WO2021250353A1 - Coating formulation for protecting against agglomeration and dust, and particle coated therewith - Google Patents

Coating formulation for protecting against agglomeration and dust, and particle coated therewith Download PDF

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Publication number
WO2021250353A1
WO2021250353A1 PCT/FR2021/051034 FR2021051034W WO2021250353A1 WO 2021250353 A1 WO2021250353 A1 WO 2021250353A1 FR 2021051034 W FR2021051034 W FR 2021051034W WO 2021250353 A1 WO2021250353 A1 WO 2021250353A1
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Prior art keywords
weight
formulation
phosphoric acid
formulation according
ethoxylated
Prior art date
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PCT/FR2021/051034
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French (fr)
Inventor
Juan GONZALEZ LEON
Dominique Imbert
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Arkema France
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Publication of WO2021250353A1 publication Critical patent/WO2021250353A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/30—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using agents to prevent the granules sticking together; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/20—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for preventing the fertilisers being reduced to powder; Anti-dusting additives
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/30—Anti-agglomerating additives; Anti-solidifying additives
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/22—Materials not provided for elsewhere for dust-laying or dust-absorbing

Definitions

  • the present invention relates to coating formulations for granular materials, such as granular fertilizers, in order to improve their intrinsic qualities so that the storage of said granular materials is simpler and safer.
  • Fertilizers and other mineral products are often stored in large quantities for different periods of time. Many of them tend to clump together during storage and generate large amounts of dust during transport. Agglomeration can make the transport and use of fertilizers and other mineral products impossible because they cannot flow. The dust generated during transport and during the loading and unloading operations of these products can generate serious health and safety problems as the atmosphere can become saturated with fine mineral particles.
  • a commonly known solution for solving these problems is to apply a fine coating of a liquid or solid formulation. This generally prevents or at least slows down the agglomeration process and suppresses or at least reduces the generation of fine dust from the surface of the fertilizer or granular mineral product.
  • the coating, in liquid form, is usually sprayed onto the granules just before storage.
  • coating formulations are mainly based on mineral oils and often include one or more surfactants in order to reduce the agglomeration.
  • Many publications also mention coatings containing oils from renewable sources, such as vegetable oils, which can prevent caking and generation of dust.
  • these publications several of them describe the use of glycerol and of formulations containing glycerol for the specific application of the coating based on glycerol.
  • document US2008072641 describes the use of compositions consisting of the reaction product of glycerol and multifunctional acids for the fight against agglomeration and dust.
  • citric acid is mentioned in combination with glycerol.
  • the actual coating constituent is then a polyester resulting from this reaction.
  • Document US2006040049 describes the use of metal salts of fatty acids as anti-caking agents.
  • the dispersion media for the coating compositions there are vegetable oils and glycerol.
  • US2015367363 claims a composition of a particulate material, glycerol and a poly (acetate). vinyl) for dust control.
  • Document US2015144836 describes, as an anti-dust agent, a copolymer of glycerol and an organic acid (namely hydrostearic acid) and document WO2014032131 discloses a anti-dust composition comprising glycerol, a sugar solution and optionally l 'citric acid.
  • a first object of the present invention is to provide a coating formulation for a granular material which is useful for preventing clumping and / or for reducing dust generated during transportation.
  • Another object of the present invention is to provide a coating formulation for a granular material which is useful for preventing agglomeration and / or for reducing dust generated during transport, said formulation not requiring processing methods. embedding complicated. Still other objects will follow from the description of the present invention, which is now disclosed below.
  • coating formulations containing polyol are already known and make it possible to obtain relatively good results in terms of anti-agglomeration and dust-proof performance, such as for example coating formulations based on glycerol, the applicants have carried out careful research to try to further improve the performance of these coating formulations containing polyol. And it has been discovered, surprisingly, that the performance of these formulations is improved by adding specific, selected surfactants to said coating formulations.
  • the present invention relates to a formulation comprising:
  • composition comprising a) 10% by weight to 99% by weight of at least one polyalcohol and b) 1% by weight to 90% by weight, preferably 1% by weight to 70% by weight, more preferably 1% by weight by weight at 50% by weight, even more preferably 1% by weight at 30% by weight of at least one alkoxylated surfactant, limit values included, relative to the total weight of the composition comprising a) + b) and 2) in minus a solvent.
  • the at least one solvent present in the formulation according to the invention can be any solvent known to those skilled in the art and preferably chosen from monoalcohols and water as well as their mixtures. Unless otherwise specified, all numeric and percentage ranges in this specification include range limits.
  • the formulation of the present invention can also comprise one or more other constituents commonly used in the art, including, without limitation, and usually chosen from additives, fillers and the like, such as for example one or several of these among:
  • anti-caking agents such as alkylamines, alkylphosphoric esters, linear alkyl alcohols, alkylether sulfates, alkylsulfonates, arylsulfonates, alkylethersulfonates and their combinations, preferably alkylamines salts with alkylphosphoric esters,
  • rheology modifiers such as biodegradable and non-biodegradable polymers, waxes, preferably waxes from renewable, mineral sources, or synthetic waxes, such as Fischer-Tropsch waxes, amidoamides, alkylamidoamides, • waterproofing agents, such as linear alkyl alcohols and microcrystalline waxes,
  • dispersing agents such as oils from vegetable and mineral sources
  • inorganic and / or organic micronutrients and trace elements which can be, but are preferably, finely dispersed and / or compatibilized, for example metal complexes,
  • pesticides such as insecticides, herbicides, fungicides, nematocides and the like
  • cationic anti-caking agents such as for example those chosen from primary, secondary and tertiary amines, as well as their salts, preferably the primary amines of formula R-NH, in which R represents a hydrocarbon chain comprising 8 to 36 carbon atoms, preferably 12 to 24 carbon atoms and more preferably the hydrocarbon chain is a linear or branched hydrocarbon chain, still more preferably a linear hydrocarbon chain and most preferably a linear C 8 alkyl chain -C 36 , most preferably a linear C12-C24 alkyl chain.
  • R represents a hydrocarbon chain comprising 8 to 36 carbon atoms, preferably 12 to 24 carbon atoms and more preferably the hydrocarbon chain is a linear or branched hydrocarbon chain, still more preferably a linear hydrocarbon chain and most preferably a linear C 8 alkyl chain -C 36 , most preferably a linear C12-C24 alkyl chain.
  • the nitrogen-containing anti-caking agent is selected from primary, secondary and tertiary amines, as well as their salts, and more preferably, the nitrogen-containing surfactant is a fatty amine, more preferably a saturated linear fatty amine. comprising 16 to 18 carbon atoms.
  • the anti-caking agent is an anionic anti-caking agent chosen from esterphosphates of fatty alcohols, such as for example those described in "Encyclopedia of Chemical Technology", 4th edition, Kirk-Othmer, volume 23, 504-505 pages (1997), in "Ullmann's Encyclopedia of Industrial Chemistry", 5th edition, B. Elvers, S. Hawkins, G.
  • esterphosphates intended for use as anti-caking agent additives in the formulation of the invention comprise, inter alia, esters having a linear hydrocarbon chain or branched, saturated or unsaturated C 6 -C 3 o, preferably C 6 - C 2 o and more preferably a linear and saturated hydrocarbon chain and more particularly the hexyl monoester of phosphoric acid, the hexyl diester of phosphoric acid , phosphoric acid n-octyl monoester, phosphoric acid n-octyl diester, phosphoric acid iso-octyl monoester, phosphoric acid iso-octyl diester, 2-ethylhexy
  • anti-caking agents which can be added to the formulation of the present invention also include anionic and cationic anti-caking agents, as well as their mixtures and for example mixtures comprising a salt formed from an anti-caking agent containing nitrogen and an acid-type anionic anti-caking agent, for example and preferably an ester of phosphoric or sulfuric or alkyl (aryl) sulfonic acid.
  • the anti-caking agent used as an additive in the formulation of the present invention is a mixture comprising at least one surfactant chosen from primary, secondary or tertiary amines, preferably from primary amines and secondary, as well as their salts, and at least one anionic surfactant chosen from monoalkyl and dialkyl esters of phosphoric acid.
  • the anti-caking agents comprise anionic and cationic anti-caking agents, as well as their mixtures and for example mixtures comprising the monoalkyl esters of phosphoric acid, the dialkyl esters of phosphoric acid, the compounds thereof. Alkyl esters of sulfuric acid, alkylsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids and their salts.
  • the anti-caking agent intended to be used in the formulation of the present invention is a mixture comprising at least one surfactant chosen from primary, secondary or tertiary amines, preferably from primary amines and secondary, as well as their salts and an anionic surfactant chosen from alkylsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids and their salts, for example the mixture formed with octadecylamine and dodecylsulfonic acid or the mixture formed with octadecylamine and dodecylbenzenesulfonic acid.
  • the formulation of the present invention is preferably and advantageously liquid at room temperature (25 ° C).
  • the viscosity of the formulation according to the present invention is usually in the range 1 mPa.s to 1000 mPa.s and more preferably 2 mPa.s to 800 mPa.s, limit values included.
  • a polyalcohol in the sense of the invention is a compound which comprises more than one -OH functional group.
  • suitable polyalcohols include, but are not limited to, glycerol (or 1,2,3-propanetriol), diglycerols, polyglycerols, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, trimethylolpropane, erythritol, xylitol, threitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol , maltotriitol, maltotetra-itol, isosorbide, iso-idide, isomannide, dextrin, dextrose, disacc
  • the polyalcohol has a viscosity of less than 5000 mPa.s at 25 ° C, as measured using a dynamic shear rheometer (Anton Paar MCR301) in a parallel plate geometry of 50 mm ( PP50) at 25 ° C and a shear rate of 80 s -1 .
  • the at least one polyalcohol is glycerol.
  • the glycerol which can be used in the context of the present invention can come from various sources, either from fossil sources or from plants or animals and, for example, and not limited to it, the glycerol is a glycerol crude such as that obtained from the production of biodiesel. Crude glycerol is particularly suitable for the preparation of the formulation of the present invention, since it can be found in large quantities at a reasonable price.
  • Crude glycerol is therefore widely available and well known to those skilled in the art, who can find a complete description of this compound in the article written by Pal and Chaurasia "Characterization of Crude and Purified glycerol from biodiesel Production and Purification Techniques ", V th international Symposium of Fusion of Science and Technology, New Delhi, India, January 2016.
  • the polyalcohol which forms part of the formulation of the present invention is used in dosages between 10% by weight and 99% by weight, relative to the total weight of the composition comprising the polyalcohol a ) and the alkoxylated surfactant b).
  • the polyalcohol is used in dosages between 20% by weight and 95% by weight, more preferably between 30% by weight and 90% by weight and even more preferably between 50% by weight and 85% by weight, based on total weight of the composition comprising the polyalcohol a) and the alkoxylated surfactant b).
  • the alkoxylated surfactant which can be used in the formulation of the present invention can be any alkoxylated surfactant known to those skilled in the art as a compound which lowers the surface tension of the polyalcohol and which comprises a sequence of one or more alkylenoxy units chosen from ethylenoxy, propylenoxy, butylenoxy or their mixtures.
  • the alkoxylated surfactant comprises at least 3 repeating alkylenoxy units originating from the opening of an oxirane ring.
  • the alkoxylated surfactant comprises at most 100, preferably at most 80, even more preferably at most 60 recurring alkylenoxy units originating from the opening of a ring. oxirane.
  • the alkoxylated surfactant comprises 3 to 100 recurring alkylenoxy units, more preferably 3 to 80 recurring alkylenoxy units and more preferably 3 to 60 recurring alkylenoxy units, originating from the opening of ' an oxirane ring.
  • the alkoxylated surfactant of the invention is an ethoxylated surfactant comprising 3 to 100 repeating ethylenoxy units, more preferably 3 to 80 recurring ethylenoxy units and more preferably 3 to 60 recurring ethylenoxy units, originating from the opening of a ring. oxirane.
  • alkoxylated surfactants include:
  • alkoxylated alkylaryl alcohols where the alkylaryl alcohol is either one of particularly ethoxylated fatty alcohols, propoxylated fatty alcohols, butoxylated, linear or branched, saturated or unsaturated fatty alcohols, such as ethoxylated glycerol, propoxylated glycerol, ethoxylated octyl alcohols, ethoxylated branched octyl alcohols, ethoxylated dodecyl alcohols, ethoxylated octadecyl alcohols, ethoxylated cardanol derivatives, nonylphenol ethoxylates and propoxylates, tristol ethoxylates and propoxylates,
  • alkoxylated alkyl esters of phosphoric acid particularly alkoxylated alkyl esters of phosphoric acid having a linear or branched, saturated or unsaturated hydrocarbon chain, preferably a linear and saturated C 6 -C 3 o hydrocarbon chain, advantageously a linear and saturated C 6 - C 2 o hydrocarbon chain and having a sequence of one or more, preferably from one to ten, more preferably from 3 to 8, groups selected from ethylene oxide, oxide propylene, butylene oxide and their mixtures,
  • alkoxylated monoalkyl esters for example ethoxylated and / or propoxylated and / or butoxylated
  • alkoxylated dialkyl esters for example ethoxylated and / or propoxylated and or butoxylated
  • alkyl esters of sulfuric acid alkoxylated alkyl esters (for example ethoxylated and / or propoxylated and / or butoxylated) of sulfuric acid, alkylsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids, as well as their salts
  • alkoxylated alkylamines particularly ethoxylated fatty amines, propoxylated fatty amines and butoxylated fatty amines, such as coconut amine ethoxylates, oleylamine ethoxylates, tallow amine ethoxylates or diamine e
  • primary, secondary or tertiary amines preferably the salts of primary or secondary amines with alkoxylated alkyl esters of phosphoric acid, such as ethoxylated monoalkyl esters of phosphoric acid, dialkyl ethoxylated esters of phosphoric acid , for example salts formed with octadecylamine and n-octadecyl monoester of phosphoric acid, salts formed with octadecylamine and ethoxylated n-octadecyl monoester of phosphoric acid, salts formed with octadecylamine and n-octadecyl propoxylated monoester of phosphoric acid, salts formed with octadecylamine and n-octadecyl diester of phosphoric acid, salts formed with octadecylamine and ethoxylated n
  • alkoxylated fatty acids particularly ethoxylated fatty acids, propoxylated fatty acids and butoxylated fatty acids, such as lauric acid ethoxylates or oleic acid ethoxylates,
  • alkoxylated natural oils and fats particularly ethoxylated, propoxylated or butoxylated natural oils, such as ethoxylated lanolin, ethoxylated castor oil or ethoxylates from rapeseed oil,
  • sorbitan ester alkoxylates particularly sorbitan ester ethoxylates, sorbitan ester propoxylates and sorbitan ester butoxylates, such as ethoxylated sorbitan monolaurates, ethoxylated sorbitan monostearates or trioleates sorbitan ethoxylates,
  • poly (alkylene oxide) copolymers in the form of either a block or random structure, such as poly (ethylene oxide) -b-polypropylene copolymer, poly (ethylene oxide) -b copolymers -poly (propylene oxide) -b-poly (ethylene oxide), copolymers of poly (propylene oxide) -b-poly (ethylene oxide) -b- poly (propylene oxide), copolymers of poly (propylene oxide) -b-poly (ethylene oxide) -b-poly (butylene oxide) and random copolymers of poly (ethylene oxide) -poly (propylene oxide),
  • alkylsulphonates • alkylsulphonates, arylsulphonates, alkylethersulphates, (alkoxylated alkyl) sulphates and
  • characteristic examples of surfactants based on alkoxylated alkyl esters of phosphoric acid include, without limitation, the ethoxylated hexyl monoester of phosphoric acid, the diester ethoxylated hexyl phosphoric acid, ethoxylated n-octyl monoester of phosphoric acid, ethoxylated n-octyl diester of phosphoric acid, ethoxylated iso-octyl monoester of phosphoric acid, ethoxylated iso-octyl diester phosphoric acid, ethoxylated phosphoric acid 2-octyl monoester, phosphoric acid ethoxylated 2-octyl diester, phosphoric acid ethoxylated 9-decenyl monoester, ethoxylated 9-decenyl diester 'phosphoric acid,
  • the invention also comprises the propoxylated and butoxylated derivatives of the phosphoric esters listed above as well as their mixtures.
  • the alkoxylated surfactant intended for use in the formulation of the present invention may inherently exhibit anti-caking activity.
  • the alkoxylated surfactant has a viscosity of less than 5000 mPa.s at 25 ° C, as measured using a dynamic shear rheometer (Anton Paar MCR301) in a geometry to 50 mm parallel plates (PP50) at 25 ° C and at a shear rate of 80 s 1 .
  • the alkoxylated surfactant is used in dosages of 1% by weight to 30% by weight and preferably from 1% by weight to 25% by weight, more preferably from 2% by weight to 20% by weight and even more preferably from 2% by weight to 15% by weight, relative to the total weight of the composition comprising the polyalcohol a) and said alkoxylated surfactant b).
  • the claimed formulation also comprises one or more solvents which are generally, but not exclusively, chosen from among water and monoalcohols.
  • monoalcohols which can be used as a solvent in the formulation of the present invention include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, cyclopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, iso-octanol, 2-octanol, n-nonanol, isononanol, n-decanol, isodecanol, 9-decenol, 10-unde
  • the amount of solvent depends considerably on the nature of the alkoxylated surfactant (s) and of the polyalcohol (s) present in the formulation, but also on the envisaged application and on the viscosity overall desired formulation.
  • the amount of solvent (s) in the formulation is within a range of 0.5 wt% to 30 wt%, preferably 2 wt% to 25 wt%, more preferably 5 wt% to 20% by weight, relative to the total weight of the formulation of the invention.
  • the present invention relates to the use of the formulation described above as a coating formulation for particles in order to reduce and even avoid the effect of agglomeration and / or the dust generation.
  • the present invention also relates to particles coated with the formulation of the present invention as described above.
  • Particles which can be coated with the formulation described above in the sense of the present invention can be soluble in water and / or solvent (s) or insoluble in water and / or / partially water-soluble solvent (s) and / or solvent (s).
  • Preferred particles for use in the present invention are preferably partially or totally, still more preferably completely soluble in water.
  • the particles intended for use in the context of the present invention can be of different shapes and nature and include, as non-limiting examples, granulated mineral or organic particles and in particular fertilizer particles or granules, coal, ores, mineral aggregates, sulfur, wood particles (such as for example chips and pellets), dirt, granulated waste, drugs, cereals, seeds, granulated or pelletized animal feed and the like and more preferably fertilizer particles or granules.
  • fertilizer particles or granules coal, ores, mineral aggregates, sulfur, wood particles (such as for example chips and pellets), dirt, granulated waste, drugs, cereals, seeds, granulated or pelletized animal feed and the like and more preferably fertilizer particles or granules.
  • fertilizer particles or granules coal, ores, mineral aggregates, sulfur, wood particles (such as for example chips and pellets), dirt, granulated waste, drugs, cereals, seeds, granulated or pelletized animal feed and the like and more preferably fertiliz
  • the fertilizer particles can be obtained from any known process for producing fertilizers, such as granulation, grinding, mixing, assembling, crystallization, compaction, pelletization, extrusion or graining and the like.
  • the fertilizer particles in the sense of the present invention include ammonium nitrates, nitrophosphates, ammonium phosphate-sulfate, ammonium sulfate, calcium ammonium nitrates.
  • the fertilizer particles are chosen from sulphates, such as ammonium sulphates or potassium sulphate and phosphates such as single or triple superphosphate and monoammonium phosphate. .
  • the invention is implemented particularly advantageously with water-soluble fertilizers.
  • the formulation of the present invention can be applied using known techniques, well known to those skilled in the art, and particularly using similar known methods used for coating particles in general and in particularly such as those used for coating granular fertilizers and particularly according to well known spray coating techniques.
  • the coating can be carried out using a batch process or a continuous process.
  • the granulated fertilizer can be introduced into a rotating coating drum while the coating is applied through one or more pressurized nozzles.
  • the coating can also be sprayed while the granulated fertilizer rotates on an inclined granulation drum or is inside a fluidized bed chamber.
  • the coating step by the coating formulation of the present invention can be carried out before and / or at the same time and or after the coating (s) of another material, such as for example the coating with additional nutrients or additional biological functions which are useful for soils or animals or plants, coating with anti-caking agents such as, for example, clays (eg kaolin), talc and the like.
  • another material such as for example the coating with additional nutrients or additional biological functions which are useful for soils or animals or plants, coating with anti-caking agents such as, for example, clays (eg kaolin), talc and the like.
  • the amount of formulation coated on said particle can vary in large proportions and amounts, advantageously and preferably between 0.01% by weight and 10% by weight , more preferably between 0.02% by weight and 5% by weight, even more preferably between 0.02% by weight and 2% by weight, limit values included, with respect to the total mass of the coated particle.
  • the present invention also relates to the formulation applied to a particle, preferably a granular material, and, according to a preferred embodiment, the invention relates to the formulation applied to a particle, preferably a granular material. , in an amount ranging from 0.01% by weight to 10% by weight, more preferably from 0.02% by weight to 5% by weight, still more preferably from 0.02% by weight to 2% by weight, values limits included, relative to the total mass of the formulation and the particle.
  • the invention also relates to a particle, preferably the granular material, coated with the formulation of the present invention.
  • a particle preferably the granular material, for example and preferably a fertilizer granule
  • the liquid formulation of the present invention is effective in achieving l '' one or more of the following purposes:
  • the formulation of the present invention makes it possible to obtain coated particles, and preferably coated fertilizers, having one or more of the advantages below, among which may be mentioned:
  • the liquid coating is in line with the current change in European law aimed at reducing / eliminating the use of non-biodegradable polymers in fertilizers, • its use is simple, ie the same current coating process can be used (spraying / coating equipment, same spraying temperatures, etc.),
  • Formulation A is prepared by mixing 47.5 g of glycerolated water (by-product of the castor oil refining process, supplied by ARKEMA under the trade name "Glycerine waters” , which contains approximately 5% water) and 2.5 g of a castor oil ethoxylated with 40 units of ethylene oxide (marketed under the name Surfaline R40L by ARKMEA), with stirring and at room temperature.
  • the formulation remains homogeneous after mixing.
  • the surface tension of formulation A is measured using a goniometer (DSA30 from Krüss) using the hanging drop configuration at 21 ° C.
  • Comparative Formulation B is prepared by mixing 46.25 g of mineral oil (Oil 700NS by Colas) and 3.75 g tallow amine (Noram ® S by ARKEMA) with stirring at a controlled temperature of 60 ° C. The formulation remains homogeneous after mixing and cooling to room temperature.
  • Comparative formulation C consists of glycerolated water (a by-product of the castor oil refining process, supplied by ARKEMA, which contains about 5% water) and is used as is.
  • the viscosity of each of the formulations is measured using a dynamic shear rheometer (Anton Paar MCR301) in a 50 mm parallel plate geometry (PP50), between 50 ° C and 10 ° C at a shear rate of 80 s -1 giving a value of 48 mPa.s at 25 ° C for comparative formulation B, 326 mPa.s for comparative formulation C and 380 mPa.s for formulation A.
  • a dynamic shear rheometer Anton Paar MCR301
  • PP50 50 mm parallel plate geometry
  • the following tests are carried out in order to evaluate the tendency to agglomeration of a sample coated with granulated ammonium sulfate, AS, having a size distribution between 1.5 mm and 4.5 mm, after having been subjected to temperature and pressure during transportation.
  • Formulation A (according to the invention) as well as formulation B and formulation C (comparative formulations) of the preceding examples are used as coating on the granules of AS.
  • 500 g of AS granules are heated at 40 ° C for four hours before being mixed in an open-ended laboratory coating drum and sprayed with 0.4 g of coating formulation sample at 90 ° vs.
  • Metal molds are filled with 150 g of coated fertilizer, closed and subjected to a constant pneumatic pressure of 3 bars for 3 days. The samples are then stored at room temperature for 6 days.
  • formulation A exhibits excellent protection against agglomeration, better than an anti-caking coating commonly used based on fatty amines and mineral oils (comparative formulation B) and also better than comparative formulation C, where no surfactant is used.
  • the following tests are carried out in order to evaluate the quantity of dust released by a sample of coated NPK during transport.
  • the tests are carried out using a Microtrack optical dust measuring device.
  • a sample of 300 g of coated fertilizer is introduced into the apparatus and the dust generated by the drop (due to the impact after the drop) is recorded by optical methods for 60 seconds.
  • the amount of dust generated is proportional to the integral of the measured optical signal (arbitrary units) as a function of the measurement time.
  • the value of the integral allows the comparison of the dust-proof efficiency of the different coatings: the lower the value, the better the coating formulation.
  • the coated fertilizers (500 g) described in Example 1 are stored in a closed container at 40 ° C for 14 days before being tested for dust. Table 3 shows the values of the dust test integral for each coating.
  • Formulation A provides the best dust protection values (less dust generated after simulated storage). The value is significantly better than that of the same glycerolated water itself (formulation C) and that of the formulation which contains a standard surfactant based on fatty amine in mineral oil (formulation B).

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Abstract

The invention relates to a formulation comprising at least one solvent and a composition comprising a) 10% by weight to 99% by weight of at least one polyalcohol and b) 1% by weight to 30% by weight of at least one alkoxylated surfactant, boundary values included, relative to the total weight of the composition comprising a) + b). The invention also relates to the use of such a formulation as a coating formulation for particles with the aim of reducing or even preventing the effect of agglomeration and/or the generation of dust. The invention also relates to the particles coated with the anti-agglomeration and/or anti-dust formulation.

Description

FORMULATION D'ENROBAGE DE PROTECTION CONTRE L'AGGLOMERATION ET LA POUSSIERE, PARTICULE ENROBÉE COATING FORMULATION FOR PROTECTION AGAINST AGGLOMERATION AND DUST, COATED PARTICLE
[0001] La présente invention concerne des formulations d'enrobage pour des matériaux granulaires, tels que des engrais granulaires, afin d'améliorer leurs qualités intrinsèques de telle sorte que le stockage desdits matériaux granulaires soit plus simple et plus sûr. The present invention relates to coating formulations for granular materials, such as granular fertilizers, in order to improve their intrinsic qualities so that the storage of said granular materials is simpler and safer.
[0002] Les engrais et autres produits minéraux sont souvent stockés en grandes quantités pour différentes périodes de temps. Bon nombre d'entre eux ont tendance à s'agglomérer pendant le stockage et à générer des grandes quantités de poussière pendant le transport. L'agglomération peut rendre le transport et l'utilisation d'engrais et d'autres produits minéraux impossibles, car ils ne peuvent pas s’écouler. La poussière générée pendant le transport et pendant les opérations de chargement et de déchargement de ces produits peut générer de sérieux problèmes de sécurité et de santé dans la mesure où l'atmosphère peut se saturer en fines particules minérales. [0002] Fertilizers and other mineral products are often stored in large quantities for different periods of time. Many of them tend to clump together during storage and generate large amounts of dust during transport. Agglomeration can make the transport and use of fertilizers and other mineral products impossible because they cannot flow. The dust generated during transport and during the loading and unloading operations of these products can generate serious health and safety problems as the atmosphere can become saturated with fine mineral particles.
[0003] Une solution couramment connue pour résoudre ces problèmes est d'appliquer un fin enrobage d'une formulation liquide ou solide. Cette opération empêche généralement ou, du moins, ralentit le processus d'agglomération et supprime ou, du moins, réduit la génération de fines poussières depuis la surface de l'engrais ou du produit minéral granulaire. L'enrobage, sous forme liquide, est usuellement pulvérisé sur les granules juste avant le stockage. A commonly known solution for solving these problems is to apply a fine coating of a liquid or solid formulation. This generally prevents or at least slows down the agglomeration process and suppresses or at least reduces the generation of fine dust from the surface of the fertilizer or granular mineral product. The coating, in liquid form, is usually sprayed onto the granules just before storage.
[0004] Ces formulations d'enrobage sont principalement à base d'huiles minérales et comprennent souvent un ou plusieurs tensioactifs afin de réduire l'agglomération. De nombreuses publications mentionnent également des enrobages contenant des huiles provenant de sources renouvelables, telles que les huiles végétales, qui peuvent empêcher l'agglomération et la génération de poussière. Parmi ces publications, plusieurs d'entre elles décrivent l'utilisation de glycérol et de formulations contenant du glycérol pour l'application spécifique de l'enrobage à base de glycérol. These coating formulations are mainly based on mineral oils and often include one or more surfactants in order to reduce the agglomeration. Many publications also mention coatings containing oils from renewable sources, such as vegetable oils, which can prevent caking and generation of dust. Among these publications, several of them describe the use of glycerol and of formulations containing glycerol for the specific application of the coating based on glycerol.
[0005] Par exemple, le document US2008072641 décrit l'utilisation de compositions constituées du produit de réaction de glycérol et d'acides multifonctionnels pour la lutte contre l'agglomération et la poussière. En particulier, on mentionne l'acide citrique en combinaison avec le glycérol. Le constituant d'enrobage réel est alors un polyester issu de cette réaction. [0005] For example, document US2008072641 describes the use of compositions consisting of the reaction product of glycerol and multifunctional acids for the fight against agglomeration and dust. In particular, citric acid is mentioned in combination with glycerol. The actual coating constituent is then a polyester resulting from this reaction.
[0006] Le document US2006040049 décrit l'utilisation de sels métalliques d'acides gras en tant qu'agents antiagglomérants. Parmi les milieux de dispersion des compositions d'enrobage, on trouve les huiles végétales et le glycérol. Le document US2015367363 revendique une composition d’un matériau particulaire, de glycérol et d'un poly(acétate de vinyle) pour la lutte contre la poussière. Le document US2015144836 décrit, en tant qu'agent antipoussière, un copolymère de glycérol et d'un acide organique (à savoir l'acide hydrostéarique) et le document WO2014032131 divulgue une composition antipoussière comprenant du glycérol, une solution de sucre et éventuellement de l'acide citrique. [0006] Document US2006040049 describes the use of metal salts of fatty acids as anti-caking agents. Among the dispersion media for the coating compositions, there are vegetable oils and glycerol. US2015367363 claims a composition of a particulate material, glycerol and a poly (acetate). vinyl) for dust control. Document US2015144836 describes, as an anti-dust agent, a copolymer of glycerol and an organic acid (namely hydrostearic acid) and document WO2014032131 discloses a anti-dust composition comprising glycerol, a sugar solution and optionally l 'citric acid.
[0007] D'autres publications mentionnent l'utilisation de glycérol en tant qu'agent antipoussière, comme le document US2002184933, qui divulgue des agents antipoussière pour les engrais soufrés et le document US5383952 qui divulgue un agent antipoussière contenant de la mélasse et un autre liquide, incluant le glycérol. [0007] Other publications mention the use of glycerol as an anti-dust agent, such as document US2002184933, which discloses anti-dust agents for sulfur-containing fertilizers and document US5383952 which discloses a dust-control agent containing molasses and another liquid, including glycerol.
[0008] Toutes ces publications montrent que l'utilisation de glycérol en tant qu'agent antipoussière est assez connue actuellement, le glycérol étant usuellement combiné avec d'autres constituants afin de former un polymère. Les occurrences de formulations à base de glycérol destinées à des fins d'antiagglomération sont moins nombreuses. [0008] All these publications show that the use of glycerol as an anti-dust agent is fairly well known at present, glycerol being usually combined with other constituents in order to form a polymer. The occurrences of glycerol-based formulations intended for anti-caking purposes are less numerous.
[0009] Toutes ces formulations ou compositions connues contenant du glycérol souffrent cependant de nombreux inconvénients. En réalité, les enrobages actuellement connus comprenant du glycérol ne protègent généralement pas efficacement contre l'agglomération et la génération de poussière, ou le procédé d'enrobage du matériau granulaire peut s'avérer difficile et/ou plutôt difficile à mettre en oeuvre, en particulier lorsqu'une réaction de prépolymérisation est nécessaire ou lorsque l'enrobage doit être fondu avant application, et analogues, pour ne montrer que quelques exemples des nombreux désavantages. [0009] All of these known formulations or compositions containing glycerol, however, suffer from numerous drawbacks. In reality, the currently known coatings comprising glycerol do not generally protect effectively against agglomeration and dust generation, or the process of coating the granular material may prove to be difficult and / or rather difficult to carry out, in particular. particularly when a prepolymerization reaction is required or when the coating must be melted before application, and the like, to show only a few examples of the many disadvantages.
[0010] Il est donc évident que, malgré toutes ces formulations ou compositions antipoussière à base de glycérol connues, le besoin de formulations d'enrobage liquides améliorées pour réduire l'agglomération et la génération de poussière de particules minérales granulées et qui ne présentent pas les inconvénients des formulations connues dans l'état de la technique existe toujours. [0010] It is therefore evident that, despite all these known glycerol-based dust control formulations or compositions, the need for improved liquid coating formulations to reduce the agglomeration and generation of dust from granulated mineral particles and which do not exhibit the drawbacks of the formulations known in the state of the art still exist.
[0011] En tant que tel, un premier objectif de la présente invention est de proposer une formulation d'enrobage pour un matériau granulaire qui est utile pour éviter l'agglomération et/ou pour réduire la poussière générée pendant le transport. As such, a first object of the present invention is to provide a coating formulation for a granular material which is useful for preventing clumping and / or for reducing dust generated during transportation.
[0012] Un autre objectif de la présente invention est de proposer une formulation d'enrobage pour un matériau granulaire qui est utile pour éviter l'agglomération et/ou pour réduire la poussière générée pendant le transport, ladite formulation ne nécessitant pas de procédés d'enrobage compliqués. D'autres objectifs encore découleront de la description de la présente invention, qui est à présent divulguée ci-dessous. Another object of the present invention is to provide a coating formulation for a granular material which is useful for preventing agglomeration and / or for reducing dust generated during transport, said formulation not requiring processing methods. embedding complicated. Still other objects will follow from the description of the present invention, which is now disclosed below.
[0013] Les demandeurs ont découvert à présent que tous les objectifs ci-dessus ou, du moins, des parties de ceux-ci, peuvent être atteints par la présente invention qui concerne une formulation améliorée d'enrobage pour des matériaux granulaires, qui, autrement, montrent une tendance à s'agglomérer ou à générer de la poussière, tels que les engrais, les céréales, les farines et analogues. Applicants have now discovered that all of the above objects, or at least parts thereof, can be achieved by the present invention which relates to an improved coating formulation for granular materials, which otherwise show a tendency to clump or generate dust, such as fertilizers, grains, flour and the like.
[0014] Étant donné que des formulations d'enrobage contenant du polyol sont déjà connues et permettent d'obtenir des résultats relativement bons en termes de performances antiagglomération et antipoussière, comme par exemple les formulations d'enrobage à base de glycérol, les demandeurs ont effectué des recherches minutieuses pour essayer d'améliorer encore davantage les performances de ces formulations d'enrobage contenant du polyol. Et il a été découvert, de manière surprenante, que les performances de ces formulations sont améliorées par l'ajout de tensioactifs spécifiques, sélectionnés, auxdites formulations d'enrobage. Since coating formulations containing polyol are already known and make it possible to obtain relatively good results in terms of anti-agglomeration and dust-proof performance, such as for example coating formulations based on glycerol, the applicants have carried out careful research to try to further improve the performance of these coating formulations containing polyol. And it has been discovered, surprisingly, that the performance of these formulations is improved by adding specific, selected surfactants to said coating formulations.
[0015] Par conséquent, et dans un premier aspect, la présente invention concerne une formulation comprenant : [0015] Therefore, and in a first aspect, the present invention relates to a formulation comprising:
1 ) une composition comprenant a) 10 % en poids à 99 % en poids d'au moins un polyalcool et b) 1 % en poids à 90 % en poids, préférablement 1 % en poids à 70 % en poids, plus préférablement 1 % en poids à 50 % en poids, encore plus préférablement 1 % en poids à 30 % en poids d'au moins un tensioactif alcoxylé, valeurs limites incluses, par rapport au poids total de la composition comprenant a) + b) et 2) au moins un solvant. 1) a composition comprising a) 10% by weight to 99% by weight of at least one polyalcohol and b) 1% by weight to 90% by weight, preferably 1% by weight to 70% by weight, more preferably 1% by weight by weight at 50% by weight, even more preferably 1% by weight at 30% by weight of at least one alkoxylated surfactant, limit values included, relative to the total weight of the composition comprising a) + b) and 2) in minus a solvent.
[0016] L'au moins un solvant présent dans la formulation selon l'invention peut être un quelconque solvant connu par l'homme du métier et préférablement choisi parmi les monoalcools et l'eau ainsi que leurs mélanges. Sans indication contraire, toutes les plages numériques et de pourcentage dans la présente description incluent les limites des plages. [0017] La formulation de la présente invention peut également comprendre un ou plusieurs autres constituants couramment utilisés dans la technique, incluant, de manière non limitative, et choisis habituellement parmi les additifs, les charges et analogues, tels que par exemple l'un ou plusieurs de ceux-ci parmi : The at least one solvent present in the formulation according to the invention can be any solvent known to those skilled in the art and preferably chosen from monoalcohols and water as well as their mixtures. Unless otherwise specified, all numeric and percentage ranges in this specification include range limits. The formulation of the present invention can also comprise one or more other constituents commonly used in the art, including, without limitation, and usually chosen from additives, fillers and the like, such as for example one or several of these among:
• les agents antiagglomérants, tels que les alkylamines, les esters alkylphosphoriques, les alcools alkyliques linéaires, les sulfates d’alkyléther, les alkylsulfonates, les arylsulfonates, les alkyléthersulfonates et leurs combinaisons, préférablement les sels d’alkylamines avec les esters alkylphosphoriques, • anti-caking agents, such as alkylamines, alkylphosphoric esters, linear alkyl alcohols, alkylether sulfates, alkylsulfonates, arylsulfonates, alkylethersulfonates and their combinations, preferably alkylamines salts with alkylphosphoric esters,
• les agents de modification de la rhéologie, tels que les polymères biodégradables et non- biodégradables, les cires, préférablement les cires provenant de sources renouvelables, minérales, ou les cires synthétiques, telles que les cires de Fischer-Tropsch, les amidoamides, les alkylamidoamides, • les agents d’hydrofugation, tels que les alcools alkyliques linéaires et les cires microcristallines, • rheology modifiers, such as biodegradable and non-biodegradable polymers, waxes, preferably waxes from renewable, mineral sources, or synthetic waxes, such as Fischer-Tropsch waxes, amidoamides, alkylamidoamides, • waterproofing agents, such as linear alkyl alcohols and microcrystalline waxes,
• les agents de dispersion, tels que les huiles provenant de sources végétales et minérales, • dispersing agents, such as oils from vegetable and mineral sources,
• les colorants, les traceurs UV, les pigments, • dyes, UV tracers, pigments,
• les micronutriments minéraux et/ou organiques et les oligoéléments, qui peuvent être, mais sont préférablement, finement dispersés et/ou compatibilisés, par exemple les complexes métalliques, • inorganic and / or organic micronutrients and trace elements, which can be, but are preferably, finely dispersed and / or compatibilized, for example metal complexes,
• les pesticides, tels que les insecticides, les herbicides, les fongicides, les nématocides et similaires, • pesticides, such as insecticides, herbicides, fungicides, nematocides and the like,
• les bactéries, la levure, les champignons, les virus, les enzymes, • bacteria, yeast, fungi, viruses, enzymes,
• les antioxydants, les conservateurs, les agents anti-UV, • antioxidants, preservatives, anti-UV agents,
• les agents de masquage d’odeur, les antiodorants, les arômes, les parfums, • odor masking agents, anti-odorants, flavors, fragrances,
• ainsi que les mélanges de deux ou plus des constituants énumérés ci-dessus. • as well as mixtures of two or more of the constituents listed above.
[0018] Parmi les agents antiagglomérants, on peut mentionner les agents antiagglomérants cationiques, tels que par exemple ceux choisis parmi les amines primaires, secondaires et tertiaires, ainsi que leurs sels, préférablement les amines primaires de formule R-NH , dans laquelle R représente une chaîne hydrocarbonée comprenant 8 à 36 atomes de carbone, préférablement 12 à 24 atomes de carbone et plus préférablement la chaîne hydrocarbonée est une chaîne hydrocarbonée linéaire ou ramifiée, encore plus préférablement une chaîne hydrocarbonée linéaire et le plus préférablement une chaîne alkyle linéaire en C8-C36, le plus préférablement une chaîne alkyle linéaire en C12-C24. Préférablement, l'agent antiagglomérant contenant de l'azote est choisi parmi les amines primaires, secondaires et tertiaires, ainsi que leurs sels, et plus préférablement, le tensioactif contenant de l'azote est une amine grasse, plus préférablement une amine grasse linéaire saturée comprenant 16 à 18 atomes de carbone. [0019] Selon un autre mode de réalisation, l'agent antiagglomérant est un agent antiagglomérant anionique choisi parmi les esterphosphates d'alcools gras, tels que par exemple ceux décrits dans "Encyclopedia of Chemical Technology", 4ème édition, Kirk- Othmer, volume 23, pages 504-505, (1997), dans "Ullmann's Encyclopedia of Industrial Chemistry", 5ème édition, Elvers B., Hawkins S., Schulz G., volume A19, pages 562-564 ou encore dans "Phosphorous-containing Anionic Surfactants", Wasow G., ou encore dans «Anionic Surfactants: Organic Chemistry », volume 56, Marcel Dekker, (1996), pages 552- [0020] Selon encore un autre mode de réalisation de la présente invention, les esterphosphates destinés à être utilisés en tant qu’additifs d’agent antiagglomérant dans la formulation de l’invention comprennent, entre autres, les esters présentant une chaîne hydrocarbonée linéaire ou ramifiée, saturée ou insaturée en C6-C3o, préférablement en C6- C2o et plus préférablement une chaîne hydrocarbonée linéaire et saturée et plus particulièrement le monoester hexylique de l’acide phosphorique, le diester hexylique de l’acide phosphorique, le monoester n-octylique de l’acide phosphorique, le diester n- octylique de l’acide phosphorique, le monoester iso-octylique de l’acide phosphorique, le diester iso-octylique de l’acide phosphorique, le monoester 2-éthylhexylique de l’acide phosphorique, le diester 2-éthylhexylique de l’acide phosphorique, le monoester 2-octylique de l’acide phosphorique, le diester 2-octylique de l’acide phosphorique, le monomère n- décylique de l’acide phosphorique, le monoester 9-décénylique de l’acide phosphorique, le diester 9-décénylique de l’acide phosphorique, le monoester isodécylique de l’acide phosphorique, le diester n-décylique de l’acide phosphorique, le diester isodécylique de l’acide phosphorique, le monoester 10-undécénylique de l’acide phosphorique, le diester 10-undécénylique de l’acide phosphorique, le monoester n-dodécylique de l’acide phosphorique, le monoester isododécylique de l’acide phosphorique, le diester n- dodécylique de l’acide phosphorique, le diester isododécylique de l’acide phosphorique, le monoester n-tétradécylique de l’acide phosphorique, le monoester isotétradécylique de l’acide phosphorique, le diester n-tétradécylique de l’acide phosphorique, le diester isotétradécylique de l’acide phosphorique, le monoester n-hexadécylique de l’acide phosphorique, le monoester isohexadécylique de l’acide phosphorique, le diester n- hexadécylique de l’acide phosphorique, le diester isohexadécylique de l’acide phosphorique, le monoester n-octadécylique de l’acide phosphorique, le monoester iso- octadécylique de l’acide phosphorique, le diester n-octadécylique de l’acide phosphorique, le diester iso-octadécylique de l’acide phosphorique et leurs mélanges. Among the anti-caking agents, mention may be made of cationic anti-caking agents, such as for example those chosen from primary, secondary and tertiary amines, as well as their salts, preferably the primary amines of formula R-NH, in which R represents a hydrocarbon chain comprising 8 to 36 carbon atoms, preferably 12 to 24 carbon atoms and more preferably the hydrocarbon chain is a linear or branched hydrocarbon chain, still more preferably a linear hydrocarbon chain and most preferably a linear C 8 alkyl chain -C 36 , most preferably a linear C12-C24 alkyl chain. Preferably, the nitrogen-containing anti-caking agent is selected from primary, secondary and tertiary amines, as well as their salts, and more preferably, the nitrogen-containing surfactant is a fatty amine, more preferably a saturated linear fatty amine. comprising 16 to 18 carbon atoms. According to another embodiment, the anti-caking agent is an anionic anti-caking agent chosen from esterphosphates of fatty alcohols, such as for example those described in "Encyclopedia of Chemical Technology", 4th edition, Kirk-Othmer, volume 23, 504-505 pages (1997), in "Ullmann's Encyclopedia of Industrial Chemistry", 5th edition, B. Elvers, S. Hawkins, G. Schulz, volume A19, pages 562-564 or in "Phosphorous-containing Anionic Surfactants ", Wasow G., or also in" Anionic Surfactants: Organic Chemistry ", volume 56, Marcel Dekker, (1996), pages 552- According to yet another embodiment of the present invention, the esterphosphates intended for use as anti-caking agent additives in the formulation of the invention comprise, inter alia, esters having a linear hydrocarbon chain or branched, saturated or unsaturated C 6 -C 3 o, preferably C 6 - C 2 o and more preferably a linear and saturated hydrocarbon chain and more particularly the hexyl monoester of phosphoric acid, the hexyl diester of phosphoric acid , phosphoric acid n-octyl monoester, phosphoric acid n-octyl diester, phosphoric acid iso-octyl monoester, phosphoric acid iso-octyl diester, 2-ethylhexyl monoester phosphoric acid, 2-ethylhexyl diester of phosphoric acid, 2-octyl monoester of phosphoric acid, 2-octyl diester of phosphoric acid, n-decyl monomer of phosphoric acid as, 9-decenyl phosphoric acid monoester, 9-decenyl phosphoric acid diester, isodecyl monoester of phosphoric acid, n-decyl diester of phosphoric acid, isodecyl diester of phosphoric acid, phosphoric acid, 10-undecenyl monoester of phosphoric acid, 10-undecenyl diester of phosphoric acid, n-dodecyl monoester of phosphoric acid, isododecyl monoester of phosphoric acid, n-dodecyl diester phosphoric acid, isododecyl diester of phosphoric acid, n-tetradecyl monoester of phosphoric acid, isotetradecyl monoester of phosphoric acid, n-tetradecyl diester of phosphoric acid, isotetradecyl diester of phosphoric acid phosphoric acid, n-hexadecyl monoester of phosphoric acid, isohexadecyl monoester of phosphoric acid, n-hexadecyl diester of phosphoric acid, isohexadecyl diester of phosphoric acid e, n-octadecyl monoester of phosphoric acid, iso-octadecyl monoester of phosphoric acid, n-octadecyl diester of phosphoric acid, iso-octadecyl diester of phosphoric acid, and mixtures thereof.
[0021 ] Des exemples spécifiques d'agents antiagglomérants qui peuvent être ajoutés à la formulation de la présente invention incluent également les agents antiagglomérants anioniques et cationiques, ainsi que leurs mélanges et par exemple les mélanges comprenant un sel formé à partir d'un agent antiagglomérant contenant de l'azote et d'un agent antiagglomérant anionique de type acide, par exemple et préférablement un ester de l'acide phosphorique ou sulfurique ou alkyl(aryl)sulfonique. Specific examples of anti-caking agents which can be added to the formulation of the present invention also include anionic and cationic anti-caking agents, as well as their mixtures and for example mixtures comprising a salt formed from an anti-caking agent containing nitrogen and an acid-type anionic anti-caking agent, for example and preferably an ester of phosphoric or sulfuric or alkyl (aryl) sulfonic acid.
[0022] Des agents antiagglomérants encore plus préférables qui peuvent être utilisés dans la composition de la présente invention incluent les mélanges comprenant au moins un agent antiagglomérant choisi parmi les amines primaires, secondaires ou tertiaires, préférablement parmi les amines primaires et secondaires, ainsi que leurs sels, et au moins un ester alkylique de l'acide phosphorique, tels que ceux décrits ci-dessous. Even more preferable anti-caking agents which can be used in the composition of the present invention include mixtures comprising at least one anti-caking agent selected from primary, secondary or tertiary amines, preferably from primary and secondary amines, as well as their salts, and at least one alkyl ester of phosphoric acid, such as those described below.
[0023] Selon un autre mode de réalisation, l'agent antiagglomérant utilisé en tant qu'additif dans la formulation de la présente invention est un mélange comprenant au moins un tensioactif choisi parmi les amines primaires, secondaires ou tertiaires, préférablement parmi les amines primaires et secondaires, ainsi que leurs sels, et au moins un tensioactif anionique choisi parmi les esters monoalkyliques et dialkyliques de l'acide phosphorique. [0024] Selon un autre mode de réalisation, les agents antiagglomérants comprennent des agents antiagglomérants anioniques et cationiques, ainsi que leurs mélanges et par exemple les mélanges comprenant les esters monoalkyliques de l'acide phosphorique, les esters dialkyliques de l'acide phosphorique, les esters alkyliques de l'acide sulfurique, les acides alkylsulfoniques, les acides arylsulfoniques, les acides alkylarylsulfoniques ainsi que leurs sels. According to another embodiment, the anti-caking agent used as an additive in the formulation of the present invention is a mixture comprising at least one surfactant chosen from primary, secondary or tertiary amines, preferably from primary amines and secondary, as well as their salts, and at least one anionic surfactant chosen from monoalkyl and dialkyl esters of phosphoric acid. According to another embodiment, the anti-caking agents comprise anionic and cationic anti-caking agents, as well as their mixtures and for example mixtures comprising the monoalkyl esters of phosphoric acid, the dialkyl esters of phosphoric acid, the compounds thereof. Alkyl esters of sulfuric acid, alkylsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids and their salts.
[0025] Selon encore un autre mode de réalisation préféré, l'agent antiagglomérant destiné à être utilisé dans la formulation de la présente invention est un mélange comprenant au moins un tensioactif choisi parmi les amines primaires, secondaires ou tertiaires, préférablement parmi les amines primaires et secondaires, ainsi que leurs sels et un tensioactif anionique choisi parmi les acides alkylsulfoniques, les acides arylsulfoniques, les acides alkylarylsulfoniques et leurs sels, par exemple le mélange formé avec de l'octadécylamine et de l'acide dodécylsulfonique ou le mélange formé avec de l'octadécylamine et de l'acide dodécylbenzènesulfonique. According to yet another preferred embodiment, the anti-caking agent intended to be used in the formulation of the present invention is a mixture comprising at least one surfactant chosen from primary, secondary or tertiary amines, preferably from primary amines and secondary, as well as their salts and an anionic surfactant chosen from alkylsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids and their salts, for example the mixture formed with octadecylamine and dodecylsulfonic acid or the mixture formed with octadecylamine and dodecylbenzenesulfonic acid.
[0026] Selon un mode de réalisation préféré, la formulation de la présente invention est préférablement et avantageusement liquide à température ambiante (25 °C). Selon un autre mode de réalisation préféré, la viscosité de la formulation selon la présente invention, telle que mesurée à l'aide d'un rhéomètre à cisaillement dynamique (Anton Paar MCR301 ) dans une géométrie à plaques parallèles de 50 mm (PP50) à 25 °C à une vitesse de cisaillement de 80 s-1, se situe habituellement dans la plage de 1 mPa.s à l OOO mPa.s et plus préférablement de 2 mPa.s à 800 mPa.s, valeurs limites incluses. According to a preferred embodiment, the formulation of the present invention is preferably and advantageously liquid at room temperature (25 ° C). According to another preferred embodiment, the viscosity of the formulation according to the present invention, as measured using a dynamic shear rheometer (Anton Paar MCR301) in a 50 mm parallel plate geometry (PP50) to 25 ° C at a shear rate of 80 s -1 , is usually in the range 1 mPa.s to 1000 mPa.s and more preferably 2 mPa.s to 800 mPa.s, limit values included.
[0027] Un polyalcool dans le sens de l’invention est un composé qui comprend plus d’un groupe fonctionnel -OH. Des exemples de polyalcools appropriés incluent, sans s’y limiter, le glycérol (ou le 1 ,2,3-propanetriol), les diglycérols, les polyglycérols, l’éthylèneglycol, le diéthylèneglycol, le polyéthylèneglycol, le propylèneglycol, le dipropylèneglycol, le polypropylèneglycol, le néopentylglycol, le triméthylolpropane, l’érythritol, le xylitol, le thréitol, le mannitol, le sorbitol, le galactitol, le fucitol, l’iditol, l’inositol, le volémitol, l’isomalt, le maltitol, le lactitol, le maltotriitol, le maltotétra-itol, l’isosorbide, l’iso-idide, l’isomannide, la dextrine, le dextrose, les disaccharides, le fructose, le sucrose, le galactose, le lactose, le maltose, la maltodextrine, le mannose, le saccharose, le xylose, ainsi que les sucres provenant de sources naturelles, par exemple le sucre de canne, le caramel, le sucre semoule, le sirop de maïs et les mélasses, ainsi que leurs mélanges. A polyalcohol in the sense of the invention is a compound which comprises more than one -OH functional group. Examples of suitable polyalcohols include, but are not limited to, glycerol (or 1,2,3-propanetriol), diglycerols, polyglycerols, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, trimethylolpropane, erythritol, xylitol, threitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol , maltotriitol, maltotetra-itol, isosorbide, iso-idide, isomannide, dextrin, dextrose, disaccharides, fructose, sucrose, galactose, lactose, maltose, maltodextrin, mannose, sucrose, xylose, as well as sugars from natural sources, for example cane sugar , caramel, caster sugar, corn syrup and molasses, as well as their mixtures.
[0028] Préférablement, le polyalcool présente une viscosité inférieure à 5000 mPa.s à 25°C, telle que mesurée à l’aide d'un rhéomètre à dsaillement dynamique (Anton Paar MCR301 ) dans une géométrie à plaques parallèles de 50 mm (PP50) à 25°C et à une vitesse de cisaillement de 80 s-1. Encore plus préférablement, l'au moins un polyalcool est le glycérol. Preferably, the polyalcohol has a viscosity of less than 5000 mPa.s at 25 ° C, as measured using a dynamic shear rheometer (Anton Paar MCR301) in a parallel plate geometry of 50 mm ( PP50) at 25 ° C and a shear rate of 80 s -1 . Even more preferably, the at least one polyalcohol is glycerol.
[0029] Le glycérol qui peut être utilisé dans le cadre de la présente invention peut provenir de diverses sources, soit de sources fossiles soit de plantes soit d’animaux et, par exemple, et sans s'y limiter, le glycérol est un glycérol brut tel que celui obtenu à partir de production de biodiesel. Le glycérol brut est particulièrement approprié pour la préparation de la formulation de la présente invention, étant donné qu'on peut le trouver en grandes quantités à un prix raisonnable. The glycerol which can be used in the context of the present invention can come from various sources, either from fossil sources or from plants or animals and, for example, and not limited to it, the glycerol is a glycerol crude such as that obtained from the production of biodiesel. Crude glycerol is particularly suitable for the preparation of the formulation of the present invention, since it can be found in large quantities at a reasonable price.
[0030] Le glycérol brut est donc largement disponible et bien connu par l'homme du métier, qui peut trouver une description complète de ce composé dans l'article écrit par Pal et Chaurasia "Characterization of Crude and Purified glycérol from biodiesel Production and Purification Techniques", Vth international Symposium of Fusion of Science and Technology, New Delhi, Inde, janvier 2016. Crude glycerol is therefore widely available and well known to those skilled in the art, who can find a complete description of this compound in the article written by Pal and Chaurasia "Characterization of Crude and Purified glycerol from biodiesel Production and Purification Techniques ", V th international Symposium of Fusion of Science and Technology, New Delhi, India, January 2016.
[0031] Comme déjà expliqué ci-dessus, le polyalcool qui fait partie de la formulation de la présente invention est utilisé à des dosages entre 10 % en poids et 99 % en poids, par rapport au poids total de la composition comprenant le polyalcool a) et le tensioactif alcoxylé b). Préférablement, le polyalcool est utilisé à des dosages entre 20 % en poids et 95 % en poids, plus préférablement entre 30 % en poids et 90 % en poids et encore plus préférablement entre 50 % en poids et 85 % en poids, par rapport au poids total de la composition comprenant le polyalcool a) et le tensioactif alcoxylé b). As already explained above, the polyalcohol which forms part of the formulation of the present invention is used in dosages between 10% by weight and 99% by weight, relative to the total weight of the composition comprising the polyalcohol a ) and the alkoxylated surfactant b). Preferably, the polyalcohol is used in dosages between 20% by weight and 95% by weight, more preferably between 30% by weight and 90% by weight and even more preferably between 50% by weight and 85% by weight, based on total weight of the composition comprising the polyalcohol a) and the alkoxylated surfactant b).
[0032] Le tensioactif alcoxylé qui peut être utilisé dans la formulation de la présente invention peut être n'importe quel tensioactif alcoxylé connu par l'homme du métier en tant que composé qui abaisse la tension superficielle du polyalcool et qui comprend une séquence d'un ou de plusieurs motifs alkylénoxy choisis parmi éthylénoxy, propylénoxy, butylénoxy ou leurs mélanges. Préférablement, le tensioactif alcoxylé comprend au moins 3 motifs alkylénoxy récurrents provenant de l'ouverture d'un cycle oxirane. Préférablement, le tensioactive alcoxylé comprend au plus 100, préférablement au plus 80, encore plus préférablement au plus 60 motifs alkylénoxy récurrents provenant de l'ouverture d'un cycle oxirane. [0032] The alkoxylated surfactant which can be used in the formulation of the present invention can be any alkoxylated surfactant known to those skilled in the art as a compound which lowers the surface tension of the polyalcohol and which comprises a sequence of one or more alkylenoxy units chosen from ethylenoxy, propylenoxy, butylenoxy or their mixtures. Preferably, the alkoxylated surfactant comprises at least 3 repeating alkylenoxy units originating from the opening of an oxirane ring. Preferably, the alkoxylated surfactant comprises at most 100, preferably at most 80, even more preferably at most 60 recurring alkylenoxy units originating from the opening of a ring. oxirane.
[0033] Selon un mode de réalisation préféré de la présente invention, le tensioactif alcoxylé comprend 3 à 100 motifs alkylénoxy récurrents, plus préférablement 3 à 80 motifs alkylénoxy récurrents et plus préférablement 3 à 60 motifs alkylénoxy récurrents, provenant de l'ouverture d'un cycle oxirane. Encore plus préférablement, le tensioactif alcoxylé de l'invention est un tensioactif éthoxylé comprenant 3 à 100 motifs éthylénoxy récurrents, plus préférablement 3 à 80 motifs éthylénoxy récurrents et plus préférablement 3 à 60 motifs éthylénoxy récurrents, provenant de l'ouverture d'un cycle oxirane. According to a preferred embodiment of the present invention, the alkoxylated surfactant comprises 3 to 100 recurring alkylenoxy units, more preferably 3 to 80 recurring alkylenoxy units and more preferably 3 to 60 recurring alkylenoxy units, originating from the opening of ' an oxirane ring. Even more preferably, the alkoxylated surfactant of the invention is an ethoxylated surfactant comprising 3 to 100 repeating ethylenoxy units, more preferably 3 to 80 recurring ethylenoxy units and more preferably 3 to 60 recurring ethylenoxy units, originating from the opening of a ring. oxirane.
[0034] Les tensioactifs alcoxylés qui peuvent être utiles dans la formulation de la présente invention peuvent être représentés par un grand nombre de composés alcoxylés qui peuvent porter un ou plusieurs hétéroatomes, présentant ainsi un ou plusieurs groupes fonctionnels portant des atomes d'oxygène et/ou d'azote et ou de soufre et/ou de phosphore. The alkoxylated surfactants which may be useful in the formulation of the present invention may be represented by a large number of alkoxylated compounds which may bear one or more heteroatoms, thus having one or more functional groups bearing oxygen atoms and / or nitrogen and or sulfur and / or phosphorus.
[0035] Des exemples caractéristiques et non limitatifs de tensioactifs alcoxylés comprennent : Typical and non-limiting examples of alkoxylated surfactants include:
• les alcools alkylaryliques alcoxylés, où l’alcool alkylarylique est l’un ou l’autre parmi les alcools gras particulièrement éthoxylés, les alcools gras propoxylés, les alcools gras butoxylés, linéaires ou ramifiés, saturés ou insaturés, tels que le glycérol éthoxylé, le glycérol propoxylé, les alcools octyliques éthoxylés, les alcools octyliques ramifiés éthoxylés, les alcools dodécyliques éthoxylés, les alcools octadécyliques éthoxylés, les dérivés de cardanol éthoxylés, les éthoxylates et propoxylates de nonylphénol, les éthoxylates et propoxylates de tristyrylphénol, • alkoxylated alkylaryl alcohols, where the alkylaryl alcohol is either one of particularly ethoxylated fatty alcohols, propoxylated fatty alcohols, butoxylated, linear or branched, saturated or unsaturated fatty alcohols, such as ethoxylated glycerol, propoxylated glycerol, ethoxylated octyl alcohols, ethoxylated branched octyl alcohols, ethoxylated dodecyl alcohols, ethoxylated octadecyl alcohols, ethoxylated cardanol derivatives, nonylphenol ethoxylates and propoxylates, tristol ethoxylates and propoxylates,
• les esters alkyliques alcoxylés de l'acide phosphorique, particulièrement les esters alkyliques alcoxylés de l’acide phosphorique présentant une chaîne hydrocarbonée linéaire ou ramifiée, saturée ou insaturée, préférablement une chaîne hydrocarbonée linéaire et saturée en C6-C3o, avantageusement une chaîne hydrocarbonée linéaire et saturée en C6- C2o et présentant une séquence d’un ou de plusieurs, préférablement d’un à dix, plus préférablement de 3 à 8, groupes choisis parmi l’oxyde d’éthylène, l’oxyde de propylène, l’oxyde de butylène et leurs mélanges, • alkoxylated alkyl esters of phosphoric acid, particularly alkoxylated alkyl esters of phosphoric acid having a linear or branched, saturated or unsaturated hydrocarbon chain, preferably a linear and saturated C 6 -C 3 o hydrocarbon chain, advantageously a linear and saturated C 6 - C 2 o hydrocarbon chain and having a sequence of one or more, preferably from one to ten, more preferably from 3 to 8, groups selected from ethylene oxide, oxide propylene, butylene oxide and their mixtures,
• les esters monoalkyliques alcoxylés (par exemple éthoxylés et/ou propoxylés et/ou butoxylés) de l'acide phosphorique, les esters dialkyliques alcoxylés (par exemple éthoxylés et/ou propoxylés et ou butoxylés) de l'acide phosphorique, les esters alkyliques de l'acide sulfurique, les esters alkyliques alcoxylés (par exemple éthoxylés et/ou propoxylés et/ou butoxylés) de l'acide sulfurique, les acides alkylsulfoniques, les acides arylsulfoniques, les acides alkylarylsulfoniques, ainsi que leurs sels, • les alkylamines alcoxylées, particulièrement les amines grasses éthoxylées, les amines grasses propoxylées et les amines grasses butoxylées, telles que les éthoxylates d'amines de coco, les éthoxylates d’oléylamines, les éthoxylates d'amines de suif ou les éthoxylates de diamines de suif, • alkoxylated monoalkyl esters (for example ethoxylated and / or propoxylated and / or butoxylated) of phosphoric acid, alkoxylated dialkyl esters (for example ethoxylated and / or propoxylated and or butoxylated) of phosphoric acid, alkyl esters of sulfuric acid, alkoxylated alkyl esters (for example ethoxylated and / or propoxylated and / or butoxylated) of sulfuric acid, alkylsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids, as well as their salts, • alkoxylated alkylamines, particularly ethoxylated fatty amines, propoxylated fatty amines and butoxylated fatty amines, such as coconut amine ethoxylates, oleylamine ethoxylates, tallow amine ethoxylates or diamine ethoxylates of tallow,
• les amines primaires, secondaires ou tertiaires, préférablement les sels d'amines primaires ou secondaires avec les esters alkyliques alcoxylés de l'acide phosphorique, tels que les esters monoalkyliques éthoxylés de l’acide phosphorique, les esters dialkyliques éthoxylés de l’acide phosphorique, par exemple les sels formés avec l’octadécylamine et le monoester n-octadécylique de l'acide phosphorique, les sels formés avec l’octadécylamine et le monoester n-octadécylique éthoxylé de l'acide phosphorique, les sels formés avec l’octadécylamine et le monoester n-octadécylique propoxylé de l'acide phosphorique, les sels formés avec l’octadécylamine et le diester n-octadécylique de l'acide phosphorique, les sels formés avec l’octadécylamine et le diester n-octadécylique éthoxylé de l'acide phosphorique, les sels formés avec l’octadécylamine et le diester n-octadécylique propoxylé de l'acide phosphorique, • primary, secondary or tertiary amines, preferably the salts of primary or secondary amines with alkoxylated alkyl esters of phosphoric acid, such as ethoxylated monoalkyl esters of phosphoric acid, dialkyl ethoxylated esters of phosphoric acid , for example salts formed with octadecylamine and n-octadecyl monoester of phosphoric acid, salts formed with octadecylamine and ethoxylated n-octadecyl monoester of phosphoric acid, salts formed with octadecylamine and n-octadecyl propoxylated monoester of phosphoric acid, salts formed with octadecylamine and n-octadecyl diester of phosphoric acid, salts formed with octadecylamine and ethoxylated n-octadecyl diester of phosphoric acid , the salts formed with octadecylamine and the propoxylated n-octadecyl diester of phosphoric acid,
• les acides gras alcoxylés, particulièrement les acides gras éthoxylés, les acides gras propoxylés et les acides gras butoxylés, tels que les éthoxylates de l'acide laurique ou les éthoxylates de l'acide oléique, • alkoxylated fatty acids, particularly ethoxylated fatty acids, propoxylated fatty acids and butoxylated fatty acids, such as lauric acid ethoxylates or oleic acid ethoxylates,
• les huiles et graisses naturelles alcoxylées, particulièrement les huiles naturelles éthoxylées, propoxylées ou butoxylées, telles que la lanoline éthoxylée, l’huile de ricin éthoxylée ou les éthoxylates de l’huile de colza, • alkoxylated natural oils and fats, particularly ethoxylated, propoxylated or butoxylated natural oils, such as ethoxylated lanolin, ethoxylated castor oil or ethoxylates from rapeseed oil,
• les alcoxylates d’ester de sorbitane, particulièrement les éthoxylates d’ester de sorbitane, les propoxylates d’ester de sorbitane et les butoxylates d’ester de sorbitane, tels que les monolaurates éthoxylés de sorbitane, les monostéarates éthoxylés de sorbitane ou les trioléates éthoxylés de sorbitane, • sorbitan ester alkoxylates, particularly sorbitan ester ethoxylates, sorbitan ester propoxylates and sorbitan ester butoxylates, such as ethoxylated sorbitan monolaurates, ethoxylated sorbitan monostearates or trioleates sorbitan ethoxylates,
• les copolymères de poly(oxyde d’alkylène), sous forme de structure soit séquencée soit aléatoire, tels que le copolymère de poly(oxyde d'éthylène)-b-polypropylène , les copolymères de poly(oxyde d'éthylène)-b-poly(oxyde de propylène)-b-poly(oxyde d'éthylène), les copolymères de poly(oxyde de propylène)-b-poly(oxyde d’éthylène)-b- poly(oxyde de propylène), les copolymères de poly(oxyde de propylène)-b-poly(oxyde d'éthylène)-b-poly(oxyde de butylène) et les copolymères statistiques de poly(oxyde d'éthylène)-poly(oxyde de propylène), • poly (alkylene oxide) copolymers, in the form of either a block or random structure, such as poly (ethylene oxide) -b-polypropylene copolymer, poly (ethylene oxide) -b copolymers -poly (propylene oxide) -b-poly (ethylene oxide), copolymers of poly (propylene oxide) -b-poly (ethylene oxide) -b- poly (propylene oxide), copolymers of poly (propylene oxide) -b-poly (ethylene oxide) -b-poly (butylene oxide) and random copolymers of poly (ethylene oxide) -poly (propylene oxide),
• les alkylsulfonates, les arylsulfonates, les alkyléthersulfates, les (alkyle alcoxylé)sulfates et • alkylsulphonates, arylsulphonates, alkylethersulphates, (alkoxylated alkyl) sulphates and
• leurs mélanges. [0036] Dans un mode de réalisation préféré de la présente invention, des exemples caractéristiques de tensioactifs à base d’esters alkyliques alcoxylés de l’acide phosphorique incluent, de manière non limitative, le monoester hexylique éthoxylé de l'acide phosphorique, le diester hexylique éthoxylé de l’acide phosphorique, le monoester n-octylique éthoxylé de l’acide phosphorique, le diester n-octylique éthoxylé de l’acide phosphorique, le monoester iso-octylique éthoxylé de l’acide phosphorique, le diester iso- octylique éthoxylé de l’acide phosphorique, le monoester 2-octylique éthoxylé de l’acide phosphorique, le diester 2-octylique éthoxylé de l’acide phosphorique, le monoester 9- décénylique éthoxylé de l’acide phosphorique, le diester 9-décénylique éthoxylé de l’acide phosphorique, le monoester isodécylique éthoxylé de l’acide phosphorique, le diester isodécylique éthoxylé de l’acide phosphorique, le monoester n-décylique éthoxylé de l’acide phosphorique, le diester n-décylique éthoxylé de l’acide phosphorique, le monoester isodécylique éthoxylé de l’acide phosphorique, le diester isodécylique éthoxylé de l’acide phosphorique, le monoester 10-undécénylique éthoxylé de l’acide phosphorique, le diester 10-undécénylique éthoxylé de l’acide phosphorique, le monoester n-dodécylique éthoxylé de l’acide phosphorique, le monoester isododécylique éthoxylé de l’acide phosphorique, le diester n-dodécylique éthoxylé de l’acide phosphorique, le diester isododécylique éthoxylé de l’acide phosphorique, le monoester n-tétradécylique éthoxylé de l’acide phosphorique, le monoester isotétradécylique éthoxylé de l’acide phosphorique, le diester n-tétradécylique éthoxylé de l’acide phosphorique, le diester isotétradécylique éthoxylé de l’acide phosphorique, le monoester n-hexadécylique éthoxylé de l’acide phosphorique, le monoester isohexadécylique éthoxylé de l’acide phosphorique, le diester n-hexadécylique éthoxylé de l’acide phosphorique, le diester isohexadécylique éthoxylé de l’acide phosphorique, le monoester n-octadécylique éthoxylé de l’acide phosphorique, le monoester iso-octadécylique éthoxylé de l’acide phosphorique, le diester n-octadécylique éthoxylé de l’acide phosphorique, le diester iso-octadécylique éthoxylé de l’acide phosphorique ainsi que leurs mélanges. • their mixtures. In a preferred embodiment of the present invention, characteristic examples of surfactants based on alkoxylated alkyl esters of phosphoric acid include, without limitation, the ethoxylated hexyl monoester of phosphoric acid, the diester ethoxylated hexyl phosphoric acid, ethoxylated n-octyl monoester of phosphoric acid, ethoxylated n-octyl diester of phosphoric acid, ethoxylated iso-octyl monoester of phosphoric acid, ethoxylated iso-octyl diester phosphoric acid, ethoxylated phosphoric acid 2-octyl monoester, phosphoric acid ethoxylated 2-octyl diester, phosphoric acid ethoxylated 9-decenyl monoester, ethoxylated 9-decenyl diester 'phosphoric acid, ethoxylated isodecyl monoester of phosphoric acid, ethoxylated isodecyl diester of phosphoric acid, ethoxylated n-decyl monoester of phosphoric acid, n-decyl diester of phosphoric acid thoxylated phosphoric acid, ethoxylated isodecyl monoester of phosphoric acid, ethoxylated isodecyl diester of phosphoric acid, ethoxylated 10-undecenyl monoester of phosphoric acid, ethoxylated 10-undecenyl diester of phosphoric acid , ethoxylated phosphoric acid n-dodecyl monoester, phosphoric acid ethoxylated isododecyl monoester, phosphoric acid ethoxylated n-dodecyl diester, phosphoric acid ethoxylated isododecyl diester, n-tetradecyl monoester ethoxylated phosphoric acid, ethoxylated isotetradecyl monoester of phosphoric acid, ethoxylated n-tetradecyl diester of phosphoric acid, ethoxylated isotetradecyl diester of phosphoric acid, ethoxylated n-hexadecyl monoester of phosphoric acid , ethoxylated isohexadecyl monoester of phosphoric acid, ethoxylated n-hexadecyl diester of phosphoric acid, ethoxylated isohexadecyl diester of phosphoric acid phosphoric acid, ethoxylated n-octadecyl monoester of phosphoric acid, ethoxylated iso-octadecyl monoester of phosphoric acid, ethoxylated n-octadecyl diester of phosphoric acid, ethoxylated iso-octadecyl diester of phosphoric acid phosphoric acid and mixtures thereof.
[0037] L'invention comprend également les dérivés propoxylés et butoxylés des esters phosphoriques énumérés ci-dessus ainsi que leurs mélanges. The invention also comprises the propoxylated and butoxylated derivatives of the phosphoric esters listed above as well as their mixtures.
[0038] Selon encore un autre mode de réalisation de la présente invention, le tensioactif alcoxylé destiné à être utilisé dans la formulation de la présente invention peut présenter intrinsèquement une activité antiagglomérante. According to yet another embodiment of the present invention, the alkoxylated surfactant intended for use in the formulation of the present invention may inherently exhibit anti-caking activity.
[0039] Selon encore un autre aspect préféré de la présente invention, le tensioactif alcoxylé présente une viscosité inférieure à 5000 mPa.s à 25°C, telle que mesurée à l'aide d’un rhéomètre à cisaillement dynamique (Anton Paar MCR301 ) dans une géométrie à plaques parallèles de 50 mm (PP50) à 25° C et à une vitesse de cisaillement de 80 s 1. [0040] Comme indiqué ci-dessus, le tensioactif alcoxylé est utilisé à des dosages de 1 % en poids à 30 % en poids et préférablement de 1 % en poids à 25 % en poids, plus préférablement de 2 % en poids à 20 % en poids et encore plus préférablement de 2 % en poids à 15 % en poids, par rapport au poids total de la composition comprenant le polyalcool a) et ledit tensioactif alcoxylé b). According to yet another preferred aspect of the present invention, the alkoxylated surfactant has a viscosity of less than 5000 mPa.s at 25 ° C, as measured using a dynamic shear rheometer (Anton Paar MCR301) in a geometry to 50 mm parallel plates (PP50) at 25 ° C and at a shear rate of 80 s 1 . As indicated above, the alkoxylated surfactant is used in dosages of 1% by weight to 30% by weight and preferably from 1% by weight to 25% by weight, more preferably from 2% by weight to 20% by weight and even more preferably from 2% by weight to 15% by weight, relative to the total weight of the composition comprising the polyalcohol a) and said alkoxylated surfactant b).
[0041] Outre les additifs et/ou les charges qui peuvent être ajoutées à la formulation de la présente invention et comme indiqué ci-dessus, la formulation revendiquée comprend également un ou plusieurs solvants qui sont généralement, mais pas exclusivement, choisi parmi l'eau et les monoalcools. Des exemples de monoalcools qui peuvent être utilisés comme solvant dans la formulation de la présente invention incluent, de manière non limitative, le méthanol, l’éthanol, le n-propanol, l’isopropanol, le n-butanol, l’isobutanol, le n- pentanol, l’isopentanol, le cyclopentanol, le n-hexanol, l’isohexanol, le n-heptanol, l’isoheptanol, le n-octanol, l’iso-octanol, le 2-octanol, le n-nonanol, l’isononanol, le n- décanol, l’isodécanol, le 9-décénol, le 10-undécénol et plus généralement n’importe lequel et tous les alcools en C1 à C10 ainsi que leurs mélanges, dans toutes les proportions. [0042] La quantité de solvant dépend considérablement de la nature du/des tensioactif(s) alcoxylé(s) et du/de(s) polyalcool(s) présents dans la formulation, mais également de l'application envisagée et de la viscosité globale souhaitée de la formulation. Généralement, la quantité de solvant(s) dans la formulation se situe dans une plage de 0,5 % en poids à 30 % en poids, préférablement de 2 % en poids à 25 % en poids, plus préférablement de 5 % en poids à 20 % en poids, par rapport au poids total de la formulation de l'invention. [0043] Dans un autre aspect, la présente invention concerne l'utilisation de la formulation décrite ci-dessus en tant que formulation d'enrobage pour des particules afin de réduire et même d'éviter l'effet d'agglomération et/ou la génération de poussière. [0041] Besides the additives and / or fillers which can be added to the formulation of the present invention and as indicated above, the claimed formulation also comprises one or more solvents which are generally, but not exclusively, chosen from among water and monoalcohols. Examples of monoalcohols which can be used as a solvent in the formulation of the present invention include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, cyclopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, iso-octanol, 2-octanol, n-nonanol, isononanol, n-decanol, isodecanol, 9-decenol, 10-undecenol and more generally any and all C1 to C10 alcohols as well as their mixtures, in all proportions. The amount of solvent depends considerably on the nature of the alkoxylated surfactant (s) and of the polyalcohol (s) present in the formulation, but also on the envisaged application and on the viscosity overall desired formulation. Generally, the amount of solvent (s) in the formulation is within a range of 0.5 wt% to 30 wt%, preferably 2 wt% to 25 wt%, more preferably 5 wt% to 20% by weight, relative to the total weight of the formulation of the invention. In another aspect, the present invention relates to the use of the formulation described above as a coating formulation for particles in order to reduce and even avoid the effect of agglomeration and / or the dust generation.
[0044] La présente invention concerne également des particules enrobées par la formulation de la présente invention comme décrit ci-dessus. The present invention also relates to particles coated with the formulation of the present invention as described above.
[0045] Des particules qui peuvent être enrobées par la formulation décrite ci-dessus dans le sens de la présente invention peuvent être solubles dans l'eau et ou un/des solvant(s) ou insolubles dans l'eau et/ou un/des solvant(s) partiellement solubles dans l'eau et/ou un/des solvant(s). Les particules préférées destinées à être utilisées dans la présente invention sont préférablement partiellement ou totalement, encore plus préférablement totalement solubles dans l'eau. Particles which can be coated with the formulation described above in the sense of the present invention can be soluble in water and / or solvent (s) or insoluble in water and / or / partially water-soluble solvent (s) and / or solvent (s). Preferred particles for use in the present invention are preferably partially or totally, still more preferably completely soluble in water.
[0046] Les particules destinées à être utilisées dans le cadre de la présente invention peuvent être de différentes formes et nature et incluent, en tant qu'exemples non limitatifs, les particules minérales ou organiques granulées et en particulier des particules ou granules d'engrais, le charbon, les minerais, les agrégats minéraux, le soufre, les particules de bois (telles que par exemple les copeaux et les pellets), les salissures, les déchets granulés, les médicaments, les céréales, les graines, la nourriture granulée ou pelletisée pour animaux et analogues et plus préférablement les particules ou granules d'engrais. [0047] Dans la présente invention, le terme « engrais », qui est très bien connu dans la technique, se réfère en général à une particule de matière inorganique ou organique qui fournit des nutriments ou d'autres substances au sol et/ou aux cultures, qui améliorent leur croissance. Les particules d'engrais peuvent provenir d'un quelconque procédé connu pour produire des engrais, tels que la granulation, le broyage, le mélange, l'assemblage, la cristallisation, le compactage, la pelletisation, l'extrusion ou le grenolage et analogues. [0048] Dans un mode de réalisation préféré, les particules d'engrais dans le sens de la présente invention incluent les nitrates ammonium, les nitrophosphates, le phosphate- sulfate d’ammonium, le sulfate d’ammonium, les nitrates de calcium-ammonium, le nitrate de calcium, de phosphate de diammonium, le chlorure de potassium, le phosphate de monoammonium, le muriate de potasse, le sulfate de potasse, le sulfate de potasse- magnésie, le superphosphate simple, le superphosphate triple, l’urée, le soufre, le polyhalite et d’autres engrais complexes ou composites qui contiennent plusieurs éléments et par exemple ceux connus sous l’acronyme NPK. [0049] Selon un mode de réalisation encore plus préféré, les particules d'engrais sont choisies parmi les sulfates, tels que les sulfates d'ammonium ou le sulfate de potasse et les phosphates tels que le superphosphate simple ou triple et le phosphate de monoammonium. L'invention est mise en œuvre de manière particulièrement avantageuse avec des engrais solubles dans l'eau. [0050] La formulation de la présente invention peut être appliquée à l'aide de techniques connues, bien connues par l'homme du métier, et particulièrement à l'aide de procédés connus similaires utilisés pour l'enrobage de particules en général et en particulier tels que ceux utilisés pour l'enrobage d'engrais granulés et particulièrement selon des techniques d'enrobage par pulvérisation bien connues. [0051] L'enrobage peut être effectué à l'aide d'un procédé par lots ou d'un procédé continu. Par exemple, l’engrais granulé peut être introduit dans un tambour d'enrobage rotatif tandis que l'enrobage est appliqué par l’intermédiaire d’une ou plusieurs buses sous pression. L'enrobage peut également être pulvérisé tandis que l’engrais granulé tourne sur un tambour de granulation incliné ou est à l’intérieur d’une chambre à lit fluidisé. [0052] L'étape d'enrobage par la formulation d'enrobage de la présente invention peut être réalisée avant et/ou en même temps et ou après le/les enrobage(s) d'un autre matériau, comme par exemple l'enrobage de nutriments supplémentaires ou de fonctions biologiques supplémentaires qui sont utiles pour les sols ou les animaux ou les plantes, l'enrobage d'agents antiagglomérants comme par exemple les argiles (par exemple le kaolin), le talc et analogue. The particles intended for use in the context of the present invention can be of different shapes and nature and include, as non-limiting examples, granulated mineral or organic particles and in particular fertilizer particles or granules, coal, ores, mineral aggregates, sulfur, wood particles (such as for example chips and pellets), dirt, granulated waste, drugs, cereals, seeds, granulated or pelletized animal feed and the like and more preferably fertilizer particles or granules. In the present invention, the term "fertilizer", which is very well known in the art, generally refers to a particle of inorganic or organic material which provides nutrients or other substances to the soil and / or to the soil. crops, which improve their growth. The fertilizer particles can be obtained from any known process for producing fertilizers, such as granulation, grinding, mixing, assembling, crystallization, compaction, pelletization, extrusion or graining and the like. . In a preferred embodiment, the fertilizer particles in the sense of the present invention include ammonium nitrates, nitrophosphates, ammonium phosphate-sulfate, ammonium sulfate, calcium ammonium nitrates. , calcium nitrate, diammonium phosphate, potassium chloride, monoammonium phosphate, muriate of potash, sulphate of potash, sulphate of potash-magnesia, simple superphosphate, triple superphosphate, urea, sulfur, polyhalite and other complex or composite fertilizers which contain several elements and for example those known by the acronym NPK. According to an even more preferred embodiment, the fertilizer particles are chosen from sulphates, such as ammonium sulphates or potassium sulphate and phosphates such as single or triple superphosphate and monoammonium phosphate. . The invention is implemented particularly advantageously with water-soluble fertilizers. The formulation of the present invention can be applied using known techniques, well known to those skilled in the art, and particularly using similar known methods used for coating particles in general and in particularly such as those used for coating granular fertilizers and particularly according to well known spray coating techniques. The coating can be carried out using a batch process or a continuous process. For example, the granulated fertilizer can be introduced into a rotating coating drum while the coating is applied through one or more pressurized nozzles. The coating can also be sprayed while the granulated fertilizer rotates on an inclined granulation drum or is inside a fluidized bed chamber. The coating step by the coating formulation of the present invention can be carried out before and / or at the same time and or after the coating (s) of another material, such as for example the coating with additional nutrients or additional biological functions which are useful for soils or animals or plants, coating with anti-caking agents such as, for example, clays (eg kaolin), talc and the like.
[0053] Une fois qu'elle a été appliquée à la surface de la particule, la quantité de formulation enrobée sur ladite particule peut varier en de grandes proportions et quantités, avantageusement et préférablement entre 0,01 % en poids et 10 % en poids, plus préférablement entre 0,02 % en poids et 5 % en poids, encore plus préférablement entre 0,02 % en poids et 2 % en poids, valeurs limites incluses, par rapport à la masse totale de la particule enrobée. Once it has been applied to the surface of the particle, the amount of formulation coated on said particle can vary in large proportions and amounts, advantageously and preferably between 0.01% by weight and 10% by weight , more preferably between 0.02% by weight and 5% by weight, even more preferably between 0.02% by weight and 2% by weight, limit values included, with respect to the total mass of the coated particle.
[0054] Comme indiqué ci-dessus, la présente invention concerne également la formulation appliquée sur une particule, préférablement un matériau granulaire, et, selon un mode de réalisation préféré, l'invention concerne la formulation appliquée sur une particule, préférablement un matériau granulaire, en une quantité allant de 0,01 % en poids à 10 % en poids, plus préférablement de 0,02 % en poids à 5 % en poids, encore plus préférablement de 0,02 % en poids à 2 % en poids, valeurs limites incluses, par rapport à la masse totale de la formulation et de la particule. As indicated above, the present invention also relates to the formulation applied to a particle, preferably a granular material, and, according to a preferred embodiment, the invention relates to the formulation applied to a particle, preferably a granular material. , in an amount ranging from 0.01% by weight to 10% by weight, more preferably from 0.02% by weight to 5% by weight, still more preferably from 0.02% by weight to 2% by weight, values limits included, relative to the total mass of the formulation and the particle.
[0055] En d'autres termes, l'invention concerne également une particule, préférablement le matériau granulaire, enrobé(e) par la formulation de la présente invention. Une fois qu'elle est appliquée à la surface de ladite particule (préférablement le matériau granulaire, par exemple et préférablement un granule d'engrais), il a été observé de manière surprenante que la formulation liquide de la présente invention est efficace pour atteindre l'un ou plusieurs parmi les buts suivants : In other words, the invention also relates to a particle, preferably the granular material, coated with the formulation of the present invention. Once it is applied to the surface of said particle (preferably the granular material, for example and preferably a fertilizer granule), it has surprisingly been observed that the liquid formulation of the present invention is effective in achieving l '' one or more of the following purposes:
• réduire ou éviter l'agglomération de la particule enrobée, • reduce or avoid the agglomeration of the coated particle,
• réduire ou éviter la libération de poussière provenant de la particule enrobée, • reduce or avoid the release of dust from the coated particle,
• réduire ou éviter l'absorption d'humidité dans la particule enrobée et • reduce or avoid the absorption of moisture in the coated particle and
• lier d’autres particules minérales ou organiques à la particule enrobée. • bind other mineral or organic particles to the coated particle.
[0056] La formulation de la présente invention permet l'obtention de particules enrobées, et préférablement d'engrais enrobés, présentant l'un ou plusieurs parmi les avantages ci- dessous, parmi lesquels on peut mentionner : The formulation of the present invention makes it possible to obtain coated particles, and preferably coated fertilizers, having one or more of the advantages below, among which may be mentioned:
• aucune réaction chimique ne se produit entre la formulation et la particule enrobée,• no chemical reaction occurs between the formulation and the coated particle,
• l'enrobage liquide est en ligne avec le changement actuel dans la loi européenne tendant à réduire/faire disparaître l'utilisation de polymères non biodégradables dans les engrais, • son utilisation est simple, c'est-à-dire que le même procédé actuel d'enrobage peut être utilisé (équipement de pulvérisation/enrobage, mêmes températures de pulvérisation, etc.),• the liquid coating is in line with the current change in European law aimed at reducing / eliminating the use of non-biodegradable polymers in fertilizers, • its use is simple, ie the same current coating process can be used (spraying / coating equipment, same spraying temperatures, etc.),
• il est essentiellement non toxique, • it is essentially non-toxic,
• il est soluble dans l’eau. [0057] La formulation de la présente invention peut donc être utilisée dans un certain nombre de champs d'application et est particulièrement adaptée aux enrobages de particules qui présentent une tendance à l'agglomération et/ou à la génération de poussière, telles que les céréales, les farines, les médicaments, les céramiques, les agrégats minéraux provenant de carrières et analogues. [0058] L'invention est à présent illustrée davantage par les exemples suivants, qui sont fournis uniquement en tant que modes de réalisation de l'invention, sans limiter de quelque manière que ce soit la portée de protection telle que définie par les revendications annexées. EXEMPLES Exemple 1 • it is soluble in water. The formulation of the present invention can therefore be used in a number of fields of application and is particularly suitable for coatings of particles which exhibit a tendency to agglomeration and / or to the generation of dust, such as cereals, flour, medicines, ceramics, mineral aggregates from quarries and the like. The invention is now further illustrated by the following examples, which are provided only as embodiments of the invention, without in any way limiting the scope of protection as defined by the appended claims. . EXAMPLES Example 1
[0059] La formulation A, selon l’invention, est préparée par mélange de 47,5 g d’eau glycérolée (sous-produit du procédé de raffinage d’huile de ricin, fourni par ARKEMA sous la dénomination commerciale "Eaux glycérineuses", qui contient environ 5 % d’eau) et de 2,5 g d’une huile de ricin éthoxylée avec 40 motifs d’oxyde d'éthylène (commercialisée sous la dénomination Surfaline R40L par ARKMEA), sous agitation et à température ambiante. [0060] La formulation reste homogène après mélange. La tension superficielle de la formulation A est mesurée à l’aide d’un goniomètre (DSA30 de Krüss) à l'aide de la configuration de la goutte pendante à 21 °C. Les taisions superficielles de deux polyalcools eux-mêmes, le glycérol (Sigma-Aldrich, référence G7757-M) et les mêmes eaux glycérolées que celles utilisées dans la formulation A, sont mesurées à titre de comparaison. Le tableau 1 ci-dessous montre les valeurs de tension superficielle mesurées pour le glycérol, les eaux glycérolées (glycérol brut) et la formulation A : Tableau 1 -
Figure imgf000015_0001
[0061] Comme on peut le voir, le tensioactif alcoxylé utilisé dans la formulation A réduit significativement la valeur de la tension superficielle du polyalcool choisi (glycérol dans ce cas) et répond donc à la définition d'un agent tensioactif. Formulation A, according to the invention, is prepared by mixing 47.5 g of glycerolated water (by-product of the castor oil refining process, supplied by ARKEMA under the trade name "Glycerine waters" , which contains approximately 5% water) and 2.5 g of a castor oil ethoxylated with 40 units of ethylene oxide (marketed under the name Surfaline R40L by ARKMEA), with stirring and at room temperature. The formulation remains homogeneous after mixing. The surface tension of formulation A is measured using a goniometer (DSA30 from Krüss) using the hanging drop configuration at 21 ° C. The surface taisions of two polyalcohols themselves, glycerol (Sigma-Aldrich, reference G7757-M) and the same glycerolated waters as those used in formulation A, are measured for comparison. Table 1 below shows the surface tension values measured for glycerol, glycerolated waters (crude glycerol) and formulation A: Table 1 -
Figure imgf000015_0001
As can be seen, the alkoxylated surfactant used in formulation A significantly reduces the value of the surface tension of the polyalcohol chosen (glycerol in this case) and therefore meets the definition of a surfactant.
Exemple 2 Example 2
[0062] La formulation comparative B est préparée par mélange de 46,25 g d’huile minérale (Huile 700NS par Colas) et de 3,75 g d'amine de suif (Noram® S par ARKEMA) sous agitation à une température régulée de 60 °C. La formulation reste homogène après le mélange et le refroidissement à température ambiante. [0062] Comparative Formulation B is prepared by mixing 46.25 g of mineral oil (Oil 700NS by Colas) and 3.75 g tallow amine (Noram ® S by ARKEMA) with stirring at a controlled temperature of 60 ° C. The formulation remains homogeneous after mixing and cooling to room temperature.
[0063] La formulation comparative C est constituée d'eaux glycérolées (sous-produit du procédé de raffinage de l’huile de ricin, fourni par ARKEMA, qui contient environ 5 % d'eau) et est utilisée telle quelle. [0063] Comparative formulation C consists of glycerolated water (a by-product of the castor oil refining process, supplied by ARKEMA, which contains about 5% water) and is used as is.
[0064] La viscosité de chacune des formulations est mesurée à l'aide d'un rhéomètre à cisaillement dynamique (Anton Paar MCR301 ) dans une géométrie à plaques parallèles de 50 mm (PP50), entre 50 °C et 10 °C à une vitesse decisaillement de 80 s-1 donnant une valeur de 48 mPa.s à 25 °C pour la formulation comparative B, de 326 mPa.s pour la formulation comparative C et de 380 mPa.s pour la formulation A. The viscosity of each of the formulations is measured using a dynamic shear rheometer (Anton Paar MCR301) in a 50 mm parallel plate geometry (PP50), between 50 ° C and 10 ° C at a shear rate of 80 s -1 giving a value of 48 mPa.s at 25 ° C for comparative formulation B, 326 mPa.s for comparative formulation C and 380 mPa.s for formulation A.
Exemple 3 Example 3
[0065] Les tests suivants sont effectués afin d'évaluer la tendance à l'agglomération d'un échantillon enrobé de sulfate d'ammonium granulé, AS, présentant une distribution des grosseurs entre 1 ,5 mm et 4,5 mm, après avoir été soumis à la température et la pression pendant le transport. The following tests are carried out in order to evaluate the tendency to agglomeration of a sample coated with granulated ammonium sulfate, AS, having a size distribution between 1.5 mm and 4.5 mm, after having been subjected to temperature and pressure during transportation.
[0066] La formulation A (selon l'invention) ainsi que la formulation B et la formulation C (formulations comparatives) des exemples précédents sont utilisées comme enrobage sur les granules d'AS. 500 g de granules d'AS sont chauffés à 40 °C pendant quatre heures avant d'être mélangés dans un tambour d'enrobage de laboratoire à extrémité ouverte et aspergés par 0,4 g d'échantillon de formulation d'enrobage à 90 °C. Formulation A (according to the invention) as well as formulation B and formulation C (comparative formulations) of the preceding examples are used as coating on the granules of AS. 500 g of AS granules are heated at 40 ° C for four hours before being mixed in an open-ended laboratory coating drum and sprayed with 0.4 g of coating formulation sample at 90 ° vs.
[0067] Un test d'agglomération accélérée est effectué sur les échantillons enrobés. Des moules métalliques sont remplis par 150 g d'engrais enrobé, fermés et soumis à une pression pneumatique constante de 3 bars pendant 3 jours. Les échantillons sont ensuite stockés à température ambiante pendant 6 jours. An accelerated agglomeration test is performed on the coated samples. Metal molds are filled with 150 g of coated fertilizer, closed and subjected to a constant pneumatic pressure of 3 bars for 3 days. The samples are then stored at room temperature for 6 days.
[0068] Trois spécimens sont préparés pour chaque échantillon enrobé. Un échantillon non enrobé est également testé à titre de comparaison. A la fin des six jours, les moules sont ouverts soigneusement et comprimés dans une machine de compression universelle (Instron 3365) où un spécimen complètement aggloméré est obtenu. La force de rupture des spécimens est enregistrée pour chaque échantillon. Three specimens are prepared for each coated sample. An uncoated sample is also tested for comparison. At the end of the six days, the molds are carefully opened and compressed in a universal compression machine. (Instron 3365) where a fully agglomerated specimen is obtained. The breaking strength of the specimens is recorded for each sample.
[0069] Dans le cas où les échantillons ne résultent pas en un spécimen complètement aggloméré, les spécimens sont passés à travers un tamis de 6 mm. Cette dimension est suffisamment grande pour laisser passer les granules individuels mais suffisamment petite pour retenir les agglomérats ou les parties partiellement agglomérées de l'échantillon. Le pourcentage en poids de la masse retenue dans le tamis par rapport à la masse totale de l'échantillon est une mesure de la tendance à l'agglomération (pourcentage d'agglomération). [0070] Un engrais s'écoulant totalement librement dans ces conditions aurait une force de rupture et un pourcentage d'agglomération égaux à zéro (0). Le tableau 2 montre les valeurs de l’intégrale des résultats obtenus pour chaque enrobage (force de rupture en kilogrammes-force, kgf). - Tableau 2 -
Figure imgf000017_0001
In the event that the samples do not result in a completely agglomerated specimen, the specimens are passed through a 6mm sieve. This dimension is large enough to pass the individual granules but small enough to retain agglomerates or partially agglomerated parts of the sample. The percentage by weight of the mass retained in the sieve relative to the total mass of the sample is a measure of the tendency to agglomeration (percentage of agglomeration). A fertilizer flowing completely free under these conditions would have a breaking force and a percentage of agglomeration equal to zero (0). Table 2 shows the values of the integral of the results obtained for each coating (breaking force in kilograms-force, kgf). - Table 2 -
Figure imgf000017_0001
[0071] On observe que la formulation A (selon l'invention) présente une excellente protection contre l'agglomération, meilleure qu'un enrobage antiagglomérant utilisé couramment basé sur des amines grasses et des huiles minérales (formulation comparative B) et également meilleure que la formulation comparative C, où aucun tensioactif n'est utilisé. It is observed that formulation A (according to the invention) exhibits excellent protection against agglomeration, better than an anti-caking coating commonly used based on fatty amines and mineral oils (comparative formulation B) and also better than comparative formulation C, where no surfactant is used.
Exemple 4 Example 4
[0072] Les tests suivants sont effectués afin d'évaluer la quantité de poussière libérée par un échantillon de NPK enrobé pendant le transport. Les essais sont effectués au moyen d’un appareil optique de mesure de poussière Microtrack. Un échantillon de 300 g d’engrais enrobé est introduit dans l’appareil et la poussière générée par la chute (en raison de l’impact après la chute) est enregistrée par des procédés optiques pendant 60 secondes. La quantité de poussière générée est proportionnelle à l’intégrale du signal optique mesuré (unités arbitraires) en fonction du temps de mesure. [0073] La valeur de l'intégrale permet la comparaison de l'efficacité antipoussière des différents enrobages : plus la valeur est basse, meilleure est la formulation d'enrobage. Les engrais enrobés (500 g) décrits dans l'exemple 1 sont conservés dans un récipient fermé à 40 °C pendant 14 jours avant d'être testés en ce qui concerne la poussière. Le tableau 3 montre les valeurs de l’intégrale du test de poussière pour chaque enrobage. The following tests are carried out in order to evaluate the quantity of dust released by a sample of coated NPK during transport. The tests are carried out using a Microtrack optical dust measuring device. A sample of 300 g of coated fertilizer is introduced into the apparatus and the dust generated by the drop (due to the impact after the drop) is recorded by optical methods for 60 seconds. The amount of dust generated is proportional to the integral of the measured optical signal (arbitrary units) as a function of the measurement time. The value of the integral allows the comparison of the dust-proof efficiency of the different coatings: the lower the value, the better the coating formulation. The coated fertilizers (500 g) described in Example 1 are stored in a closed container at 40 ° C for 14 days before being tested for dust. Table 3 shows the values of the dust test integral for each coating.
-- Tableau 3 -
Figure imgf000018_0001
- Table 3 -
Figure imgf000018_0001
[0074] Bien que chacune des formulations d’enrobage testés fournisse un certain degré de protection contre la poussière, la formulation A selon l'invention fournit les meilleures valeurs de protection contre la poussière (moins de poussière générée après un stockage simulé). La valeur est significativement meilleure que celle de la même eau glycérolée en elle-même (formulation C) et que celle de la formulation qui contient un tensioactif standard à base d'amine grasse dans de l'huile minérale (formulation B). [0074] Although each of the coating formulations tested provide some degree of dust protection, Formulation A according to the invention provides the best dust protection values (less dust generated after simulated storage). The value is significantly better than that of the same glycerolated water itself (formulation C) and that of the formulation which contains a standard surfactant based on fatty amine in mineral oil (formulation B).

Claims

REVENDICATIONS
1. Formulation comprenant : 1. Formulation comprising:
1 ) une composition comprenant a) 10 % en poids à 99 % en poids d'au moins un polyalcool et b) 1 % en poids à 90 % en poids, préférablement 1 % en poids à 70 % en poids, plus préférablement 1 % en poids à 50 % en poids, encore plus préférablement 1 % en poids à 30 % en poids d'au moins un tensioactif alcoxylé, valeurs limites incluses, par rapport au poids total de la composition comprenant a) + b) et 2) au moins un solvant. 1) a composition comprising a) 10% by weight to 99% by weight of at least one polyalcohol and b) 1% by weight to 90% by weight, preferably 1% by weight to 70% by weight, more preferably 1% by weight by weight at 50% by weight, even more preferably 1% by weight at 30% by weight of at least one alkoxylated surfactant, limit values included, relative to the total weight of the composition comprising a) + b) and 2) in minus a solvent.
2. Formulation selon la revendication 1 , l'au moins un solvant étant choisi parmi les monoalcools et l’eau, ainsi que leurs mélanges. 2. Formulation according to claim 1, the at least one solvent being chosen from monoalcohols and water, as well as mixtures thereof.
3. Formulation selon la revendication 1 ou 2, comprenant en outre un ou plusieurs autres constituants, choisis parmi les additifs, les charges et analogues. 3. A formulation according to claim 1 or 2, further comprising one or more other constituents, selected from additives, fillers and the like.
4. Formulation selon la revendication 3, l'autre ou les autres constituants étant choisis parmi : 4. Formulation according to claim 3, the other or the other constituents being chosen from:
• les agents antiagglomérants, tels que les alkylamines, les esters alkylphosphoriques, les alcools alkyliques linéaires, les sulfates d’alkyléther, les alkylsulfonates, les arylsulfonates, les alkyléthersulfonates et leurs combinaisons, préférablement les sels d’alkylamines avec les esters alkylphosphoriques, • anti-caking agents, such as alkylamines, alkylphosphoric esters, linear alkyl alcohols, alkylether sulfates, alkylsulfonates, arylsulfonates, alkylethersulfonates and their combinations, preferably alkylamines salts with alkylphosphoric esters,
• les agents de modification de la rhéologie, tels que les polymères biodégradables et non- biodégradables, les cires, préférablement les cires provenant de sources renouvelables, minérales, ou les cires synthétiques, telles que les cires de Fischer-Tropsch, les amidoamides, les alkylamidoamides, • rheology modifiers, such as biodegradable and non-biodegradable polymers, waxes, preferably waxes from renewable, mineral sources, or synthetic waxes, such as Fischer-Tropsch waxes, amidoamides, alkylamidoamides,
• les agents d’hydrofugation, tels que les alcools alkyliques linéaires et les cires microcristallines, • water repellants, such as linear alkyl alcohols and microcrystalline waxes,
• les agents de dispersion, tels que les huiles provenant de sources végétales et minérales, • dispersing agents, such as oils from vegetable and mineral sources,
• les colorants, les traceurs UV, les pigments, • dyes, UV tracers, pigments,
• les micronutriments minéraux et/ou organiques et les oligo-éléments, qui peuvent être, mais sont préférablement, finement dispersés et/ou compatibilisés, par exemple des com- plexes métalliques, • mineral and / or organic micronutrients and trace elements, which can be, but are preferably, finely dispersed and / or compatibilized, for example compounds metal plexes,
• les pesticides, tels que les insecticides, les herbicides, les fongicides, les nématocides et similaires, • pesticides, such as insecticides, herbicides, fungicides, nematocides and the like,
• les bactéries, la levure, les champignons, les virus, les enzymes, • bacteria, yeast, fungi, viruses, enzymes,
• les antioxydants, les conservateurs, les agents anti-UV, • antioxidants, preservatives, anti-UV agents,
• les agents de masquage d’odeur, les antiodorants, les arômes, les parfums, • odor masking agents, anti-odorants, flavors, fragrances,
• ainsi que les mélanges de deux ou plus des constituants énumérés ci-dessus. • as well as mixtures of two or more of the constituents listed above.
5. Formulation selon l'une quelconque des revendications précédentes, dont la viscosité se situe dans la plage de 1 mPa.s à 1000 mPa.s, préférablement de 2 mPa.s à 800 mPa.s, valeur limites incluses, telle que mesurée à l'aide d'un rhéomètre à cisaillement dynamique (Anton Paar MCR301) dans une géométrie à plaques parallèles de 50 mm (PP50) à 25 °C et à une vitesse de cisaillement de80 s-1. 5. Formulation according to any one of the preceding claims, the viscosity of which is in the range of 1 mPa.s to 1000 mPa.s, preferably 2 mPa.s to 800 mPa.s, limit values included, as measured. using a dynamic shear rheometer (Anton Paar MCR301) in a 50 mm parallel plate geometry (PP50) at 25 ° C and a shear rate of 80 s -1 .
6. Formulation selon l’une quelconque des revendications précédentes, l'au moins un polyalcool incluant le glycérol (ou le 1 ,2,3-propanetriol), l’éthylèneglycol, le diéthylèneglycol, le propylèneglycol, le dipropylèneglycol, l’érythritol, le xylitol, le thréitol, le mannitol, le sorbitol, le galactitol, le fucitol, l’iditol, l’inositol, le volémitol, Tisonnait, le maltitol, le lactitol, le maltotriitol, le m altotétra- ito I , la dextrine, le dextrose, les disaccharides, le fructose, le sucrose, le galactose, le lactose, le maltose, la maltodextrine, le mannose, le saccharose, le xylose, les sucres provenant de sources naturelles, ainsi que leurs mélanges. 6. Formulation according to any one of the preceding claims, the at least one polyalcohol including glycerol (or 1, 2,3-propanetriol), ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, erythritol, xylitol, threitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, Tisonnait, maltitol, lactitol, maltotriitol, m altotetra- ito I, dextrin, dextrose, disaccharides, fructose, sucrose, galactose, lactose, maltose, maltodextrin, mannose, sucrose, xylose, sugars from natural sources, as well as mixtures thereof.
7. Formulation selon l'une quelconque des revendications précédentes, Tau moins un polyalcool étant le glycérol. 7. Formulation according to any one of the preceding claims, at least one polyalcohol being glycerol.
8. Formulation selon Tune quelconque des revendications précédentes, le polyalcool étant utilisé à des dosages entre 20 % en poids et 95 % en poids, plus préférablement entre 30 % en poids et 90 % en poids, encore plus préférablement entre 50 % en poids et 85 % en poids, par rapport au poids total de la composition comprenant le polyalcool a) et le tensioactif alcoxylé b). 8. Formulation according to any one of the preceding claims, the polyalcohol being used in dosages between 20% by weight and 95% by weight, more preferably between 30% by weight and 90% by weight, still more preferably between 50% by weight and 85% by weight, relative to the total weight of the composition comprising the polyalcohol a) and the alkoxylated surfactant b).
9. Formulation selon Tune quelconque des revendications précédentes, le tensioactif alcoxylé comprenant une séquence d’un ou de plusieurs motif(s) d’alkylénoxy, choisi(s) parmi Téthylénoxy, le propylénoxy, le butylénoxy et leurs mélanges. 9. Formulation according to any one of the preceding claims, the alkoxylated surfactant comprising a sequence of one or more units of alkylenoxy, chosen (s) from ethylenoxy, propylenoxy, butylenoxy and their mixtures.
10. Formulation selon l’une quelconque des revendications précédentes, le tensioactif alcoxylé comprenant 3 à 100 motifs alkylénoxy récurrents, préférablement 3 à 80 motifs alkylénoxy récurrents, plus préférablement 3 à 60 motifs alkylénoxy récurrents, provenant de l’ouverture d’un cycle oxirane. 10. A formulation according to any one of the preceding claims, the alkoxylated surfactant comprising 3 to 100 repeating alkylenoxy units, preferably 3 to 80 recurring alkylenoxy units, more preferably 3 to 60 recurring alkylenoxy units, originating from the opening of an oxirane ring. .
11. Formulation selon l’une quelconque des revendications précédentes, le tensioactif alcoxylé étant utilisé à des dosages de 1 % en poids à 30 % en poids et préférablement de 1 % en poids à 25 % en poids, plus préférablement de 2 % en poids à 20 % en poids et encore plus préférablement de 2 % en poids à 15 % en poids, par rapport au poids total de la composition comprenant le polyalcool a) et ledit tensioactif alcoxylé b). 11. A formulation according to any one of the preceding claims, the alkoxylated surfactant being used in dosages of 1 wt% to 30 wt% and preferably 1 wt% to 25 wt%, more preferably 2 wt%. at 20% by weight and even more preferably from 2% by weight to 15% by weight, relative to the total weight of the composition comprising the polyalcohol a) and the said alkoxylated surfactant b).
12. Formulation selon l’une quelconque des revendications précédentes, la quantité de solvant(s) allant de 0,5 % en poids à 30 % en poids, préférablement de 2 % en poids à 25 % en poids, plus préférablement de 5 % en poids à 20 % en poids, par rapport au poids total de la formulation. 12. Formulation according to any one of the preceding claims, the amount of solvent (s) ranging from 0.5% by weight to 30% by weight, preferably from 2% by weight to 25% by weight, more preferably from 5%. by weight to 20% by weight, relative to the total weight of the formulation.
13. Utilisation de la formulation selon l’une quelconque des revendications précédentes, en tant que formulation d'enrobage pour des particules afin de réduire et même d'éviter l'effet d'agglomération et/ou la génération de poussière. 13. Use of the formulation according to any one of the preceding claims, as a coating formulation for particles in order to reduce and even avoid the effect of agglomeration and / or generation of dust.
14. Particule enrobée par la formulation selon l'une quelconque des revendications 1 à 9. 14. A particle coated with the formulation according to any one of claims 1 to 9.
15. Particule selon la revendication 14, choisie parmi les particules minérales ou organiques granulées, le charbon, les minerais, les agrégats minéraux, le soufre, les particules de bois, les salissures, les déchets granulés, les médicaments, les céréales, les graines, la nourriture granulée ou pelletisée pour animaux et analogues, préférablement choisie parmi les particules ou les granules d'engrais. 15. Particle according to claim 14, chosen from granulated mineral or organic particles, coal, ores, mineral aggregates, sulfur, wood particles, dirt, granulated waste, drugs, cereals, seeds. , granulated or pelletized animal feed and the like, preferably selected from particles or granules of fertilizer.
16. Particule selon l'une quelconque des revendications 14 et 15, la quantité de formulation enrobée sur ladite particule s'élevant entre 0,01 % en poids et 10 % en poids, plus préférablement entre 0,02 % en poids et 5 % en poids, encore plus préférablement entre 0,02 % en poids et 2 % en poids, valeurs limites incluses, par rapport à la masse totale de la particule enrobée. 16. Particle according to any one of claims 14 and 15, the amount of formulation coated on said particle being between 0.01% by weight and 10% by weight, more preferably between 0.02% by weight and 5%. by weight, even more preferably between 0.02% by weight and 2% by weight, limit values included, based on the total mass of the coated particle.
PCT/FR2021/051034 2020-06-09 2021-06-09 Coating formulation for protecting against agglomeration and dust, and particle coated therewith WO2021250353A1 (en)

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