-double-butadiene units derived from butadiene are distinguished. 1-4-Butadiene-derived double-cross units are understood to mean the units obtained via a 1,4-addition during the polymerization of butadiene. 1,2-Butadiene double-bonded units are understood to mean the units obtained via a 1,2-addition during the polymerization of butadiene. The result of this addition 1,2 is a so-called "pendant" vinyl double bond.
    [0025] The styrene-butadiene copolymer has a content of 1,2-butadiene-derived double-chain units of from 5% to 50% by weight, based on the total weight of the butadiene units, preferably from 10% to 40%, plus 1CG70042 Text deposit 3034778 21 preferably between 15% and 30%, even more preferably between 20% and 25%, even more preferably between 18% and 23%. The styrene-butadiene hydrocarbon copolymer has an average molecular weight Mw of between 4,000 and 500,000 daltons, preferably between 10,000 and 200,000, more preferably between 50,000 and 150,000, even more preferably between 80,000 and 150,000. 000 and 130,000, even more preferably between 100,000 and 120,000. The molecular weight of the copolymer is measured by GPC chromatography with a polystyrene standard according to ASTM D3536 (replaced by ASTM D5296-05).
    [0026] The styrene-butadiene copolymer may be linear or starred, diblock, triblock and / or multi-branched. The styrene-butadiene hydrocarbon copolymer may also optionally include a statistical hinge. A mixture of copolymers of styrene and butadiene may be envisaged. In general, a quantity of polymer of 1 to 20% by weight relative to the weight of bituminous binder is used, preferably from 5 to 10%, more preferably from 2 to 4%. This polymer may optionally be crosslinked. The crosslinking agents that can be used are of a very varied nature and are chosen as a function of the type (s) of polymer (s) contained in the bituminous binder according to the invention. Preferably, the crosslinking agent 20 is selected from sulfur alone or in admixture with vulcanization accelerators. These vulcanization accelerators are either hydrocarbyl polysulfides, sulfur-donor vulcanization accelerators, or non-sulfur donor vulcanization accelerators. The hydrocarbyl polysulfides may be chosen from those defined in the patent FR2528439. The sulfur donor vulcanization accelerators may be selected from thiuram polysulfides, such as, for example, tetrabutylthiuram disulfides, tetraethylthiuram disulfides and tetramethylthiuram disulfides. The non-sulfur-donor vulcanization accelerators that may be used according to the invention may be sulfur compounds chosen in particular from mercaptobenzothiazole and its derivatives, dithiocarbamates and its derivatives, and thiuram monosulphides and its derivatives. There may be mentioned, for example, zinc-2-mercaptobenzothiazole, zinc dibutyldithiocarbamate and tetramethylthiuram monosulfide. For more details on the sulfur-donor and non-sulfur-donor vulcanization accelerators that can be used according to the invention, reference can be made to patents EP0360656, EP0409683 and FR2528439. In general, a quantity of crosslinking agent of 0.05 to 2% by weight relative to the mass of bituminous binder is used, preferably from 0.1 to 1%, even more preferably from 0.2 to 0.5% by weight. . The bituminous binder according to the invention may also comprise fluxing agents such as oils based on animal and / or vegetable fats or hydrocarbon oils of petroleum origin. The oils of animal and / or vegetable origin may be in the form of free fatty acids, triglycerides, diglycerides or monoglycerides, in esterified form, for example in the form of a methyl ester. The bituminous binder according to the invention may also comprise waxes of animal, plant or hydrocarbon origin, in particular long chain hydrocarbon waxes, for example polyethylene waxes or Fischer-Trospch waxes. Polyethylene waxes or Fischer-Trospch waxes may optionally be oxidized.
    [0027] Amide waxes such as ethylene bis-stearamide may also be added. The bituminous binder according to the invention may also comprise resins of vegetable origin such as rosins. The bituminous binder according to the invention may also comprise acids such as polyphosphoric acid or diacids, in particular fatty diacids.
    [0028] The bituminous binder may also comprise tackifiers and / or surfactants. They are advantageously chosen from alkylamine derivatives, alkyl-polyamine derivatives, alkylamidopolyamine derivatives, alkyl amidopolyamine derivatives and quaternary ammonium salt derivatives, taken alone or as a mixture. The most used are the tallow tallow propylenes, the tallow amine amines, the quaternary ammoniums obtained by quaternizing the tallow propylene diamines, the tallow propylene-polyamines. It is also possible to add sorbitol derivatives, hydrazide derivatives and imidazolidinone derivatives. The modified alkylphenol-aldehyde resin additive makes it possible to prepare asphalts and asphalts at lower manufacturing, processing and compacting temperatures than those conventionally used and at very low levels in the bituminous binder. This is known as a process for the preparation of bituminous mixes and so-called "warm" and not "hot" asphalts. This additive allows a very good adhesiveness and wettability of the bituminous binder vis-à-vis the aggregates, the bituminous binder is very manageable, and this even at lower temperatures than those used traditionally. The use of this additive makes it possible to lower the said temperatures of all bitumens (hard grade bitumens, intermediate grade bitumens, soft grade bitumens), irrespective of their penetrability. Thus the additive is suitable for penetration bitumens of between 35 and 50 1/10 mm and bitumens of penetrability of between 10 and 20 1/10 mm. This additive makes it possible to lower these temperatures while preserving the mechanical properties of bituminous mixes and cast asphalts, and at very low additive contents. The subject of the invention is also the use of bituminous binders, asphalt mixes and cast asphalts according to the invention for the manufacture of road, carriageway, sidewalk, roadway and urban pavement coverings. of floors, waterproofing of buildings or structures, in particular for the manufacture in road application, of foundation layers, base layers, foundation layers, surface layers such as tie layers and / or the wearing courses.
    [0029] Figure: Figure 1: Schematic representation of the pressure performance evaluation pilot Experimental part: A- Materials and methods Crude oils: Three crude oils of different compositions were used. HB1: Oil comprising 15% by weight of asphaltenes, characterized by an ASCI score 9 HB2: Oil comprising 10% by weight of asphaltenes, characterized by an ASCI 11 HB3 rating: An oil comprising 5% by weight of asphaltenes, characterized by a ASCI 12 rating The ASCI method (for Asphaltene Solubility Class Index or solubility class index of asphaltenes) is described in N. Passade Boupat et al., SPE-164184-MS, Society of Petroleum Engineers, 2013; M. Rondon-Gonzalez et al., SPE-171891-MS, Society of Petroleum Engineers, 2014. Additives: Ad1: Nonylphenol modified aldehyde resin prepared according to procedure No. 1 Step 1 followed by Step 2 below - Formulated in a C10 aromatic solvent (of the Solvarex 10 type) at a concentration of 50% by mass of active ingredient Ad2: Polyisobutylene succinimide sold by the company Total ACS (Total Marketing & Services) - formulated in a C10 aromatic solvent ( Solvarex type 10) at a concentration of 50% by mass of active ingredient. Ad3: Octadecylsuccinimide - marketed by Total ACS under the reference HFAS 100 - formulated in a C10 aromatic solvent (of the Solvarex 10 type) at a concentration of 27.5% by mass of active ingredient ICG70042 Deposit text 3034778 24 Ad4: Resin unmodified nonylphenol aldehyde - formulated in a C10 aromatic solvent (Solvarex 10 type) - obtained by procedure No. 1 Step 1 described below. Ad5: Unmodified low molecular weight nonylphenol aldehyde formulated in a C10 aromatic solvent (Solvarex 10 type) - obtained by procedure No. 1 Step 1 described below. The characteristics of the Ad4 and Ad5 resins are listed in the following Table 1: Reference Chain alkyl Mat content Mw (Da) (**) active (*) Ad4 C9 67.10% 5000 Ad5 C9 70.60% 2500 (*) % by mass, in solution in toluene (**) Mass average mass by weight Ad6: C12-C14 polyacrylate, of mass average molecular weight Mw = 12000 Da - formulated in a C10 aromatic solvent (of the Solvarex type 10 ) at a concentration of 35% by mass of active material Ad7: C18-C22 polyacrylate, of weight average molar mass Mw = 12000 Da - formulated in a C10 aromatic solvent (of the Solvarex 10 type) at a concentration of 35% Active Ingredient No. 1: Synthesis of the Modified Alkylphenol Aldehyde Resin Step 1: In a first step, an alkylphenol-aldehyde resin is prepared by condensation of para-nonylphenol and formaldehyde (for example according to the procedure described in EP 857 776) of viscosity at 50 C between 1800 and 4800 mPa.s (viscosity measured at 50 ° C. using a dynamic rheometer with a shear rate of 10% on the resin diluted with 30% by mass of aromatic solvent (Solvesso 150 (ID)). Step 2: In a second step, the alkylphenol-aldehyde resin resulting from the first step is modified by Mannich reaction by adding 2 molar equivalents of formaldehyde and 2 molar equivalents of tallow dipropylenetriamine, known under the name N- (Tallowalkyl) dipropylenetriamine and sold for example under the name Trinoram S®, relative to the alkylphenol-aldehyde resin from the first step. The characteristics of the resin obtained at the end of step 2 are listed in Table 2 below: No. Alkylamine resin Dry materials Viscosity NPhe (**) used (1 g / 30 min / 200 °) C) 50 ° C. (mPa.%) (*) Adl Trinoram S® 70.10% 4855 14.1 Table 2 5 (*) Viscosity at 50 ° C.: measured on a resin diluted with 70% by mass of Solvesso 150 ® shear rate 10 s-1, using a Haake RheoWin e rheometer. (**) Evaluation of the average number of phenolic nuclei per molecule of resin or Nphe: measured by nuclear magnetic resonance of the proton.
    [0030] Experiments: - Study of resistance to clogging: The study is carried out in a pilot (1), the different components of which are illustrated in FIG. 1: The objective of the test is to study the kinetics of precipitation and clogging asphaltenes in a capillary tube under continuous flow conditions. The principle of measurement consists in injecting into a capillary tube a mixture of crude oil and solvent at a fixed and constant rate. The pressure drop is measured along the capillary tube. The pressure difference AP (in Pa) is related to the flow (in m3 / s) by the law 20 of Hagen Poiseuille: 8n in which R and L respectively represent the radius (in meters) and the length (in meters) of the capillary, n represents the viscosity of the fluid (in Pa $). When a deposit of asphaltenes is formed in the capillary, R decreases, which causes an increase in P. The pumps are equipped with a safety system which stops the injection when the pressure reaches 8 bar. The sample may be composed of crude oil, solvent and additives in various proportions. The precipitation of asphaltenes can be caused by mixing a light aliphatic solvent with the crude oil. The experimental device shown in FIG. 1 comprises four syringes actuated by pumps (PHD Ultra 4400, Harvard Apparatus) which converge in a static mixer (4) located at the inlet (5.1) of the capillary. The pump (2) is used to inject the crude oil. The pumps (3.1) and (3.2) are used to inject respectively an additive solution (in toluene) and a solvent such as heptane. The last pump (3.3) is used to clean the circuit or to calibrate the system with toluene. Before entering the static mixer (4), the crude oil, the additive (s), the solvents are conditioned in the oven (7) at a controlled temperature of 45 ° C. The assembly is mixed by means of the static mixer (4) and then injected at the inlet (5.1) of the capillary tube (5) 3 m in length and 0.38 mm in diameter. The entire device is placed in the oven (7) so as to maintain a controlled temperature of 45 ° C. The pressure drop between the inlet (5.1) and the outlet (5.2) of the capillary (5) is measured in real time by means of piezoelectric transducers (6) connected to the ends (5.1) and (5.2) of the capillary.
    [0031] Principle of the test: In a first step (protocol 1), the oil / heptane ratio is determined prior to the capillary test in order to determine the conditions of precipitation of the asphaltenes. Then, the non-additive oil and heptane are injected into the capillary (5) with the heptane / oil ratio identified in the first step, which makes it possible to determine the initial blocking time of the capillary (5). Then (protocol 2) thanks to the additive, this blocking time is shifted to larger times. Protocol 1: Additive concentration scanning test In this test, the additive is injected into the capillary (5) in several steps, following a decreasing ramp of additive concentration relative to the oil.
    [0032] The additive is in solution in heptane, the additive solution dissolved in heptane has a fixed concentration. Firstly, toluene, then heptane and oil are injected. The ratio of the crude oil / heptane is kept constant during the test, and the ratio of the additive / heptane solution decreases at each step as summarized in Table 3. Each step has a duration of 210 minutes. The objective of this experiment is to determine the additive concentration ranges in which this has an effect on asphaltene dispersion. For the crude oil tested (HB2, but this protocol can be used with any crude oil), the onset of precipitation of the crude (control) oil was determined as a ratio of 3 volumes of heptane to a crude oil. oil volume: Heptane / Oil = 3. ICG70042 Deposition text 3034778 27 Flow rates (pL / min) Stage Time Quantity Toluene Heptane oil Additive solution (min) of crude additive in heptane (PPm) 1 90 0 150 0 0 0 2 210 10000 0 50 50 100 3 210 3000 0 50 120 30 4 210 1000 0 50 140 10 5 210 300 0 50 147 3 Table 3 Protocol 2: Additive concentration test After a concentration analysis As a limit, a given concentration for each additive can be selected, for which the threshold performance is identified. Thus, for this part of the test, for the additive according to the invention, Ad1, a constant flow of 1000 ppm of the additive dissolved in heptane is injected into the capillary with the crude oil, keeping the ratio of volume 3: 1 heptane: crude oil. The corresponding flow rates are summarized in Table 4. The temperature was set at 45 ° C in each test. The purpose of this test is to determine the action of the additive over time, at a given dose, under flow conditions. The time is measured after which the pressure of 8 bar is reached. Flow rate (ml / min) Oil Crude solution of additive Step Time Amount of additive Toluene (min) (PPm) 1 90 0 150 0 0 2 840 1000 0 50 150 Table 4 Then determined for different concentrations and for various additives, the time after which the pressure of 8 bar is reached. The longer the time to reach this pressure of 8 bars, the higher the effectiveness of the additive as asphaltenes dispersant is high.
    [0033] C-Results: The results are reported in Tables 5, 6 and 7 below: ICG70042 Deposit Text 3034778 28 HB1 Oil Additive Concentration Additive Determination in Result (h) Additive (*) Active Ingredient (PPm) No additive 3 , 5 Adl 50% 1000 8 Adl 50% 700 9.5 Ad2 50% 1000 3.5 Ad3 27.5% 550 6.2 Ad3 27.5% 1000 7 Ad4 67.1% 1000 5.3 Ad5 70.6 % 1000 3 Table 5: Results of Pressure Performance Tests for HB1 Oil HB2 Oil Additive Concentration Additive Dosage in Result (h) additive (*) active ingredient (PPm) No additive 3.5 Adl 50% 1000> 12 Adl 50% 700 - Ad2 50% 1000 9 Ad3 27.5% 700 - Ad3 27.5% 550 4.5 Ad4 67.1% 700 - Ad5 70.6% 700 - Ad6 35% 700 - Ad7 35% 700 9 Table 6: Results of Pressure Performance Tests for HB2 Oil ICG70042 Filtration Text 3034778 29 HB3 Oil Additive Concentration Additive Dosage in Result (h) Additive (*) Active Ingredient (PPm) No Additive 3 Adl 50% 1000> 12 Ad2 50% 1000 9 Ad3 27.5% 550 7 Ad7 35% 700 8 Tab Water 7: Results of Pressure Performance Tests for HB3 Oil (*) Mass concentration of the additive in the solvent The modified alkyl phenol aldehyde resins according to the present invention are remarkable in that they are particularly effective in dispersing asphaltenes and / or to prevent and / or retard and / or prevent and / or reduce the precipitation of asphaltenes over a wide range of crude oils as compared to asphaltene dispersant additives of the prior art. ICG70042 Deposit text
    权利要求:
    Claims (19)
    [0001]
    REVENDICATIONS1. Use of at least one modified alkylphenol aldehyde resin in a crude oil composition or in a product derived from a crude oil composition and comprising asphaltenes, for dispersing asphaltenes and / or for preventing and / or retarding and and / or to prevent and / or reduce the precipitation of asphaltenes, said modified alkylphenol-aldehyde resin being obtainable by Mannich reaction of an alkylphenol-aldehyde condensation resin with at least one aldehyde and / or a ketone having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms; and at least one hydrocarbon compound having at least one alkylamine group, having between 1 and 30 carbon atoms, preferably between 4 and 30 carbon atoms, said alkylphenol-aldehyde condensation resin itself being capable of being obtained by condensation - of at least one alkylphenol substituted with at least one linear or branched alkyl group having from 1 to 30 carbon atoms, preferably a monoalkylphenol, with at least one aldehyde and / or a ketone having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms.
    [0002]
    2. Use according to claim 1, for its implementation in a crude oil composition or in a product derived from a crude oil composition and comprising asphaltenes subjected to one or more of the following conditions: an elevation of pressure, - a rise in temperature, - a mixture with at least one other fluid.
    [0003]
    3. Use according to any one of claims 1 and 2, wherein the modified alkylphenol-aldehyde resin is obtainable from pnonylphenol, formaldehyde and at least one hydrocarbon compound having at least one alkylmonoamine group or alkyl polyamine.
    [0004]
    4. Use according to any one of claims 1 to 3, wherein the modified alkylphenol-aldehyde resin is carried out in diluted form in a solvent, preferably in an aromatic solvent, or in an oil. ICG70042 Filing text 3034778 31
    [0005]
    5. Use according to any one of claims 1 to 4, in a crude oil composition or in a hydrocarbon fraction of crude oils comprising asphaltenes. 5
    [0006]
    6. Use according to claim 5, in equipment selected from: a reservoir, a refinery, a pipeline, a wellbore, a transport equipment, a filter. 10
    [0007]
    7. Use according to any one of claims 1 to 4, in a product derived from a composition of crude oils selected from: bituminous binders, bituminous mixes and asphalts.
    [0008]
    8. The use as claimed in claim 7, for reducing the preparation temperature or the temperature of use of the bituminous binder, and / or for reducing the manufacturing, working and / or compacting temperatures during the preparation of the binder. bituminous mix, and / or to reduce the temperatures of manufacture and / or implementation during the preparation of an asphalt. 20
    [0009]
    9. Composition comprising asphaltenes, chosen from: bitumen compositions, bituminous binders, bituminous mixes and asphalts, said composition comprising at least one modified alkylphenol-aldehyde resin obtainable by Mannich reaction of a resin alkylphenol-aldehyde condensation compound with at least one aldehyde and / or ketone having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms; and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms, preferably from 4 to 30 carbon atoms, said alkylphenol-aldehyde condensation resin being itself capable of being obtained by condensation - of at least one alkylphenol substituted with at least one linear or branched alkyl group having from 1 to 30 carbon atoms, preferably a monoalkylphenol, with at least one aldehyde and / or a ketone having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. ICG70042 Filing text 3034778 32
    [0010]
    10. Composition according to claim 9 which is a bituminous binder comprising from 0.1 to 5% by weight of modified alkylphenol aldehyde resin, relative to the total mass of binder. 5
    [0011]
    11. A bituminous mix according to claim 9, comprising from 1 to 10% by weight of bituminous binder according to claim 10 and from 90 to 99% by weight of aggregates, relative to the total mass of the bituminous mix.
    [0012]
    Asphalt according to claim 9, comprising from 1 to 20% by weight of bituminous binder according to claim 10 and from 80 to 99% by weight, based on the total mass of the asphalt.
    [0013]
    13. Use of bituminous binders, asphalt and asphalt according to any one of claims 9 to 12, for the manufacture of pavements of roads, pavements, sidewalks, roads, urban developments, soils , waterproofing of buildings or structures, in particular for the manufacture in road application, of foundation layers, base layers, foundation layers, surface layers such as tie layers and / or wearing courses. 20
    [0014]
    A process for treating a crude oil composition or a product derived from a crude oil composition and comprising asphaltenes, which process comprises at least: (i) introducing at least one resin alkylphenol aldehyde modified in the crude oil composition or in the product derived from a crude oil composition and comprising asphaltenes, (ii) a treatment step selected from: a pressure rise, a temperature rise, a mixture with at least one other fluid, said modified alkylphenol-aldehyde resin being obtainable by Mannich reaction of an alkylphenol-aldehyde condensation resin with at least one aldehyde and / or a ketone having from 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms; and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms, preferably from 4 to 30 carbon atoms, said alkylphenol-aldehyde condensation resin being itself capable of being obtained by condensation ICG70042 Text deposition 3034778 33 - at least one alkylphenol substituted by at least one linear or branched alkyl group having from 1 to 30 carbon atoms, preferably a monoalkylphenol, with at least one aldehyde and / or one ketone having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.
    [0015]
    15. The method of claim 14, wherein step (ii) is selected from: extraction of a crude oil from a reservoir, a refining step of a crude oil or a by-product, a transport a crude oil or a by-product, a filtration of a crude oil or a by-product, an injection of gas into a crude oil or a by-product, a mixture of crude oils or products derivatives, a mixture of a crude oil or a by-product with a solvent.
    [0016]
    16. A process according to claim 14 or claim 15 which is carried out in equipment selected from: a reservoir, a wellbore, a refinery, a pipeline, a storage tank, a transport equipment , a filter.
    [0017]
    17. A method according to claim 14 for preparing a bituminous binder, comprising a step (ii) of mixing the bitumen and the modified alkylphenol aldehyde resin in which the temperature at which this mixture is produced is between 100 ° C. and 170 ° C.
    [0018]
    18. The method of claim 14 for preparing a bituminous mix comprising a step (ii) of coating the bituminous binder and aggregates, the coating temperature being between 100 ° C and 150 ° C.
    [0019]
    19. The method of claim 14 for preparing an asphalt, comprising a step (ii) of mixing the bituminous binder and fillers, the mixing temperature being between 140 ° C and 180 ° C.
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    同族专利:
    公开号 | 公开日
    EP3280783A1|2018-02-14|
    WO2016162392A1|2016-10-13|
    US10611972B2|2020-04-07|
    CN107592870A|2018-01-16|
    RU2017135229A3|2019-07-31|
    CA2981750A1|2016-10-13|
    US20180079976A1|2018-03-22|
    RU2017135229A|2019-05-13|
    FR3034778B1|2017-04-28|
    RU2699566C2|2019-09-06|
    BR112017021726B1|2021-08-03|
    BR112017021726A2|2018-07-10|
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    法律状态:
    2016-03-22| PLFP| Fee payment|Year of fee payment: 2 |
    2016-10-14| PLSC| Search report ready|Effective date: 20161014 |
    2017-03-22| PLFP| Fee payment|Year of fee payment: 3 |
    2018-03-22| PLFP| Fee payment|Year of fee payment: 4 |
    2020-03-19| PLFP| Fee payment|Year of fee payment: 6 |
    2021-04-23| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1553102A|FR3034778B1|2015-04-10|2015-04-10|ASPHALTENING DISPERSANT ADDITIVE AND USES THEREOF|FR1553102A| FR3034778B1|2015-04-10|2015-04-10|ASPHALTENING DISPERSANT ADDITIVE AND USES THEREOF|
    PCT/EP2016/057553| WO2016162392A1|2015-04-10|2016-04-07|Asphaltene dispersant additive and uses thereof|
    US15/565,660| US10611972B2|2015-04-10|2016-04-07|Dispersing additive for asphaltenes and its uses|
    RU2017135229A| RU2699566C2|2015-04-10|2016-04-07|Dispersant additive for asphaltenes and use thereof|
    BR112017021726-0A| BR112017021726B1|2015-04-10|2016-04-07|USE OF AT LEAST ONE MODIFIED ALKYLPHENOL-ALDEHYDE RESIN, COMPOSITION, BITUMINOUS MIXTURE, ASPHALT, USE OF BITUMINOUS BINDERS, MIXTURES AND ASPHALT AND PROCESS FOR THE TREATMENT OF A CRUDE OIL COMPOSITION|
    EP16718222.9A| EP3280783A1|2015-04-10|2016-04-07|Asphaltene dispersant additive and uses thereof|
    CN201680026797.XA| CN107592870A|2015-04-10|2016-04-07|Dispersing additive of asphalitine and application thereof|
    CA2981750A| CA2981750A1|2015-04-10|2016-04-07|Asphaltene dispersant additive and uses thereof|
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