WO2003007715A1 - Method for treating water and surfaces in contact with same for controlling macro-organisms and corresponding composition - Google Patents

Method for treating water and surfaces in contact with same for controlling macro-organisms and corresponding composition Download PDF

Info

Publication number
WO2003007715A1
WO2003007715A1 PCT/FR2002/002378 FR0202378W WO03007715A1 WO 2003007715 A1 WO2003007715 A1 WO 2003007715A1 FR 0202378 W FR0202378 W FR 0202378W WO 03007715 A1 WO03007715 A1 WO 03007715A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
emulsion
water
radical
polyamine
Prior art date
Application number
PCT/FR2002/002378
Other languages
French (fr)
Inventor
Antoine Vanlaer
Original Assignee
Mexel Sa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mexel Sa filed Critical Mexel Sa
Publication of WO2003007715A1 publication Critical patent/WO2003007715A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/04—Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/20—Prevention of biofouling

Definitions

  • the present invention relates to a method of treating water and the surfaces in contact with it in order to prevent and / or eliminate and / or control the fixation of macro-organisms on said surfaces in contact with it.
  • water it also relates to a composition to
  • the water circulates or is stored, first microorganisms develop which form on said surfaces a biological or bacterial veil made up of organic matter, bacteria, algae, protozoa or other microorganisms.
  • This biological veil can lead to significant yield losses in heat exchangers by
  • this biological veil can cause localized corrosions, which are linked to the physical presence and to the metabolism of the microorganisms constituting said veil. It also develops later, on surfaces in contact with water, macro-organisms, which can be algae, molluscs
  • halogens or halogenated organic or mineral derivatives such as chlorine, bromine, iodine, potassium chloride, hypochlorous acid and its sodium or calcium salts, are used.
  • hypobromous acid, the salts of dichloro- and trichloroisocyanuric acids or halogenated hydantoins are used.
  • a composition according to French patent 2,727,958, having a defined formulation and presented in the form of an emulsion should comprise at least two families of globules of lipophilic phase (s), these two families differing in the average size of the globules which constitute them.
  • the term "globule” is not associated with a particular physical structure and must be considered as a generic term designating the entities or fluid particles which constitute the discontinuous phase of the emulsion; it is believed however, although this should in no way be considered as limiting, that said globules are micelles.
  • the parameters of the manufacturing process allowing the emulsion to be obtained are kept constant, a substantially constant effectiveness of the emulsion obtained when it is used for water treatment and / or surfaces in contact with water.
  • the parameters of the emulsion manufacturing process can be adjusted so as to obtain optimum efficiency of the emulsion produced, by acting on the mean size of the globules of each family and / or on the relative proportion of the globules of the two families.
  • the determination of the average size of the globules can be carried out in a known manner by measurements relating to the light scattered under the incidence of a light ray passing through the composition.
  • the characteristics of the scattered light make it possible to identify the different populations of particles in a liquid phase, that is to say in the case of the compositions according to the invention, the different populations of globules in the continuous aqueous phase of the emulsion.
  • One of the devices allowing this type of determination is, for example, the "zetasizer" supplied by the company called “MALVERN INSTRUMENTS”.
  • the international standard ISO 5341: 1996 was used, which was approved as a European standard.
  • This standard refers to the determination of the inhibition of the mobility of the macro-organism "Daphnia magna Straus”; the concentration (ie the concentration present at the start of the test) is determined under the conditions defined in the standard which, in 24 hours, immobilizes 50% of the "Daphnia magna” put into experimentation: this concentration is called “effective initial inhibitory concentration” which is designated by CE 50 (24h); this concentration is expressed in micrograms per liter.
  • CE 50 24h
  • the present invention therefore relates to a process for treating water and surfaces in contact with said water with a view to preventing and / or eliminating and / or controlling the fixation of molluscs, crustaceans, hydraires, bryzoans and hydrozoans on said surfaces in contact with water, process in which at least one active product is injected into water comprising, first of all, at least one polyamine of formula I
  • Ri is a C 8 -C 22 alkyl or alkenyl radical and n is an integer between 0 and 3 (limits included), and / or at least one mono amine of formula II
  • R 2 is a Cs-C 22 alkyl or alkenyl radical, and, secondly, at least one hydroxylated organic solvent, the active product (s) being injected into the water in the form of an emulsion with a continuous aqueous phase, characterized in that an emulsion comprising at least two families of globules dispersed in its phase is used as emulsion comprising the active product (s) continuous aqueous, the first family consisting of globules whose average size is between 170 and 250 nanometers while the second family consists of globules, the average size of which is between 400 and 800 nanometers, each of these two families constituting at least 30% of the total volume of the dispersed phase of the emulsion .
  • an emulsifying agent is preferably used; advantageously, such an emulsifying agent comprises at least one polyoxyethylenated tertiary amine of
  • R 3 is a Cs-C 22 alkyl or alkylene radical and x and y are integers such that (x + y) is between 5 and 50
  • At least one hydroxylated organic solvent is used in a proportion of between 1% and 15% by weight relative to the total weight of the amines of formula I and II, which are found in the emulsion injected into the water to be treated .
  • the solvents are advantageously chosen from the group formed by diethylene glycol, hexylene glycol, monopropylene glycol and an amino alcohol of formula IV
  • A is an alkylene radical, linear or branched, C 2 -C 4 , R 4 and R 5 , identical or different, representing H or an alkyl radical C1-C3.
  • 0.001 to 20 kg of amine (s) of formula I and II are injected per m of water to be treated.
  • the emulsion is prepared by means of a high shear turbine by simultaneously entering, into a chamber where said turbine acts, the water of the emulsion, the active product (s) and the possible emulsifying agent.
  • composition for carrying out the process defined above, said composition comprising at least one polyamine of formula I
  • Ri is a Cs-C 2 2 alkyl or alkenyl radical and n is an integer between 0 and 3 (limits included), and / or at least one mono amine of formula II
  • R 2 is a C 8 -C 225 alkyl or alkenyl radical
  • said composition being in the form of an emulsion in aqueous phase, characterized in that said emulsion comprises at least two families of globules dispersed in its aqueous phase continuous, the first family consisting of globules, the average dimension of which is between 170 and 250 nanometers, while the second family consists of globules, the average dimension of which is between 400 and 800 nanometers, each of these two families constituting at least 20% of the total volume of the dispersed phase of the emulsion and the sum of these two percentages being greater than 85%.
  • the composition according to the invention comprises, as active products of formula I, on the one hand, at least one polyamine of formula I, in which Ri is a dodecyl radical and / or at least one polyamine of formula I, in which i is a tetradecyl radical, and on the other hand, at least one polyamine of formula I, in which Ri is an octadecenyl radical.
  • the composition according to the invention can comprise a mixture of polyamine (s) derived from tallow and / or polyamine (s) derived from a vegetable or animal oil containing olein with at least one polyamine derived from coconut.
  • a composition according to the invention contains at most 15% by weight of amine (s) of formula II.
  • the composition according to the invention can comprise an emulsifying agent; this emulsifying agent may advantageously comprise at least one polyoxyethylenated tertiary compound of formula III
  • R 3 is a C 8 -C 2 2 alkyl or alkylene radical, x and y being whole numbers such that (x + y) is between 5 and 50 (limits included).
  • the emulsifying agent preferably represents from 5 to 45% by weight relative to the weight of the active product (s) of formula (s) I and IL
  • composition according to the invention can also comprise, in the aqueous phase of the emulsion, at least one organic solvent chosen from the group formed by diethylene glycol, hexylene glycol, monopropylene glycol and an amino alcohol of formula IV
  • A is an alkylene radical, linear or branched, C 2 -C 4 , R 4 and R 5 , identical or different, representing H or an alkyl radical C 1 -C 3 .
  • the emulsion injected into the water to be treated preferably comprises from 60% to 99% by weight of water relative to the total weight of said emulsion.
  • FIG. 1 shows, in axial section, an emulsifier device for obtaining the compositions according to the invention
  • - Figure 2 is a partial and schematic representation of the rotor vanes and the stator, vanes whose cooperation allows obtaining a high shear rate and, consequently, an emulsion sufficiently fine to enter the framework of the present invention.
  • the stator of the emulsifier has been designated by 1 as a whole.
  • the stator 1 essentially consists of two parts 1a and 1b joined together by means of studs 2.
  • the stator 1 receives a rotor designated by 3 as a whole, the rotor 3 being driven in rotation relative to the stator by a shaft 4.
  • the rotation of the rotor 3 and of the shaft 4 with respect to the stator 1 is allowed thanks to a system of sealed bearings 5.
  • the part lb of the stator comprises the inlet pipes for the products intended to constitute the emulsion: the water of the emulsion is sent according to the arrow FI and all the other products constituting the emulsion are sent according to the arrow F2.
  • the assembly enters the stator which comprises a circular blade holder 6 fixed by screws on the part lb of the stator, the blades 6a of the blade holder 6 being radial and directed towards the rotor side 3, that is to say of the side opposite to the arrival of the products to be emulsified.
  • the end of the rotor 3 which faces the blade holder 6 has the form of a plate which carries radial blades 3a.
  • the blades 3a and 6a are arranged in concentric circles, the blades 3a being located in the circular annular spaces, which exist between two successive circles of blades 6a.
  • the products to be emulsified enter the zone between the blade holder 6 and the rotor 3 through a central circular orifice of the blade holder
  • Formulations 1 to 3 correspond to Examples 62, 39 and 75 respectively of French Patent No. 2,727,958 and are recalled below (values given in parts by weight):

Abstract

The invention concerns a method for preventing macro-organisms from fixing on surfaces in contact with water. The invention also concerns a composition to be injected in water for said treatment in the form of an aqueous emulsion. The composition is a mixture of amines; the emulsion forming it comprises at least two families of globules, the first having an average dimension from 170 to 250 nanometers and the second an average dimension from 400 to 800 nanometers.

Description

PROCEDE DE TRAITEMENT D ' EAU ET DES SURFACES LA CONTACTANT POUR CONTROLLER LES MACRO-ORGANISMES ET COMPOSITION CORRESPONDANTEPROCESS FOR TREATING WATER AND SURFACES CONTACTING IT TO CONTROL MACROORGANISMS AND COMPOSITION THEREOF
La présente invention concerne un procédé de traitement d'eau et des surfaces en contact avec celle-ci en vue d'empêcher et/ou d'éliminer et/ou de contrôler la fixation de macro-organismes sur lesdites surfaces en contact avec l'eau ; elle concerne également une composition àThe present invention relates to a method of treating water and the surfaces in contact with it in order to prevent and / or eliminate and / or control the fixation of macro-organisms on said surfaces in contact with it. water; it also relates to a composition to
10 injecter dans l'eau pour ledit traitement.10 inject into water for said treatment.
De nombreuses industries utilisent soit de l'eau douce, telle que l'eau de rivière, de fleuve, de lac, de réservoir naturel, de barrage, de forage dans le sol ou de puisage, soit de l'eau salée telle que l'eau de mer. Cette eau est, par exemple, mise en oeuvre dans des circuits de chaudièreMany industries use either fresh water, such as river water, river water, lake water, natural reservoir, dam, drilling in the ground or drawing, or salt water such as l sea water. This water is, for example, used in boiler circuits
15 ou dans des circuits d'eau de ref oidissement. L'eau circule dans les installations industrielles soit en circuit ouvert, l'eau étant prélevée, par exemple, dans une rivière et rejetée ensuite en aval, soit en circuit fermé ou semi fermé, l'eau étant alors réutilisée plusieurs fois.15 or in cooling water circuits. Water circulates in industrial installations either in an open circuit, the water being taken, for example, from a river and then discharged downstream, or in a closed or semi-closed circuit, the water then being reused several times.
Il est connu que, sur les surfaces des installations dans lesquellesIt is known that on the surfaces of installations in which
20 l'eau circule ou est stockée, se développe d'abord des micro-organismes qui forment sur lesdites surfaces un voile biologique ou bactérien constitué de matières organiques, de bactéries, d'algues, de protozoaires ou autres micro-organismes. Ce voile biologique peut conduire à des pertes importantes de rendement, dans les échangeurs thermiques par20 the water circulates or is stored, first microorganisms develop which form on said surfaces a biological or bacterial veil made up of organic matter, bacteria, algae, protozoa or other microorganisms. This biological veil can lead to significant yield losses in heat exchangers by
25 exemple. De plus, la présence de ce voile biologique peut provoquer des corrosions localisées, qui sont liées à la présence physique et au métabolisme des micro-organismes constituant ledit voile. Il se développe également ultérieurement, sur les surfaces en contact avec l'eau, des macro-organismes, qui peuvent être des algues, des mollusques25 example. In addition, the presence of this biological veil can cause localized corrosions, which are linked to the physical presence and to the metabolism of the microorganisms constituting said veil. It also develops later, on surfaces in contact with water, macro-organisms, which can be algae, molluscs
30 tels que des moules, clams et bernacles, des serpulides, des crustacés, des hydraires, des bryozoaires et des hydrozoaires. Ces macro-organismes forment des enrochages sur les surfaces des installations en contact avec l'eau ; ces enrochages sont difficiles à éliminer et il est souvent nécessaire d'arrêter l'installation et de la vider de son eau puis d'enlever30 such as mussels, clams and barnacles, serpulids, crustaceans, hydraires, bryozoans and hydrozoans. These macro-organisms form deposits on the surfaces of installations in contact with water; these stones are difficult to remove and it is often necessary to stop the installation and empty it of water and then remove
35 mécaniquement ou manuellement lesdits enrochages. On a donc cherché à introduire dans l'eau, comme produits actifs, des composés ayant une action biocide et/ou biostatique susceptible d'empêcher la croissance des micro-organismes et des macro-organismes ainsi que leur fixation sur les surfaces en contact avec l'eau.35 mechanically or manually said skins. We therefore sought to introduce into water, as active products, compounds having a biocidal and / or biostatic action capable of preventing the growth of microorganisms and macroorganisms as well as their fixation on surfaces in contact with water.
De nombreux composés dits "biocides" ont été proposés et mis en oeuvre pour le traitement de l'eau. On utilise le plus souvent, en pratique, des halogènes ou des dérivés organiques ou minéraux halogènes, tels que le chlore, le brome, l'iode, le chlorure de potassium, l'acide hypochloreux et ses sels de sodium ou de calcium, l'acide hypobromeux, les sels des acides dichloro- et trichloro- isocyanuriques ou les hydantoïnes halogénées ; mais ces composés ont l'inconvénient d'être corrosifs et de former avec les matières organiques contenues dans l'eau des composés chlorés fortement toxiques. On a également proposé l'utilisation de dérivés peroxygénés, de phénols et de dérivés de phénols, de métaux lourds ou de leurs dérivés organiques, de formol, d'acide benzoïque et de benzoates pour de traitements par injection ou par contact avec un revêtement. Mais la plupart de ces composés sont coûteux et il n'est pas pensable de les utiliser dans les installations industrielles mettant en œuvre de grandes quantités d'eau. D'autre part, nombre d'entre eux laissent des résidus toxiques ou corrosifs dans l'eau traitée. Les composés biocides sont généralement utilisés sous forme de solutions ou de dispersions dans une phase aqueuse contenant éventuellement des solvants organiques ; dans ce cas, ils sont le plus souvent injectés dans l'eau à traiter.Many so-called "biocidal" compounds have been proposed and used for the treatment of water. Most often, in practice, halogens or halogenated organic or mineral derivatives, such as chlorine, bromine, iodine, potassium chloride, hypochlorous acid and its sodium or calcium salts, are used. hypobromous acid, the salts of dichloro- and trichloroisocyanuric acids or halogenated hydantoins; but these compounds have the drawback of being corrosive and of forming highly toxic chlorine compounds with the organic materials contained in water. It has also been proposed to use peroxygen derivatives, phenols and phenol derivatives, heavy metals or their organic derivatives, formaldehyde, benzoic acid and benzoates for treatments by injection or by contact with a coating. However, most of these compounds are expensive and it is unthinkable to use them in industrial installations using large quantities of water. On the other hand, many of them leave toxic or corrosive residues in the treated water. Biocidal compounds are generally used in the form of solutions or dispersions in an aqueous phase optionally containing organic solvents; in this case, they are most often injected into the water to be treated.
Dans le brevet français 2 727 958, on a indiqué que les aminés, plus spécialement un mélange particulier de polyamines, présentent toutes les propriétés requises pour un composé biocide utilisable dans un procédé de traitement d'eau industrielle, en particulier dans une installation en circuit ouvert, et qu'elles permettent avantageusement d'éliminer les macro-organismes, plus particulièrement les mollusques, des surfaces en contact avec l'eau. Elles permettent plus particulièrement d'éliminer le problème posé par les moules zébrées ou dreissénes dans les installations industrielles dans lesquelles l'eau circule en circuit ouvert, telles que les installations de refroidissement dans les centrales thermiques ou nucléaires. Dans ce brevet, on a notamment proposé d'introduire le(s) produit(s) actif(s) dans les compositions utilisées pour pratiquer ledit traitement sous forme d'une emulsion qu'on injecte dans l'eau à traiter, ladite emulsion comportant une phase aqueuse et des globules de phase(s) lipophile(s). On a cependant constaté qu'une telle emulsion pouvait avoir une efficacité variable pour une même formulation de la composition sans que, jusqu'à présent, il ait été possible de définir les paramètres influant sur cette efficacité.In French patent 2,727,958, it was indicated that the amines, more especially a particular mixture of polyamines, have all the properties required for a biocidal compound usable in a process for treating industrial water, in particular in a circuit installation. open, and that they advantageously make it possible to eliminate macro-organisms, more particularly molluscs, from surfaces in contact with water. They more particularly make it possible to eliminate the problem posed by zebra or dreissene mussels in industrial installations in which water circulates in an open circuit, such as cooling installations in thermal or nuclear power plants. In this patent, it has in particular been proposed to introduce the active product (s) into the compositions used to practice said treatment in the form of an emulsion which is injected into the water to be treated, said emulsion comprising an aqueous phase and globules of lipophilic phase (s). However, it has been found that such an emulsion could have variable effectiveness for the same formulation of the composition without, until now, it has been possible to define the parameters influencing this efficiency.
Selon la présente invention, on a maintenant trouvé que, de façon surprenante, pour avoir une efficacité optimum, une composition selon le brevet français 2 727 958, ayant une formulation définie et présentée sous forme d'émulsion, devait comporter au moins deux familles de globules de phase(s) lipophile(s), ces deux familles différant par la taille moyenne des globules qui les constituent. Dans le cadre de la présente demande de brevet, le terme "globule" n'est pas associé à une structure physique particulière et doit être considéré comme un vocable générique désignant les entités ou particules fluides qui constituent la phase discontinue de l'émulsion ; on pense cependant, bien que cela ne doive en aucun cas être considéré comme limitatif, que lesdits globules sont des micelles. On a constaté que, lorsque le procédé de fabrication mis en œuvre permet d'obtenir ces deux familles de globules, dans ce cas, si l'on maintient constants les paramètres du procédé de fabrication permettant l'obtention de l'émulsion, on obtient une efficacité sensiblement constante de l'émulsion obtenue lorsqu'on l'utilise pour un traitement d'eau et/ou des surfaces en contact avec l'eau. En outre, pour une formulation donnée de la composition selon l'invention, on peut régler les paramètres du procédé de fabrication de l'émulsion de façon à obtenir une efficacité optimum de l'émulsion fabriquée, en agissant sur la dimension moyenne des globules de chaque famille et/ou sur la proportion relative des globules des deux familles.According to the present invention, it has now been found that, surprisingly, in order to have optimum effectiveness, a composition according to French patent 2,727,958, having a defined formulation and presented in the form of an emulsion, should comprise at least two families of globules of lipophilic phase (s), these two families differing in the average size of the globules which constitute them. In the context of the present patent application, the term "globule" is not associated with a particular physical structure and must be considered as a generic term designating the entities or fluid particles which constitute the discontinuous phase of the emulsion; it is believed however, although this should in no way be considered as limiting, that said globules are micelles. It has been found that, when the manufacturing process used makes it possible to obtain these two families of globules, in this case, if the parameters of the manufacturing process allowing the emulsion to be obtained are kept constant, a substantially constant effectiveness of the emulsion obtained when it is used for water treatment and / or surfaces in contact with water. In addition, for a given formulation of the composition according to the invention, the parameters of the emulsion manufacturing process can be adjusted so as to obtain optimum efficiency of the emulsion produced, by acting on the mean size of the globules of each family and / or on the relative proportion of the globules of the two families.
La détermination de la taille moyenne des globules peut être effectuée de façon connue par des mesures portant sur la lumière diffusée sous incidence d'un rayon lumineux traversant la composition. Les caractéristiques de la lumière diffusée permettent d'identifier les différentes populations de particules dans une phase liquide, c'est à dire dans le cas des compositions selon l'invention, les différentes populations de globules dans la phase aqueuse continue de l'émulsion. L'un des appareils permettant ce type de détermination est, par exemple, le "zetasizer" fourni par la société dite "MALVERN INSTRUMENTS". Pour déterminer l'efficacité de l'injection dans l'eau d'une composition selon l'invention vis à vis des macro-organismes, on a utilisé la norme internationale ISO 5341 : 1996, qui a été approuvée comme norme européenne. Cette norme se réfère à la détermination de l'inhibition de la mobilité du macro-organisme "Daphnia magna Straus" ; on détermine, dans les conditions définies dans la norme, la concentration (c'est à dire la concentration présente au début de l'essai) qui, en 24 heures, immobilise 50 % des "Daphnia magna" mises en expérimentation : cette concentration est dite "concentration efficace initiale inhibitrice" qui est désignée par CE50(24h) ; cette concentration est exprimée en microgrammes par litre. En d'autres termes, plus la CE50 (24h) d'une composition testée est faible plus ladite composition est efficace vis à vis des macro-organismes.The determination of the average size of the globules can be carried out in a known manner by measurements relating to the light scattered under the incidence of a light ray passing through the composition. The characteristics of the scattered light make it possible to identify the different populations of particles in a liquid phase, that is to say in the case of the compositions according to the invention, the different populations of globules in the continuous aqueous phase of the emulsion. One of the devices allowing this type of determination is, for example, the "zetasizer" supplied by the company called "MALVERN INSTRUMENTS". To determine the effectiveness of the injection into water of a composition according to the invention with respect to macro-organisms, the international standard ISO 5341: 1996 was used, which was approved as a European standard. This standard refers to the determination of the inhibition of the mobility of the macro-organism "Daphnia magna Straus"; the concentration (ie the concentration present at the start of the test) is determined under the conditions defined in the standard which, in 24 hours, immobilizes 50% of the "Daphnia magna" put into experimentation: this concentration is called "effective initial inhibitory concentration" which is designated by CE 50 (24h); this concentration is expressed in micrograms per liter. In other words, the lower the EC 50 (24 h) of a composition tested, the more said composition is effective with respect to macro-organisms.
La présente invention a, en conséquence, pour objet un procédé de traitement d'eau et de surfaces en contact avec ladite eau en vue d'empêcher et/ou d'éliminer et/ou de contrôler la fixation de mollusques, crustacés, hydraires, bryzoaires et hydrozoaires sur lesdites surfaces en contact avec l'eau, procédé dans lequel on injecte dans l'eau au moins un produit actif comportant, en premier lieu, au moins une polyamine de formule IThe present invention therefore relates to a process for treating water and surfaces in contact with said water with a view to preventing and / or eliminating and / or controlling the fixation of molluscs, crustaceans, hydraires, bryzoans and hydrozoans on said surfaces in contact with water, process in which at least one active product is injected into water comprising, first of all, at least one polyamine of formula I
Ri - NH[(CH2)3 - NH]n - (CH2)3 NH2 (I)Ri - NH [(CH 2 ) 3 - NH] n - (CH 2 ) 3 NH 2 (I)
formule dans laquelle Ri est un radical alkyl ou alkényl en C8-C22 et n est un nombre entier compris entre 0 et 3 (bornes incluses), et/ou au moins une mono aminé de formule IIformula in which Ri is a C 8 -C 22 alkyl or alkenyl radical and n is an integer between 0 and 3 (limits included), and / or at least one mono amine of formula II
R2 - NH2 (II)R 2 - NH 2 (II)
formule dans laquelle R2 est un radical alkyl ou alkényl en Cs-C22, et, en second lieu, au moins un solvant organique hydroxylé, le(s) produit(s) actif(s) étant injecté(s) dans l'eau sous forme d'une emulsion à phase aqueuse continue, caractérisé par le fait que l'on utilise, comme emulsion comprenant le(s) produit(s) actif(s) une emulsion comportant au moins deux familles de globules dispersés dans sa phase aqueuse continue, la première famille étant constituée de globules dont la dimension moyenne est comprise entre 170 et 250 nanomètres alors que la seconde famille est constituée de globules, dont la dimension moyenne est comprise entre 400 et 800 nanomètres, chacune de ces deux familles constituant au moins 30 % du volume total de la phase dispersée de l'émulsion. Pour favoriser la stabilité de l'émulsion de produit(s) actif(s), on utilise, de préférence, un agent émulsifiant ; avantageusement, un tel agent émulsifiant comprend au moins une aminé tertiaire polyoxyéthylénée de formule IIIformula in which R 2 is a Cs-C 22 alkyl or alkenyl radical, and, secondly, at least one hydroxylated organic solvent, the active product (s) being injected into the water in the form of an emulsion with a continuous aqueous phase, characterized in that an emulsion comprising at least two families of globules dispersed in its phase is used as emulsion comprising the active product (s) continuous aqueous, the first family consisting of globules whose average size is between 170 and 250 nanometers while the second family consists of globules, the average size of which is between 400 and 800 nanometers, each of these two families constituting at least 30% of the total volume of the dispersed phase of the emulsion . To promote the stability of the emulsion of active product (s), an emulsifying agent is preferably used; advantageously, such an emulsifying agent comprises at least one polyoxyethylenated tertiary amine of formula III
(CH2CH20)x - H(CH 2 CH 2 0) x - H
R3 - N """" (III)R 3 - N """" (III)
^ (CH2CH20)y - H^ (CH 2 CH 2 0) y - H
formule dans laquelle R3 est un radical alkyl ou alkylène en Cs-C22 et x et y sont des nombres entiers tels que (x+y) soit compris entre 5 et 50formula in which R 3 is a Cs-C 22 alkyl or alkylene radical and x and y are integers such that (x + y) is between 5 and 50
(bornes incluses).(terminals included).
Dans le procédé selon l'invention, on utilise avantageusement, comme produit actif de formule I, un mélange contenant, d'une part, au moins une polyamine de formule I, dans laquelle Ri est un radical dodécyl, et/ou au moins une polyamine de formule I, dans laquelle Ri est un radical tétradécyl, et d'autre part, au moins une polyamine de formuleIn the process according to the invention, there is advantageously used, as active product of formula I, a mixture containing, on the one hand, at least one polyamine of formula I, in which R 1 is a dodecyl radical, and / or at least one polyamine of formula I, in which Ri is a tetradecyl radical, and on the other hand, at least one polyamine of formula
I dans laquelle Ri est un radical octadécényl.I in which Ri is an octadecenyl radical.
De préférence, on utilise au moins un solvant organique hydroxylé dans une proportion comprise entre 1 % et 15 % en poids par rapport au poids total des aminés de formule I et II, qui se trouvent dans l'émulsion injectée dans l'eau à traiter. Les solvants sont avantageusement choisis dans le groupe formé par le diéthylène glycol, l'hexylène glycol, le monopropylène glycol et un amino alcool de formule IVPreferably, at least one hydroxylated organic solvent is used in a proportion of between 1% and 15% by weight relative to the total weight of the amines of formula I and II, which are found in the emulsion injected into the water to be treated . The solvents are advantageously chosen from the group formed by diethylene glycol, hexylene glycol, monopropylene glycol and an amino alcohol of formula IV
Figure imgf000007_0001
Figure imgf000007_0001
formule dans laquelle A est un radical alkylène, linéaire ou ramifié, en C2-C4, R4 et R5, identiques ou différents, représentant H ou un radical alkyl en C1-C3. On peut prévoir d'injecter le(s) produit(s) actif(s) dans l'eau de façon continue ou de façon intermittente. Avantageusement, on injecte de 0,001 à 20 kg d'amine(s) de formule I et II par m d'eau à traiter.formula in which A is an alkylene radical, linear or branched, C 2 -C 4 , R 4 and R 5 , identical or different, representing H or an alkyl radical C1-C3. Provision may be made to inject the active product (s) into the water continuously or intermittently. Advantageously, 0.001 to 20 kg of amine (s) of formula I and II are injected per m of water to be treated.
Avantageusement, on prépare l'émulsion au moyen d'une turbine à fort cisaillement en faisant entrer simultanément, dans une chambre où agit ladite turbine, l'eau de l'émulsion, le(s) ρroduit(s) actif(s) et l'éventuel agent émulsionnant.Advantageously, the emulsion is prepared by means of a high shear turbine by simultaneously entering, into a chamber where said turbine acts, the water of the emulsion, the active product (s) and the possible emulsifying agent.
L'invention a également pour objet une composition pour la mise en œuvre du procédé ci-dessus défini, ladite composition comportant au moins une polyamine de formule IThe subject of the invention is also a composition for carrying out the process defined above, said composition comprising at least one polyamine of formula I
R, - NH[(CH2)3 - NH]n - (CH2)3 NH2 (I)R, - NH [(CH 2 ) 3 - NH] n - (CH 2 ) 3 NH 2 (I)
formule dans laquelle Ri est un radical alkyl ou alkényl en Cs-C22 et n est un nombre entier compris entre 0 et 3 (bornes incluses), et/ou au moins une mono aminé de formule IIformula in which Ri is a Cs-C 2 2 alkyl or alkenyl radical and n is an integer between 0 and 3 (limits included), and / or at least one mono amine of formula II
R2 -NH2 (II)R 2 -NH 2 (II)
formule dans laquelle R2 est un radical alkyl ou alkényl en C8-C225 ladite composition étant sous la forme d'une emulsion en phase aqueuse, caractérisée par le fait que ladite emulsion comporte au moins deux familles de globules dispersés dans sa phase aqueuse continue, la première famille étant constituée de globules, dont la dimension moyenne est comprise entre 170 et 250 nanomètres, alors que la seconde famille est constituée de globules, dont la dimension moyenne est comprise entre 400 et 800 nanomètres, chacune de ces deux familles constituant au moins 20 % du volume total de la phase dispersée de l'émulsion et la somme de ces deux pourcentages étant supérieure à 85 %.formula in which R 2 is a C 8 -C 225 alkyl or alkenyl radical, said composition being in the form of an emulsion in aqueous phase, characterized in that said emulsion comprises at least two families of globules dispersed in its aqueous phase continuous, the first family consisting of globules, the average dimension of which is between 170 and 250 nanometers, while the second family consists of globules, the average dimension of which is between 400 and 800 nanometers, each of these two families constituting at least 20% of the total volume of the dispersed phase of the emulsion and the sum of these two percentages being greater than 85%.
Avantageusement, la composition selon l'invention comporte, comme produits actifs de formule I, d'une part, au moins une polyamine de formule I, dans laquelle Ri est un radical dodécyl et/ou au moins une polyamine de formule I, dans laquelle i est un radical tétradécyl, et d'autre part, au moins une polyamine de formule I, dans laquelle Ri est un radical octadécényl. La composition selon l'invention peut comporter un mélange de polyamine(s) dérivée(s) du suif et/ou de polyamine(s) dérivée(s) d'une huile végétale ou animale contenant de l'oléine avec au moins une polyamine dérivée du coprah. De préférence, une composition selon l'invention contient au plus 15 % en poids d'amine(s) de formule II. Pour améliorer la stabilité de l'émulsion, la composition selon l'invention peut comporter un agent émulsifiant ; cet agent émulsifiant peut avantageusement comprendre au moins une a iné tertiaire polyoxyéthylénée de formule IIIAdvantageously, the composition according to the invention comprises, as active products of formula I, on the one hand, at least one polyamine of formula I, in which Ri is a dodecyl radical and / or at least one polyamine of formula I, in which i is a tetradecyl radical, and on the other hand, at least one polyamine of formula I, in which Ri is an octadecenyl radical. The composition according to the invention can comprise a mixture of polyamine (s) derived from tallow and / or polyamine (s) derived from a vegetable or animal oil containing olein with at least one polyamine derived from coconut. Preferably, a composition according to the invention contains at most 15% by weight of amine (s) of formula II. To improve the stability of the emulsion, the composition according to the invention can comprise an emulsifying agent; this emulsifying agent may advantageously comprise at least one polyoxyethylenated tertiary compound of formula III
(CH2CH20)x - H(CH 2 CH 2 0) x - H
R3 - N ^"" (III)R 3 - N ^ " " (III)
^- (CH2CH20)y - H^ - (CH 2 CH 2 0) y - H
formule dans laquelle R3 est un radical alkyl ou alkylène en C8-C22 , x et y étant des nombres entiers tels que (x + y) soit compris entre 5 et 50 (bornes incluses). L'agent émulsifiant représente, de préférence, de 5 à 45 % en poids par rapport au poids du (des) produit(s) actif(s) de formule(s) I et ILformula in which R 3 is a C 8 -C 2 2 alkyl or alkylene radical, x and y being whole numbers such that (x + y) is between 5 and 50 (limits included). The emulsifying agent preferably represents from 5 to 45% by weight relative to the weight of the active product (s) of formula (s) I and IL
La composition selon l'invention peut aussi comprendre, dans la phase aqueuse de l'émulsion, au moins un solvant organique choisi dans le groupe formé par le diéthylène glycol, l'hexylène glycol, le monopropylène glycol et un amino alcool de formule IVThe composition according to the invention can also comprise, in the aqueous phase of the emulsion, at least one organic solvent chosen from the group formed by diethylene glycol, hexylene glycol, monopropylene glycol and an amino alcohol of formula IV
Figure imgf000009_0001
Figure imgf000009_0001
formule dans laquelle A est un radical alkylène, linéaire ou ramifié, en C2-C4, R4 et R5, identiques ou différents, représentant H ou un radical alkyl en C1-C3.formula in which A is an alkylene radical, linear or branched, C 2 -C 4 , R 4 and R 5 , identical or different, representing H or an alkyl radical C 1 -C 3 .
L'émulsion injectée dans l'eau à traiter comporte, de préférence, de 60 % à 99 % en poids d'eau par rapport au poids total de ladite emulsion.The emulsion injected into the water to be treated preferably comprises from 60% to 99% by weight of water relative to the total weight of said emulsion.
Pour mieux faire comprendre l'objet de l'invention, on va décrire ci-après, d'une part, un appareil susceptible de permettre l'obtention des compositions selon l'invention et, d'autre part, des exemples de réalisation desdites compositions dans ledit appareil. Les descriptions, qui vont suivre, sont données à titre d'exemples purement illustratifs et non limitatifs ; le dessin de l'appareil émulsionneur est un dessin schématique destiné uniquement à illustrer le principe de l'appareil mis en œuvre pour la réalisation des exemples de composition selon l'invention.To better understand the object of the invention, there will be described below, on the one hand, an apparatus capable of making it possible to obtain the compositions according to the invention and, on the other hand, examples of embodiment of said compositions in said apparatus. The descriptions which follow are given by way of purely illustrative and nonlimiting examples; the drawing of the emulsifying device is a drawing schematic intended only to illustrate the principle of the apparatus used for producing the examples of composition according to the invention.
Sur le dessin : - la figure 1 représente, en coupe axiale, un appareil émulsionneur permettant d'obtenir les compositions selon l'invention ; - la figure 2 est une représentation partielle et schématique des palettes du rotor et du stator, palettes dont la coopération permet l'obtention d'un fort taux de cisaillement et, en conséquence, d'une emulsion suffisamment fine pour entrer dans le cadre de la présente invention. Bien que l'appareil émulsionneur représenté sur les figures 1 et 2 ne fasse pas partie de l'invention, on va en donner ci-après une rapide description. On a désigné par 1 dans son ensemble le stator de l'émulsionneur. Le stator 1 est constitué essentiellement de deux parties la et lb assemblées l'une à l'autre au moyen de goujons 2. Le stator 1 reçoit un rotor désigné par 3 dans son ensemble, le rotor 3 étant entraîné en rotation par rapport au stator par un arbre 4. La rotation du rotor 3 et de l'arbre 4 par rapport au stator 1 est permise grâce à un système de paliers étanches 5.In the drawing: - Figure 1 shows, in axial section, an emulsifier device for obtaining the compositions according to the invention; - Figure 2 is a partial and schematic representation of the rotor vanes and the stator, vanes whose cooperation allows obtaining a high shear rate and, consequently, an emulsion sufficiently fine to enter the framework of the present invention. Although the emulsifier device shown in FIGS. 1 and 2 is not part of the invention, a brief description will be given below. The stator of the emulsifier has been designated by 1 as a whole. The stator 1 essentially consists of two parts 1a and 1b joined together by means of studs 2. The stator 1 receives a rotor designated by 3 as a whole, the rotor 3 being driven in rotation relative to the stator by a shaft 4. The rotation of the rotor 3 and of the shaft 4 with respect to the stator 1 is allowed thanks to a system of sealed bearings 5.
La partie lb du stator comporte les canalisations d'arrivée des produits destinés à constituer l'émulsion : l'eau de l'émulsion est envoyée selon la flèche FI et tous les autres produits constitutifs de l'émulsion sont envoyés selon la flèche F2. L'ensemble pénètre dans le stator qui comporte un porte-lames circulaire 6 fixé par des vis sur la partie lb du stator, les lames 6a du porte-lames 6 étant radiales et dirigées du côté du rotor 3, c'est à dire du côté opposé à l'arrivée des produits à émulsionner. L'extrémité du rotor 3 qui fait vis-à-vis au porte-lames 6 a la forme d'un plateau qui porte des lames radiales 3a. Les lames 3a et 6a sont disposées selon des cercles concentriques, les lames 3a étant situées dans les espaces annulaires circulaires, qui existent entre deux cercles successifs de lames 6a.The part lb of the stator comprises the inlet pipes for the products intended to constitute the emulsion: the water of the emulsion is sent according to the arrow FI and all the other products constituting the emulsion are sent according to the arrow F2. The assembly enters the stator which comprises a circular blade holder 6 fixed by screws on the part lb of the stator, the blades 6a of the blade holder 6 being radial and directed towards the rotor side 3, that is to say of the side opposite to the arrival of the products to be emulsified. The end of the rotor 3 which faces the blade holder 6 has the form of a plate which carries radial blades 3a. The blades 3a and 6a are arranged in concentric circles, the blades 3a being located in the circular annular spaces, which exist between two successive circles of blades 6a.
Les produits à émulsionner entrent dans la zone comprise entre le porte-lames 6 et le rotor 3 par un orifice circulaire central du porte-lamesThe products to be emulsified enter the zone between the blade holder 6 and the rotor 3 through a central circular orifice of the blade holder
6, traversent de façon centrifuge l'espace compris entre le porte-lames 6 et le rotor 3 et sont éjectés à la périphérie dudit espace pour pouvoir être évacués hors de l'appareil selon la flèche F3. Il est clair que le flux de produits entrants subit des cisaillements successifs entre les lames fixes 6a et les lames 3 a entraînées en rotation par l'arbre 4. De façon connue, la finesse de l'émulsion obtenue est fonction, notamment, du nombre de cercles concentriques de lames 3a et 6a, de l'espace radial entre les bordures desdites lames et de la vitesse de rotation de l'arbre 4. En d'autres termes, pour un appareil donné et un débit donné, les caractéristiques de l'émulsion obtenue sont fonction de la vitesse de rotation du rotor.6, pass through the space between the blade holder centrifugally and the rotor 3 and are ejected at the periphery of said space in order to be able to be evacuated from the apparatus according to arrow F3. It is clear that the flow of incoming products undergoes successive shearing between the fixed blades 6a and the blades 3 a driven in rotation by the shaft 4. In known manner, the fineness of the emulsion obtained is a function, in particular, of the number of concentric circles of blades 3a and 6a, of the radial space between the edges of said blades and of the speed of rotation of the shaft 4. In other words, for a given device and a given flow, the characteristics of l emulsion obtained are a function of the speed of rotation of the rotor.
On a repris un certain nombre des exemples donnés dans le brevet français 2 727 958 en comparant les résultats des CE 50 (24h) pour différentes conditions de production. Pour chaque formulation, on a examiné les résultats que l'on obtient : - soit en fabriquant la composition par mélange dans une cuve cylindrique, qui comporte une agitation de brassage : la cuve a un diamètre de 2 m, une hauteur de 2 m et le brassage est obtenu par une agitation à 100 tours/mn avec un agitateur à pales pendant 30 minutes ; - soit en utilisant l'appareil émulsionneur ci-dessus décritA number of the examples given in French patent 2,727,958 were used by comparing the results of the EC 50 (24h) for different production conditions. For each formulation, the results obtained are examined: either by manufacturing the composition by mixing in a cylindrical tank, which includes stirring stirring: the tank has a diameter of 2 m, a height of 2 m and stirring is obtained by stirring at 100 rpm with a paddle stirrer for 30 minutes; - either by using the emulsifier device described above
(volume interne d'environ 1 litre) à un débit de production de 2 m /heure. Dans tous les cas, on a noté la dimension des globules de l'émulsion et les valeurs de CE 50 (24 h). On constate que, pour la fabrication en cuve, on obtient deux familles de globules, dont les dimensions moyennes sont toujours en dehors des valeurs données dans la définition du procédé selon l'invention mais présentent selon les essais une grande dispersion. Les valeurs de CE 50 (24 h) sont assez importantes et présentent aussi une grande dispersion selon les essais. La mesure des dimensions moyennes des globules a été effectuée à la sortie de la cuve de préparation mais non au moment de la mise en œuvre de la composition par injection dans l'eau à traiter.(internal volume of approximately 1 liter) at a production rate of 2 m / hour. In all cases, the size of the emulsion globules and the EC 50 values (24 h) were noted. It is noted that, for the manufacture in tanks, two families of globules are obtained, the mean dimensions of which are always outside the values given in the definition of the process according to the invention but according to the tests exhibit a great dispersion. The values of EC 50 (24 h) are quite large and also have a great dispersion according to the tests. The measurement of the average dimensions of the globules was carried out at the outlet of the preparation tank but not at the time of the implementation of the composition by injection into the water to be treated.
Dans le cas de la fabrication en émulsionneur, on constate également la présence de deux familles de globules mais les dimensions moyennes de ces globules sont très peu variables pour une vitesse de rotation donnée. Si la vitesse de rotation est suffisante (c'est à dire, pour les essais effectués, 4000 et 6000 t/minute), les dimensions moyennes des deux familles (FI = petit diamètre moyen et F2 = grand diamètre moyen) sont dans les limites indiquées dans la définition du procédé selon l'invention et les valeurs de CE50 (4 h) sont beaucoup plus basses que pour le cas où l'une au moins des valeurs de diamètre moyen se trouve à l'extérieur desdites limites ; on constate également dans ce cas une constance des valeurs CE 50 (24 h) pour une vitesse de rotation donnée.In the case of manufacture in an emulsifier, there is also the presence of two families of globules but the average dimensions of these globules are very little variable for a given speed of rotation. If the rotational speed is sufficient (i.e., for testing performed, 4000 and 6000 t / minute), the average dimensions of the two families (FI = small average diameter and F2 = large average diameter) are within the limits indicated in the definition of the process according to the invention and the values of EC50 (4 h) are much lower than for the case where at least one of the values of mean diameter lies outside said limits; in this case there is also a constancy of the CE 50 values (24 h) for a given speed of rotation.
L'ensemble des résultats obtenus a été fourni dans le tableau ci-après.All the results obtained have been provided in the table below.
TABLEAUBOARD
Figure imgf000012_0001
Figure imgf000012_0001
Formulations testées :Formulations tested:
Les formulations 1 à 3 correspondent aux exemples 62, 39 et 75 respectivement du brevet français n° 2 727 958 et sont rappelées ci- dessous (valeurs données en parties en poids) :Formulations 1 to 3 correspond to Examples 62, 39 and 75 respectively of French Patent No. 2,727,958 and are recalled below (values given in parts by weight):
- formulation 1 :- formulation 1:
N-coprah-l,3-propylène diamine 8N-copra-1,3-propylene diamine 8
N-oléyl-[NH-(CH2)3]3 NH2 2N-oleyl- [NH- (CH 2 ) 3 ] 3 NH 2 2
2-amino-2-méthyl-l-propanol 2,52-amino-2-methyl-1-propanol 2.5
Aminé d'oléine à 20 moles d'oxyde d'éthylène (Genamin ® -0-200) 2,5 Eau 85Oleine amine to 20 moles of ethylene oxide (Genamin ® -0-200) 2.5 Water 85
- formulation 2 :- formulation 2:
N-oléyl- 1 ,3 -propylène diamine 5N-oleyl- 1, 3 -propylene diamine 5
2-amino-2-méthyl-l-propanol 2,5 N-coprah-l,3-propylène diamine 52-amino-2-methyl-1-propanol 2.5 N-copra-1, 3-propylene diamine 5
Aminé d'oléine à 20 moles d'oxyde d'éthylèneOleine amine to 20 moles of ethylene oxide
(Gena in ® -0-200) 2,5(Gena in ® -0-200) 2.5
Eau 85Water 85
- formulation 3 : N-coprah-l,3-propylène diamine 4- formulation 3: N-copra-1,3-propylene diamine 4
N-oléyl- 1 ,3 -propylène diamine 6N-oleyl- 1, 3 -propylene diamine 6
2-diéthylamino- 1 -éthanol 2,52-diethylamino- 1-ethanol 2.5
Aminé d'oléine à 25 moles d'oxyde d'éthylène (Genamin ® -0-250) 2,5 Eau 85Oleine amine to 25 moles of ethylene oxide (Genamin ® -0-250) 2.5 Water 85
Il ressort du tableau que la constance des valeurs CE 50 (24 h) et leur réduction très sensible (c'est à dire l'augmentation sensible de l'efficacité de la composition) se produisent dès lors que la composition contient deux familles de globules telles que définies dans la définition générale du procédé et de la composition, qui a été donnée dans le texte de la présente description. It appears from the table that the constancy of the EC 50 values (24 h) and their very significant reduction (that is to say the appreciable increase in the effectiveness of the composition) occur as soon as the composition contains two families of globules as defined in the general definition of the process and of the composition, which has been given in the text of the present description.

Claims

REVENDICATIONS 1. Procédé de traitement d'eau et de surfaces en contact avec ladite eau en vue d'empêcher et/ou d'éliminer et/ou de contrôler la fixation des mollusques, crustacés, hydraires, bryozoaires et hydrozoaires sur lesdites surfaces en contact avec l'eau, procédé dans lequel on injecte dans l'eau au moins un produit actif comportant, en premier lieu, au moins une polyamine de formule ICLAIMS 1. Method for treating water and surfaces in contact with said water in order to prevent and / or eliminate and / or control the fixing of molluscs, crustaceans, hydraires, bryozoans and hydrozoans on said surfaces in contact with water, process in which at least one active product is injected into water comprising, first of all, at least one polyamine of formula I
Ri - NH[(CH2)3 - NH]n - (CH2)3 NH2 (I)Ri - NH [(CH 2 ) 3 - NH] n - (CH 2 ) 3 NH 2 (I)
fonnule dans laquelle Ri est un radical alkyl ou alkényl en Cs-C22 et n est un nombre entier compris entre 0 et 3 (bornes incluses), et/ou au moins une mono aminé de formule IIformula in which Ri is a Cs-C 22 alkyl or alkenyl radical and n is an integer between 0 and 3 (limits included), and / or at least one mono amine of formula II
R2 - NH2 (II)R 2 - NH 2 (II)
formule dans laquelle R2 est un radical alkyl ou alkényl en C8-C22, et, en second lieu, au moins un solvant organique hydroxylé, le(s) produit(s) actif(s) étant injecté(s) dans l'eau à traiter sous forme d'une emulsion à phase aqueuse continue, caractérisé par le fait que l'on utilise, comme emulsion comprenant le(s) produit(s) actif(s) une emulsion comportant au moins deux familles de globules dispersés dans sa phase aqueuse continue, la première famille étant constituée de globules, dont la dimension moyenne est comprise entre 170 et 250 nanomètres alors que la seconde famille est constituée de globules, dont la dimension moyenne est comprise entre 400 et 800 nanomètres, chacune de ces deux familles constituant au moins 20 % du volume total de la phase dispersée de l'émulsion et la somme de ces deux pourcentages étant supérieure à 85 %. formula in which R 2 is a C8-C 22 alkyl or alkenyl radical, and, secondly, at least one hydroxylated organic solvent, the active product (s) being injected into the water to be treated in the form of an emulsion with a continuous aqueous phase, characterized in that, as emulsion comprising the active product (s), an emulsion comprising at least two families of globules dispersed in its continuous aqueous phase, the first family consisting of globules, the average size of which is between 170 and 250 nanometers while the second family consists of globules, the average dimension of which is between 400 and 800 nanometers, each of these two families constituting at least 20% of the total volume of the dispersed phase of the emulsion and the sum of these two percentages being greater than 85%.
2. Procédé selon la revendication 1, caractérisé par le fait que l'on utilise une emulsion de produit(s) actif(s) comportant un agent émulsifiant.2. Method according to claim 1, characterized in that an emulsion of active product (s) comprising an emulsifying agent is used.
3. Procédé selon la revendication 2, caractérisé par le fait que l'agent émulsifiant comprend au moins une aminé tertiaire polyoxyéthylénée de formule III
Figure imgf000015_0001
3. Method according to claim 2, characterized in that the emulsifying agent comprises at least one polyoxyethylenated tertiary amine of formula III
Figure imgf000015_0001
formule dans laquelle R3 est un radical alkyl ou alkylène en C8-C22 et x et y sont des nombres entiers tels que (x + y) soit compris entre 5 et 50 (bornes incluses).formula in which R 3 is a C 8 -C 2 alkyl or alkylene radical and x and y are whole numbers such that (x + y) is between 5 and 50 (limits included).
4. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que l'on injecte le(s) ρroduit(s) actif(s) dans l'eau à traiter de façon continue.4. Method according to one of claims 1 to 3, characterized in that one injects (s) ρroduct (s) active (s) in the water to be treated continuously.
5. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que l'on injecte le(s) produit(s) actif(s) dans l'eau à traiter de façon intermittente. 5. Method according to one of claims 1 to 3, characterized in that the active product (s) is (are) injected into the water to be treated intermittently.
6. Procédé selon l'une des revendications 1 à 5, caractérisé par le fait que l'on utilise, comme produits actifs de formule (I) un mélange contenant, d'une part, au moins une polyamine de formule (I), formule dans laquelle Ri est un radical dodécyl, et/ou au moins une polyamine de formule (I), formule dans laquelle Ri est un radical tétradécyl, et d'autre part, au moins une polyamine de formule I dans laquelle Ri est un radical octadécényl.6. Method according to one of claims 1 to 5, characterized in that one uses, as active products of formula (I) a mixture containing, on the one hand, at least one polyamine of formula (I), formula in which Ri is a dodecyl radical, and / or at least one polyamine of formula (I), formula in which Ri is a tetradecyl radical, and on the other hand, at least one polyamine of formula I in which Ri is a radical octadecenyl.
7. Procédé selon l'une des revendications 1 à 6, caractérisé par le fait que l'on utilise une emulsion comportant de 1 % à 15 % en poids de solvant(s) organique(s) hydroxylé(s) par rapport au poids total des aminés de formule I et II se trouvant dans l'émulsion.7. Method according to one of claims 1 to 6, characterized in that an emulsion is used comprising from 1% to 15% by weight of organic solvent (s) hydroxylated (s) relative to the weight total of the amines of formula I and II found in the emulsion.
8. Procédé selon l'une des revendications 1 à 7, caractérisé par le fait que l'on choisit le(s) solvant(s) organique(s) hydroxylé(s) dans le groupe formé par le diéthylène glycol, l'hexylène glycol, le monopropylène glycol et un amino alcool de formule IV8. Method according to one of claims 1 to 7, characterized in that one chooses (s) solvent (s) organic (s) hydroxylated (s) in the group formed by diethylene glycol, hexylene glycol, monopropylene glycol and an amino alcohol of formula IV
HO - A - NR4R5 (IV)HO - A - NR 4 R 5 (IV)
formule dans laquelle A est un radical alkylène, linéaire ou ramifié, en C2-C , R4 et R5, identiques ou différents, représentant H ou un radical alkyl en Ci -C3. formula in which A is an alkylene radical, linear or branched, C 2 -C, R 4 and R 5 , identical or different, representing H or an alkyl radical C 1 -C 3 .
9. Procédé selon l'une des revendications 1 à 8, caractérisé par le fait que l'on injecte de 0,001 à 20 kg d'amine(s) de formule I et II par m3 d'eau à traiter.9. Method according to one of claims 1 to 8, characterized in that one injects from 0.001 to 20 kg of amine (s) of formula I and II per m 3 of water to be treated.
10. Composition pour la mise en œuvre du procédé selon la revendication 1, ladite composition comportant, en premier lieu, au moins une polyamine de formule I10. Composition for carrying out the method according to claim 1, said composition comprising, firstly, at least one polyamine of formula I
R, - NH[(CH2)3 - NH]n - (CH2)3 NH2 (I)R, - NH [(CH 2 ) 3 - NH] n - (CH 2 ) 3 NH 2 (I)
formule dans laquelle Ri est un radical alkyl ou alkényl en C8-C22 et n est un nombre entier compris entre 0 et 3 (bornes incluses), et/ou au moins une monoamine de formule IIformula in which Ri is a C 8 -C 22 alkyl or alkenyl radical and n is an integer between 0 and 3 (limits included), and / or at least one monoamine of formula II
R2 - NH2 (II)R 2 - NH 2 (II)
formule dans laquelle R2 est un radical alkyl ou alkényl en C8-C22, et, en second lieu, au moins un solvant organique hydroxylé, ladite composition étant sous la forme d'une emulsion à phase aqueuse continue, caractérisée par le fait que ladite emulsion comporte au moins deux familles de globules dispersés dans sa phase aqueuse continue, la première famille étant constituée de globules dont la dimension moyenne est comprise entre 170 et 250 nanomètres alors que la seconde famille est constituée de globules, dont la dimension moyenne est comprise entre 400 et 800 nanomètres, chacune de ces deux familles constituant au moins 20 % du volume total de la phase dispersée de l'émulsion et la somme de ces deux pourcentages étant supérieure à 85 %.formula in which R 2 is a C 8 -C 22 alkyl or alkenyl radical, and, secondly, at least one hydroxylated organic solvent, said composition being in the form of an emulsion with a continuous aqueous phase, characterized by the fact that said emulsion comprises at least two families of globules dispersed in its continuous aqueous phase, the first family consisting of globules whose average size is between 170 and 250 nanometers while the second family consists of globules, whose average dimension is between 400 and 800 nanometers, each of these two families constituting at least 20% of the total volume of the dispersed phase of the emulsion and the sum of these two percentages being greater than 85%.
11. Composition selon la revendication 10, caractérisée par le fait que le(s) solvant(s) organique(s) hydroxylé(s) qu'elle contient est (sont) présent(s) dans une proportion comprise entre 1 et 15 % en poids par rapport au poids total des aminés de formule I et II, qui se trouvent dans l'émulsion injectée dans l'eau à traiter.11. Composition according to claim 10, characterized in that the organic solvent (s) hydroxylated (s) it contains is (are) present (s) in a proportion of between 1 and 15% by weight relative to the total weight of the amines of formula I and II, which are in the emulsion injected into the water to be treated.
12. Composition selon l'une des revendications 10 et 11, caractérisé par le fait que la phase aqueuse continue de l'émulsion comprend au moins un solvant organique choisi dans le groupe formé par le diéthylène glycol, l'hexylène glycol, le monopropylène glycol et un amino alcool de formule IV
Figure imgf000017_0001
12. Composition according to one of claims 10 and 11, characterized in that the continuous aqueous phase of the emulsion comprises at least one organic solvent chosen from the group formed by diethylene glycol, hexylene glycol, monopropylene glycol and an amino alcohol of formula IV
Figure imgf000017_0001
formule dans laquelle A est un radical alkylène, linéaire ou ramifié, en C2-C , R4 et R5, identiques ou différents, représentant H ou un radical alkyl en C1-C3.formula in which A is an alkylene radical, linear or branched, C 2 -C, R 4 and R 5 , identical or different, representing H or an alkyl radical C 1 -C 3 .
13. Composition selon l'une des revendications 10 à 12, caractérisée par le fait qu'elle comporte un agent émulsifiant.13. Composition according to one of claims 10 to 12, characterized in that it comprises an emulsifying agent.
14. Composition selon la revendication 13, caractérisée par le fait que l'agent émulsifiant comprend au moins une aminé tertiaire polyoxyéthylénée de formule III14. Composition according to Claim 13, characterized in that the emulsifying agent comprises at least one polyoxyethylenated tertiary amine of formula III
(CH2CH20)x - H R3 - N ^ (III) ^ (CH2CH20)y - H(CH 2 CH 2 0) x - HR 3 - N ^ (III) ^ (CH 2 CH 2 0) y - H
formule dans laquelle R3 est un radical alkyl ou alkylène en C8-C22 et x et y sont des nombres entiers tels que (x + y) soit compris entre 5 et 50 (bornes incluses). formula in which R 3 is a C 8 -C 2 alkyl or alkylene radical and x and y are whole numbers such that (x + y) is between 5 and 50 (limits included).
15. Composition selon l'une des revendications 13 ou 14, caractérisée par le fait que l'agent émulsifiant représente de 5 à 45 % en poids par rapport au poids de la (ou des) amine(s) de formules I et II.15. Composition according to one of claims 13 or 14, characterized in that the emulsifying agent represents from 5 to 45% by weight relative to the weight of the (or) amine (s) of formulas I and II.
16 Composition selon l'une des revendications 10 à 15, caractérisée par le fait qu'elle comporte, comme produits actifs de formule I, d'une part, au moins une polyamine de formule I, dans laquelle Ri est un radical dodécyl et/ou au moins une polyamine de formule I, dans laquelle Ri est un radical tétradécyl, et d'autre part, au moins une polyamine de formule I, dans laquelle Ri est un radical octadécényl. 16 Composition according to one of claims 10 to 15, characterized in that it comprises, as active products of formula I, on the one hand, at least one polyamine of formula I, in which Ri is a dodecyl radical and / or at least one polyamine of formula I, in which R 1 is a tetradecyl radical, and on the other hand, at least one polyamine of formula I, in which R 1 is an octadecenyl radical.
17. Composition selon l'une des revendications 10 à 16, caractérisée par le fait qu'elle contient au plus 15 % en poids d'amine(s) de formule II par rapport au poids total des aminés de formule I et II contenues dans la composition.17. Composition according to one of claims 10 to 16, characterized in that it contains at most 15% by weight of amine (s) of formula II relative to the total weight of the amines of formula I and II contained in the composition.
18. Composition selon l'une des revendications 10 à 17, caractérisée par le fait qu'elle contient de 60 % à 99 % en poids d'eau par rapport au poids total de l'émulsion. 18. Composition according to one of claims 10 to 17, characterized in that it contains from 60% to 99% by weight of water relative to the total weight of the emulsion.
PCT/FR2002/002378 2001-07-11 2002-07-08 Method for treating water and surfaces in contact with same for controlling macro-organisms and corresponding composition WO2003007715A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0109192A FR2827271B1 (en) 2001-07-11 2001-07-11 PROCESS FOR TREATING WATER AND SURFACES IN CONTACT WITH SAID WATER WITH A VIEW TO PREVENTING AND / OR ELIMINATING AND / OR CONTROLLING FIXATION OF MACROORGANISMS AND COMPOSITION FOR CARRYING OUT SAID METHOD
FR01/09192 2001-07-11

Publications (1)

Publication Number Publication Date
WO2003007715A1 true WO2003007715A1 (en) 2003-01-30

Family

ID=8865356

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2002/002378 WO2003007715A1 (en) 2001-07-11 2002-07-08 Method for treating water and surfaces in contact with same for controlling macro-organisms and corresponding composition

Country Status (2)

Country Link
FR (1) FR2827271B1 (en)
WO (1) WO2003007715A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8794571B2 (en) 2009-03-16 2014-08-05 Airbus Operations Gmbh Cooler for an aircraft cooling system, aircraft cooling system and method for operating an aircraft cooling system
EP3260576A1 (en) * 2016-06-22 2017-12-27 Kurita Water Industries Ltd. Aqueous oil-in-water emulsions of organic amines

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ2010856A3 (en) * 2010-11-23 2012-01-25 Vysoká škola chemicko-technologická v Praze Antimicrobial formulation for conditioning cooling circuits

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2727958A1 (en) * 1994-12-08 1996-06-14 Vanlaer Antoine PROCESS FOR TREATMENT OF WATER AND SURFACES IN CONTACT WITH THE SAID WATER WITH A VIEW TO PREVENTING THE FIXATION AND / OR ELIMINATION AND / OR CONTROL OF MACROORGANISMS, COMPOSITION AND PAINT FOR SUCH TREATMENT
FR2727874A1 (en) * 1994-12-13 1996-06-14 Intevep Sa PROCESS FOR THE PREPARATION OF VISCOUS HYDROCARBON IN AQUEOUS BUFFER SOLUTION EMULSIONS

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2727958A1 (en) * 1994-12-08 1996-06-14 Vanlaer Antoine PROCESS FOR TREATMENT OF WATER AND SURFACES IN CONTACT WITH THE SAID WATER WITH A VIEW TO PREVENTING THE FIXATION AND / OR ELIMINATION AND / OR CONTROL OF MACROORGANISMS, COMPOSITION AND PAINT FOR SUCH TREATMENT
FR2727874A1 (en) * 1994-12-13 1996-06-14 Intevep Sa PROCESS FOR THE PREPARATION OF VISCOUS HYDROCARBON IN AQUEOUS BUFFER SOLUTION EMULSIONS

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8794571B2 (en) 2009-03-16 2014-08-05 Airbus Operations Gmbh Cooler for an aircraft cooling system, aircraft cooling system and method for operating an aircraft cooling system
EP3260576A1 (en) * 2016-06-22 2017-12-27 Kurita Water Industries Ltd. Aqueous oil-in-water emulsions of organic amines

Also Published As

Publication number Publication date
FR2827271B1 (en) 2003-09-05
FR2827271A1 (en) 2003-01-17

Similar Documents

Publication Publication Date Title
FR2948964A1 (en) METHOD FOR CONTINUOUS DISSOLUTION OF POLYACRYLAMIDE EMULSIONS FOR ASSISTED OIL RECOVERY (RAP)
WO2014140498A1 (en) Biocidal composition and method for treating water or surfaces in contact with water
EP0254704A1 (en) Dispersant compositions for treating oil slicks on the surface of water
EP3026999B1 (en) Novel method of soil conditioning by application of water-soluble or water-swelling polymer
EP0716045B1 (en) Use for treating water and surfaces in contact with water to prevent the deposition of and/or the removal of and/or for the control of macroorganisms, as well as composition and paint therefor
WO2014076435A1 (en) Potabilization process
EP3676423A1 (en) Metal corrosion inhibitors
WO2003007715A1 (en) Method for treating water and surfaces in contact with same for controlling macro-organisms and corresponding composition
EP1778395A1 (en) Use of an optionally modified and optionally insoluble vegetable gum for eliminating natural or synthetic organic substances in liquids
CN1304429C (en) Purified chitin and its production method
FR2786064A1 (en) Biocide material for inhibiting the growth of microorganisms in an aqueous solution comprises a water-insoluble polymer support carrying an immobilized biocide containing water
CN1032619C (en) Antimicrobial composition and and method of use
WO2014016529A1 (en) Method of water purification
EP0071547A1 (en) Aqueous dispersions of organopolysiloxanes as anti foaming agents
CN1089953A (en) The method for making of new highly filled non-aqueous polymer composition
CN87102237A (en) Bicarbaminate-based herbicidal compositions and methods of using them to control weeds
EP2621867B1 (en) Biostatic neutralizing composition for aqueous fluids
CN1089954A (en) The method for making of new highly filled non-aqueous polymer composition
EP1525164A2 (en) Method and installation for the production of lime water from deionised water
WO2011138537A1 (en) Process for treating waste water resulting from the synthesis of a halogenated vinyl polymer
WO2003021111A1 (en) Method of treating flowing water and the surfaces in contact with said flowing water
EP1952687B1 (en) Emulsion containing a polysaccharide and its use in sprayable liquid compositions
EP0785010A1 (en) Method of treating an aqueous medium conteminated with hydrocarbons and defoaming and dispersant composition sedon polyglycerolesters.
FR3071251A1 (en) REVERSE EMULSION OF CATIONIC STARCH AND CATIONIC POLYACRYLAMIDE WITH LOW VISCOSITY AND INCREASED STABILITY
WO2003037496A1 (en) Emulsion containing an oppositely-charged surfactant and polymer and the production method therefor

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase