WO2003021111A1

WO2003021111A1 - Method of treating flowing water and the surfaces in contact with said flowing water

Info

Publication number: WO2003021111A1
Application number: PCT/FR2002/003011
Authority: WO
Inventors: Ludovic Jourdan; Antoine Vanlaer
Original assignee: Ludovic Jourdan; Antoine Vanlaer
Priority date: 2001-09-05
Filing date: 2002-09-05
Publication date: 2003-03-13
Also published as: FR2829127A1; FR2829127B1

Abstract

The invention relates to a method of treating flowing water and the surfaces in contact with said flowing water. The invention is characterised in that the following compounds are introduced together into the water, preferably close to said surface and, even better, in the peripheral area of the flow: at least one polymer compound having a high molecular mass and hydrodynamic friction reducing properties; and at least one monoamine or polyamine compound comprising a fatty alkyl or alkenyl chain with biocide properties. The invention also relates to a composition which is formulated as: a powder that is to be scattered; an injectable liquid, particularly an emulsion; a gel that is left to spread; or a coating that is applied to the surface in contact with the water, preferably a paint. Said formulation is such that it progressively salts out at least the friction reducing polymer compound in said water in contact with the surface.

Description

Method for treating flowing water and surfaces in contact with said flowing water.

The present invention relates to a method for treating flowing water and surfaces in contact with said flowing water.

More particularly, the present invention relates to a treatment method which makes it possible to reduce the hydrodynamic friction exerted on said surfaces. The present invention also relates to a process for combating the development of soiling and chemical or biological corrosion, in particular in open, semi-open or closed hydraulic circuits, or on the submerged external surfaces of installation or moving machine in water, especially the hulls of boats and underwater vehicles. More particularly still, the method according to the invention makes it possible to eliminate and / or prevent the fixing and / or to control the development of micro- and macro-organisms participating in the biological veil on these surfaces.

The present invention also relates to compositions for injection into water, compositions to let diffuse in water, in the form of a gel, or compositions for coating, in particular paint to be applied to surfaces in contact with water. , to carry out a treatment according to the invention.

Many industries use either fresh water, such as river, river, lake, natural reservoir, dam, in-ground drilling or well water, or salt water, such as than sea water. This water is for example used in boiler circuits 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. Likewise, water can flow on the submerged external surfaces of installation or machine, such as coastal structures, barges, surface vessels, vehicles or underwater towed bodies. It is known that on the surfaces of these installations and machines in which or outside of which the water circulates, the flow of water can reach a turbulent regime. This regime is associated with the existence of dynamic mechanisms, located mainly in the region close to the wall, and more precisely in the buffer zone of the boundary layer, which govern the energy exchanges within the flow. These energy exchanges reflect a balance between energy production processes and energy dissipation, particularly in the form of friction exerted on said surfaces. The manifestation of friction energy losses at surfaces in contact with water is illustrated, for example, by the drop in static pressure, or pressure drop, recorded in the hydraulic circuits along the path of the flow, or by the hydrodynamic resistance force associated with the drag drag exerted on the moving bodies in the water.

Different techniques for reducing the friction generated by a flowing fluid at a solid-fluid interface have been described. In particular, friction reduction methods are known which involve dynamic coupling phenomena which modify the energy exchange processes in the boundary layer. Among these methods, very effective techniques are based on the addition of additives in the flowing liquid medium, which make it possible to generate a reduction in friction.

In particular, it has been proposed to introduce into water as active product having a friction-inhibiting action, water-soluble macromolecular compounds of high molecular weight, synthetic or natural.

Several families of water-soluble macromolecules with the ability to reduce hydrodynamic friction have been described. In US 5,045,588 and US 5,571,314, polymers of the polyacrylamide or poly (ethylene oxide) type are described formulated in the form of a suspension in various carrier liquids, including in particular mineral fillers and surfactants promoting their dilution in water. . In these patents, it is proposed to reduce the hydrodynamic friction exerted on the surfaces in contact with water flows when the regime is turbulent by injecting into the flow a composition comprising one of said polymers. It is also known, from US 5,554,214, that it is possible to reduce the hydrodynamic friction exerted on the surfaces in contact with water flows when the regime is turbulent, by applying to these surfaces a coating incorporating said said water-soluble polymers which are formulated so as to be gradually released into water by controlled dissolution of the coating.

It is also known that on the surfaces of installations in which water circulates, microorganisms develop which form on said surfaces a biological or bacterial veil consisting of organic materials, bacteria, algae, protozoa or other microorganisms. This biological veil can lead to significant losses in yield in hydraulic circuits, heat exchangers for example, and cause localized corrosions and lead to the subsequent development or fixation of macro-organisms, such as algae, molluscs, etc. It has been proposed to introduce into water as active product compounds having a biocidal and / or biostatic action, capable of preventing the growth of microorganisms and macroorganisms as well as their fixation on the surfaces in contact with the water.

Many so-called "biocidal" compounds have been proposed and used for water treatment. 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. The use of quaternary ammonium derivatives or peroxygen derivatives, phenols and phenol derivatives, heavy metals or their organic derivatives, formaldehyde, benzoic acid and benzoates has also been proposed for treatments by injection or by contact. with a coating. Biocidal compounds are generally used in the form of a solution or dispersion in an aqueous phase optionally containing organic solvents. In this case they are most often injected into the water to be treated.

In EP 716045, it has been indicated that fatty amines exhibit biocidal activity. In this patent, it was notably proposed to introduce a particular mixture of fatty polyamines in the compositions used for practicing 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. More particularly, in EP 716045, a composition is described comprising:

- at least one polyamine of formula (I)

(I) RrNH [(CH ₂ ) 3-NH] n- (CH ₂ ) ₃ NH ₂

in which Ri is a C ₈ -C ₂₂ alkyl or alkenyl radical and 'n' is an integer from 0 to 3, and / or

- at least one monoamine of formula (II)

in which R ₂ is a C ₈ -C ₂ 2- alkyl or alkenyl radical

To date, it has not been possible to provide a process which makes it possible to offer the combined performance of a preventive and / or curative treatment in the fight against the development of chemical and biological soiling in hydraulic systems, and also allowing to improve the hydrodynamic efficiency, so that to date, two treatments must be carried out independently according to protocols and using independent means.

The object of the present invention is therefore to provide such a method combining the two treatments in one. Another object of the present invention is to provide a treatment method making it possible to improve the performance of the treatment methods aiming to improve the hydrodynamic yields and more particularly to increase the reduction of hydrodynamic friction exerted on the surfaces in contact with water flows when the regime is turbulent, using compounds having friction-inhibiting properties.

The inventors have discovered that it is possible to provide a combined treatment which makes it possible jointly to improve the hydrodynamic efficiency and to combat the development of chemical and biological soiling; and of in addition, surprisingly making it possible to increase the effectiveness of the friction-reducing compounds by jointly using the said friction-reducing compounds in combination with certain biocidal amino compounds, namely the fatty chain amino and polyamine compounds of formula (I) and ( II) described above, even though these fatty amine compounds do not exhibit activity as a hydrodynamic friction reducer.

More precisely, the present invention provides a method for treating flowing water and surfaces in contact with said flowing water, characterized in that it is introduced together into said water, preferably near said surface, more preferably in the internal zone of the turbulent boundary layer:

at least one high molecular weight macromolecular compound having hydrodynamic friction reducing properties, and

- At least one monoamine or polyamine compound comprising an alkyl or alkenyl fatty chain having biocidal properties.

A priori, by their film-forming properties, the fatty amine compounds of formulas (I) and (II) tend to increase the viscosity in the flow near the surface, and therefore to induce an increase in the hydrodynamic friction resulting for part of a dissipation of energy by viscous effect. Without wishing to be bound by a theory, the inventors make the explanation that the biocidal products selected according to the present invention have a physicochemical compatibility and affinity with macromolecular compounds reducing friction on the one hand, and that, on the other hand, by their film-forming properties, said biocidal compounds have an affinity for solid surfaces and contribute to improving the distribution of macromolecules in the vicinity of said surfaces. In particular, by virtue of the ionic nature which they possess, or which can be conferred on them, said biocidal compounds can cause in their migration towards solid surfaces the friction inhibiting compounds, or reduce their diffusion far from said surfaces, when these inhibitors have in their molecular lattice free charges of opposite polarity. This results in an increase in the population of inhibitors in the internal region of the boundary layer or seat the processes which govern the production and dissipation of energy in the flow. This increase then results in a better efficiency in reducing friction.

According to the present invention, said friction reducing compound comprises water-soluble polymers of molecular weight preferably greater than ⁵ × 10 ⁵ Dalton, more preferably still greater than 5 × 10 ⁶ .

More particularly, said friction reducing polymer is chosen from the following polymers of the polyacrylamide, poly (ethylene oxide), and polysaccharide type extracted from plants or produced by algae, marine microorganisms or bacteria. As polysaccharide, mention is made in particular of guar gum, production of marine algae such as Carragaheen, and Porphyridium cruentum, or of marine organisms such as Chaetoceros didymus (diatom), and Protoperidinium (dinoflagellate).

These macromolecules, due to their large size and the viscoelastic properties which they exhibit in solution, participate in coupling with coherent structures, in particular vortex structures, of the flow involved in the energy transfer mechanisms in the vicinity of the wall in the turbulent boundary layer. This coupling results in particular in the stretching of the macromolecular networks in the zones where strong variations in speed occur locally due to the vorticity. This results in a disturbance of the energy balance existing between the processes of production and dissipation of energy in the flow, which is manifested by the effect of reduction of friction.

These friction reducing polymers can be non-ionic or ionic macromolecules, of linear or branched structure. However, according to the present invention, the inventors have found that polymers when they are in nonionic form or in ionic form, so that the charges of said polymers are balanced with those of said biocidal compounds in said composition comprising said biocidal compounds and said polymers, are probably more effective because said composition is less sensitive to interactions with ionic charges possibly transported in water. Likewise, the inventors have found that, according to the present invention, the linear polymers have a better efficiency when they are injected into low shear flows, probably because their network stretches more easily, while the branched polymers resist better. mechanical degradation in high shear flows.

More particularly, the inventors have selected the polymers sold under the following commercial references:

- Poly (ethylene oxide): Polyox® WSR-205, -301 (Union Carbide Chemical Company), - Polyacrylamide: Separan® AP-30, -273 (Dow Chemical Company);

Nalcolyte® 674 (Nalco Chemical Company); AN934, AN900-VHM (SNF Floerger Company); Polyhall® 295 (Stein-Hall Company).

Preferably, the biocidal compound comprises at least one polyamine of formula (I),

(I) R NH [(CH ₂ ) ₃ -NH] n- (CH ₂ ) ₃ NH ₂

in which Ri is a C-8-C-2 ₂ alkyl or alkenyl radical and 'n' is an integer from 0 to 3, and / or at least one monoamine of formula (II)

(II) R ₂ NH ₂

in which R ₂ is a C ₈ -C ₂₂ alkyl or alkenyl radical.

More preferably, said biocidal compounds comprise a mixture containing on the one hand at least one polyamine of formula (I) in which the radical Ri 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) in which R 1 is an octadecenyl radical.

More particularly, said biocidal compounds comprise a mixture of polyamines derived from tallow and / or polyamines derived from a vegetable or animal oil containing olein with at least one polyamine derived from coconut. According to the present invention, the amines and polyamines are used as such and not in the form of salts or other derivatives.

According to the present invention, the inventors have found that said composition is effective when the ratio of the concentrations in water of said biocidal compound (s) to the concentrations in water of said friction reducing compound (s) is between 10 ^"6 and 10 ⁴ , and 10 ^{" 2} and 1.

More particularly, the concentration by weight in water of said biocidal compounds is from 0.01 to 100 ppm, preferably from 0.05 to 10 ppm, more preferably from 0.1 to 2 ppm. More particularly still, the concentration by weight in water of said friction reducing polymer compounds is from 0.01 to 7500 ppm, preferably from 0.1 to 2500 ppm, more preferably from 1 to 500 ppm.

The upper limits of the concentrations indicated above are in fact linked to environmental constraints, in particular to the toxicity of the products with regard to the biocidal compound, and to the sharp increase in viscosity of the liquid medium, with regard to the reducing polymer. friction, this increase in viscosity can result in difficulties of implementation of said polymers and a loss of efficiency associated with the modification of the flow regime. It is also understood that the concentration of said compounds according to the invention depends on the type of treatment used. In fact, for a treatment in which the products are introduced into the water intermittently or sequentially, the concentrations must be higher than in the case of treatment by addition in water continuously. In one embodiment, at least one of said biocidal compound and friction reducing compound is introduced into the water continuously, preferably near said surfaces, more preferably in the internal zone of the boundary layer.

In another embodiment, at least one of said biocidal compound and friction reducing compound is introduced into the water, intermittently, preferably near said surfaces, more preferably in the internal zone of the boundary layer. In the case of continuous introduction into water, preferably introduce a dose necessary to obtain a concentration by weight between 0.1 and 2 ppm of bioactive products of formula (I) and / or (II) and between 1 and 500 ppm of friction reducing agents in water in the vicinity of the surfaces to obtain a sufficient effect.

In the case of an introduction, in particular an intermittent injection, the times of introduction, in particular of injection and the necessary concentrations of active products of formula (I) and / or (II) and of friction reducing agents depend on the micro- and macro-organisms to be controlled, the hydrodynamic performances sought, the dimensions of the installations and the surfaces in contact with water as well as the water flow rate and can be determined by a person skilled in the art depending on these criteria. It will be noted that the effectiveness of the friction reducing compounds will be maximum if the mixture is not subjected to strong shears during the injection process.

In the event of intermittent introduction, the daily introductions of products of formula (I) and / or (II) should preferably make it possible to obtain a concentration by weight of the order of 5 to 15 ppm for one to two hours.

In one embodiment of the method according to the invention, the biocidal compound can be introduced intermittently and the friction reducing agent continuously and vice versa as required.

In one embodiment, said biocidal compound is introduced in the form of an emulsion in a continuous aqueous phase.

For better stability of the emulsion of bioactive product (s), an emulsifying agent is advantageously used. Preferably this emulsifying agent

(CH ₂ CH ₂ 0) _x -H

(III) R ₃ -N

^ (CH ₂ CH ₂ 0) _y -H

comprises at least one polyoxyethylenated tertiary amine of formula (III), formula in which R ₃ is a C ₈ -C ₂₂ alkyl or alkylene radical, preferably a hexadecyl, stearyl or oleyl radical and 'x' and y are integers such that x + y is between 5 and 50, of preferably between 10 and 20.

The emulsifying agent can represent 5% to 45% by weight, preferably 15% to 35% relative to the weight of the assembly formed by the active product (s) of formula (s) (I ) and (II).

The aqueous phase may contain at least one organic solvent in addition to water 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. This solvent is suitably chosen from the group formed by diethylene glycol, hexylene glycol, monopropylene glycol and an amino alcohol of formula (IV)

(IV) HO-A-NR ₄ R ₅

formula in which A is a C ₂ -C ₄ linear or branched alkylene radical and R and R ₅ , which are identical or different, are H or a C ₁ -C ₃ alkyl radical.

The inventors have found that, surprisingly, in order to be optimal, a composition having a defined formulation and presented in the form of an emulsion must preferably contain 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 first family consisting of globules, the average dimension of which is between 170 and 250 nanometers, while the second family consists of globules, the mean dimension of which is understood 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%.

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 constants are kept constant the parameters of the manufacturing process allowing the emulsion to be obtained, a substantially constant efficiency of the emulsion obtained is 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 process for manufacturing the emulsion 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 emulsion of said biocidal compounds injected into the water to be treated preferably comprises from 60% to 98% by weight of water relative to the total weight of said emulsion.

According to the present invention, water can also be treated by applying to the surfaces in contact with water a coating containing at least one bioactive product of formula (s) (I) and / or (II), in particular a paint. . According to a particular embodiment of such a paint, the bioactive products of formula (s) (I) and / or (II) are mixed with a pulverulent mineral filler, for example micronized silica, so as to obtain a pulverulent product which is then introduced into a painting in the same way as a pigment. Advantageously, said friction-reducing compound in water is notably introduced by injection in the form of a powder directly disseminated in water, or of an aqueous solution, or of a suspension, or else of an emulsion in phase. oily continues.

Preferably, an injection of a composition is carried out in the form of a suspension or an emulsion due to the risk of formation of aggregates in water by direct dissemination of the friction reducing compound in the case of a powder, or the short lifetime as well as the limitation to be able to concentrate the friction reducing compound in water, taking into account the rapid increase in viscosity, in the case of an aqueous solution. According to a particular embodiment of a suspension, the friction reducing compound is dispersed in an organic carrier liquid, non-solvent with respect to said compound, soluble in water. This carrier liquid or carrier liquid can be chosen by way of example from the group formed by alcohols primers, Pisopropanol, polyethylene glycol, polypropylene glycol or propylene carbonate. In known manner, to promote the stability of the suspension, an organic dispersing agent derived from a mineral compound is advantageously used, which is added to the dispersion, such as an organic clay derivative. More preferably and in a known manner, so as to increase the solubilization of the friction reducing compound in water during the injection, the combination of an amphoteric surfactant and an anionic surfactant can be added to the suspension.

According to a particular embodiment of an emulsion, the friction reducing compound is dispersed in an organic carrier liquid, non-solvent, soluble in water, such as for example chosen from the products mentioned previously for the case of a suspension , in the presence of an organic dispersant derived from a mineral compound as defined above. The suspension is then emulsified in a liquid which is not soluble in water, for example kerosene or a vegetable or animal oil, containing an emulsifying agent, for example a polyoxyethylenated nonyl phenol having 10 to 20 ethylene oxide groups or a dioctylsulfosuccinate.

In a second alternative embodiment, the friction reducing compound can be introduced into the water in the form of a gel to be dissolved in water.

According to a particular embodiment of such a gel, the procedure is identical to the formulation of an emulsion by adding a gelling agent such as a polar solvent such as ethylene glycol.

According to the present invention, it is also possible to introduce the friction reducing compound into water by applying to the surfaces in contact with water a formulation in the form of a coating containing the friction reducing compound, preferably a paint. said formulation being such that it gradually releases said friction reducing polymer compound into said water in contact with said surface. According to a particular embodiment of a paint, the friction reducing compound is introduced in pulverulent form, in the same way as a pigment, in a paint allowing the penetration of water and the ablation of said compound. The present invention also provides a composition to be injected, a composition to be allowed to diffuse in water in the form of a gel, or a composition to be applied in the form of a coating, in particular a paint, for the treatment of water and wet surfaces, with a view to to prevent and / or eliminate, and / or control the development of micro-organisms and macro-organisms, and to reduce the hydrodynamic friction exerted on these same surfaces in the presence of a flow of water.

According to the present invention, a said composition comprises:

- at least one said biocidal compound of formula (I) and / or (II) as defined above, and

- At least one said friction reducing compound as defined above. The weight ratio of said biocidal compounds to said friction reducing compound in said composition is preferably from 1/100 to 1, more preferably from 1/50 to 1/2, in particular for continuous treatment, more particularly about 1/25.

In a first alternative embodiment, a composition according to the invention is formulated in the form of a powder to be disseminated in water.

According to a particular embodiment of such a powder, said bioactive compound of formula (s) (I) and / or (II) is mixed in the liquid state with a powdery mineral filler, for example micronized silica, so as to obtain a powdery product. The powder obtained is then mixed with the friction reducing compound, itself in powdery dehydrated form, in proportions determined by the application.

In a second variant embodiment, a composition according to the invention is formulated in a form injectable in water.

In a third alternative embodiment, a composition according to the invention is formulated in the form of a gel to be allowed to diffuse in water.

Advantageously, when said composition is an injectable liquid composition or a gel, it is in the form of an emulsion. More particularly, said bioactive compound is contained in the oily phase of the emulsion and said friction reducing compound is contained in the aqueous phase of the emulsion. According to a particular embodiment, the friction reducing compound is dispersed in a non-solvent, water-soluble organic carrier liquid, for example chosen from primary alcohols, isopropanol, polyethylene glycol, polypropylene glycol or carbonate propylene, in the presence of an organic dispersing agent derived from a mineral compound. The suspension is then emulsified in a continuous oily phase, for example kerosene or a vegetable or animal oil, containing an emulsifying agent, for example a polyoxyethylenated nonyl phenol having 10 to 20 ethylene oxide groups or a dioctylsulfosuccinate. The biocidal compound in the liquid state is then dispersed in the emulsion, and is found in the oily phase.

According to a particular embodiment of such a gel, the procedure is identical to the formulation of an emulsion by adding a gelling agent.

According to the present invention, the composition can also be formulated as a coating intended to be applied to said surface in contact with water, preferably a paint, said formulation being such that it gradually releases at least said polymeric compound. friction reducer in said water in contact with said surface.

According to a particular embodiment of such a paint, said bioactive products of formula (s) (I) and / or (II) are mixed in the liquid state with a pulverulent filler, for example micronized silica, so obtaining a bioactive compound in the form of a powder. The bioactive composition obtained is then mixed with the friction reducing compound, itself dehydrated in powder form, in proportions determined by the application. The bioactive / friction reducing coating is finally obtained by introducing the powdery mixture of the bioactive filler with the friction reducing compound, in the same way as a pigment, into a paint allowing the penetration of water and the ablation of said coating. mixed.

By way of illustration, the installations which the methods and compositions according to the invention make it possible to cite are cited below, as well as the embodiments recommended for each of them according to the following nomenclature: (1): dissemination of said composition in powder form directly in the flow of said water,

(2): injection of said composition in the form of an emulsion into the flow of said water, preferably in the vicinity of said surface in contact with said water,

(3): diffusion of said composition conditioned in the form of a form, consisting of a gel, placed in the flow of said water, preferably in the vicinity of said surface in contact with said water,

(4): application of said composition in the form of a paint releasing the active compounds in the flow of said water in the vicinity of said surface in contact with said water,

- hull of a ship or submerged vehicle: (2), (4),

- immersed external surface of structure: (1), (2), (4),

- oil wells: (1), (2), (3), - geothermal wells: (1), (2), (3),

- power plant cooling circuit: (1), (2),

- industrial and / or domestic air cooling circuit and tower supplied with fresh and / or brackish water: (1), (2),

- industrial hydraulic network: (1), (2), - irrigation network: (1), (2),

- urban sewage disposal network: (1), (2),

- fire fighting device: (1), (2), (3),

- pickling system, hydro demolition, cutting, by high pressure jet: (1), (2), (3), Another advantage of the process and composition according to the invention is to respect the environment by a choice of unsuitable compounds.

As an advantage of the methods and composition according to the invention, it is possible to cite the improvement in the performance of hulls, pumping systems, dispersion systems, pickling systems, demolition systems, or water jet cutting, l 'increase in throughputs or volumes of transit of liquid materials and decrease in the energies involved for the displacement or the transport of suspended solids in liquid media. Other characteristics and advantages of this invention will appear in the light of the detailed description which follows.

Figures 1 and 2 show the change in pressure drop (Fig.1) and the change in the percentage of friction reduction (Fig.2) measured in the flows of different preparations described below; depending on the flow.

Tests have been carried out aimed at characterizing the ability to reduce hydrodynamic friction of the formulations of biocidal compounds, and of a mixture of biocidal compounds and hydrodynamic friction reducing agents.

1 FORMULATIONS TESTED

1.1 - Formulation of friction reducing agents.

The following formulations have been tested, comprising nonionic and anionic macromolecules, the hydrodynamic friction inhibitor agent being in the form of a powder or in the form of an emulsion in an organic phase ("water" emulsion in the oil, containing an emulsifying agent to stabilize the emulsion and facilitate dissolution in water later). a) Powder formulation.

- Formulation n ° 1:

This formulation corresponds to a non-linear polydisperse polyacrylamide with a molecular weight of the order of 10 ⁷ Dalton in the form of a white powder, (this polymer is sold under the reference AN900-VHM by the company SNF Floerger).

- Formulation # 2:

This formulation corresponds to a non-linear, polydisperse, anionic polyacrylamide with a percentage of anionicity per mole equal to 30, of molecular weight of the order of 10 ⁷ Dalton, having the appearance of a white powder, (this polymer is marketed under the reference AN934 by the company

SNF Floerger). b) Formulation in the form of an emulsion.

- Formulation n ° 3: Powder formulation No. 1 is dispersed in propylene carbonate or polypropylene glycol. The dispersion obtained is emulsified in a continuous oily phase in the presence of an emulsifying agent. This emulsifying agent is a nonyl phenol having 10 to 20 ethylene oxide groups.

These formulations were tested below on a range of weight concentrations ranging from 500 to 20 ppm obtained by successive dilutions of a stock solution at 1000 ppm produced by direct dispersion of the powder, or of the emulsion, in water. At these concentrations, the performance of solutions in hydrodynamic friction reduction is significant.

1.2 - Biocidal formulations.

The formulations corresponding to Examples 39 and 75 of patent EP 716045 recalled below (values given in part by weight) were tested: - Formulation No. 4:

N-oleyl-1,3-propylene diamine 5

N-copra-1, 3propylene diamine 5

2-amino-2-methyl-1-propanol 2.5

Oleine amine to 20 moles of ethylene oxide (Genamin® -0-200) 2.5

Water 85

This emulsion comprises two families of globules of different size dispersed in the continuous aqueous phase:

- a first family representing 36% by volume, the average size of the globules of which is 200 nanometers, and

- a second family representing approximately 62% by volume, the average size of the globules of which is 600 nanometers.

This formulation corresponds to an initial effective inhibitory concentration designated by EC ₅₀ (24h) = 25%. The value CE ₅₀ (24h) corresponds to the determination of the biocidal character with respect to micro- and macro-organisms according to the international standard ISO 5341. - Formulation n ° 5:

N-oleyl-1,3-propylene diamine 6

N-copra-1, 3propyIene diamine 4

2-diethylamino-1-ethanol 2.5 Amine of olein to 20 moles of ethylene oxide

(Genamin® -0-200) 2.5

Water 85

This emulsion comprises two families of globules of different size dispersed in the continuous aqueous phase: a first family representing 28% by volume, the average size of the globules is 200 nanometers, and

- a second family representing approximately 69% by volume, the average size of the globules of which is 600 nanometers.

This formulation corresponds to an effective initial inhibitory concentration designated by EC ₅₀ (24h) = 50%.

1.3 - Formulations of the mixtures.

To test the ability to reduce friction of a mixture of biocidal formulation and formulation of friction reducing agent, aqueous solutions were produced under the following conditions: - Formulation No. 6:

1) Biocide Formulation No. 4 was diluted in water to obtain an aqueous solution, hereinafter designated Solution A, with a concentration of active biocidal compounds (fatty polyamines) of 10 ppm for a volume of solution of 120 liters. 2) 6 grams of a powdery Formulation No. 1 of friction reducing agent were then diluted in the 120 liters of Solution A described above so as to obtain an aqueous solution containing the biocidal products at a rate of 10 ppm and the friction reducing agent in a weight concentration of 50 ppm. - Formulation n ° 7:

1) The biocidal composition of fatty polyamine contained in Formulation no. 4 biocide was directly dispersed in the oily phase of formulation no. 3 emulsified from the friction-inhibiting agent in a ratio by weight equal to 1/5 between the biocidal composition and the composition of the friction-inhibiting agent.

2) The emulsion obtained, containing the biocidal composition and the friction reducing agent, was dispersed in water, so as to obtain an aqueous solution containing the biocidal active products and the friction reducing agent in respective concentrations 10 ppm and 50 ppm.

2 EXAMPLES OF FORMULATIONS

Examples of formulations combining the biocidal compounds with the friction-inhibiting agents, in the same way as formulation No. 7, under the various embodiments indicated are given in tables 1 to 3.

2.1: Examples of pulverulent formulations of biocidal compositions reducing friction. The friction-inhibiting agent designates a high polymer belonging to the families mentioned.

Table 1

Table 1 (continued)

EXAMPLES 6 7 8 9 10

PRODUCTS COMPOSITION IN% BY WEIGHT

Friction inhibiting agent 98 96 84 72 34 N-oleyl-1, 3 propylene diamine 0.6 1, 2 4.8 8.4 19.8 N-copra-1, 3 propylene diamine 0.4 0.8 3, 2 5.6 13.2 Micronized silica (Silobloc 45®) 1 2 8 14 33

Table 1 (continued)

EXAMPLES 11 12 13 14 15

PRODUCTS COMPOSITION IN% BY WEIGHT

Friction-inhibiting agent 98 96 84 72 34 N-oleyl-1, 3 propylene diamine 0.4 0.8 3.2 5.6 13.2 N-copra-1, 3 propylene diamine 0.6 1, 2 4, 8 8.4 19.6 Micronized silica (Silobloc 45®) 1 2 8 14 33 Table 1 (continued)

EXAMPLES 16 17 18 19 20

PRODUCTS COMPOSITION IN% BY WEIGHT

Friction-inhibiting agent 98 96 84 72 34 N-oleyl-1, 3 propylene diamine 0.2 0.4 1, 6 2.8 6.6 N-copra-1, 3 propylene diamine 0.8 1, 6 6, 4 11, 2 26.4 Micronized silica (Silobloc 45®) 1 2 8 14 33

2.2: Examples of emulsified formulations of biocidal compositions reducing friction. A viscous gel is obtained by adding polar solvent such as ethylene glycol in an amount of 5 to 25% by weight in the emulsion.

Table 2

Table 2 (continued)

2.3: Examples of paint formulations containing biocidal friction reducing compositions. Table 3

3 PRINCIPLE OF TESTS AND CHOICE OF PARAMETERS. Insofar as the tests must make it possible to locate the performances of the preparations over a range compatible with the use, the test protocols were chosen based on the following criteria:

- Installation of a bench to test the preparations over a significant range of flow rates,

- Implementation of products near the recommended concentration of use according to comparable preparation protocols,

- Use of test procedures allowing validation of the results taking into account the particular properties of the fluids studied.

Taking into account the criteria selected here corresponds to a device consisting of a pressurized cylindrical tank with a capacity of 120 liters, 0.2 m in diameter, in which the preparations are stored, connected to a conduit via a solenoid valve. The flows are carried out by propelling the preparations in the smooth rectilinear cylindrical conduit of circular section, of diameter 0.019 m, the length of which is sufficient to overcome the effects of entry and exit on the measurement section where the performances are evaluated. in reduction of friction.

In this configuration, different flow rates ranging from 200 to 1600 cm ³ / s have been achieved by varying the driving pressure in the tank, serving to propel the preparations, over the range 0.1-1, 2 bars.

Establishing performance consists in measuring on the one hand the flow rate as the ratio of the volume of fluid expelled in the installation by the flow time of this same volume, and on the other hand the pressure drop (ΔP) between two sections of the measurement section 1 m apart.

The volume removed is measured directly at the pressure tank containing the preparations after each shot. The flow time is evaluated using a precision chronometer and the pressure drop estimated using a differential pressure sensor connected to the two static pressure taps (1 mm in diameter) 1 m apart .

The differential pressure sensor used is a Valydine DP15TL ensuring a measurement accuracy of about ± 15 Pa. The signals are recorded on a DATA6100 type spectrum analyzer and the results consist of overall averages obtained over 10 frames acquisition of 1024 points.

The preparations tested are carried out with stirring for comparable times (20 min) and the shots carried out for identical static pressure and temperature conditions. Between each test, the installation is rinsed, then calibrated in water so as to avoid contamination of the measurements relating to a preparation with residual traces of the preparation previously tested.

4 TEST RESULTS. The results of the reported tests were obtained for test conditions at ambient pressure and temperature of 1011 mbar and 15 ° C respectively (temperature of the preparations tested). These correspond to three series of measurements carried out respectively in:

- an aqueous solution of Formulation No. 1 pulverulent of friction-inhibiting agent at 50 ppm (hereinafter X ₅₀ ),

- an aqueous solution of Formulation No. 4 biocide at 10 ppm (hereinafter Y-ι ₀ ), and

- a Formulation No. 6 containing the biocidal composition and the friction-inhibiting agent in respective weight concentrations of 10 ppm and 50 ppm (hereinafter X ₅₀ + Y10). These results are representative of the behaviors observed whatever the family of inhibitors considered; namely poly (ethylene oxide), polyacrylamide or polysaccharide.

Identical results are obtained with formulation No. 7. In Fig. 1 are illustrated the changes in the pressure drop Δp (Pa) measured for each preparation, at the respective weight concentrations of use recommended, for the different volume flow rates produced (Q (cm ³ / s)). Fig.1 also presents similar measurements made in the water flow taken as a reference.

On the other hand, the performances of the preparations have been reported in FIG. 2 in terms of percentage of reduction of friction DR% at constant flow, such as:

DR% = 100 X [(Δp _EaU - Δppreparation) / Δp _E au] θ

The values corresponding to the points shown on the graph Fig. 2 are as follows:

Q (cm3 / s) DR% Q (cm3 / s) DR%

Y10 X50 + Y10

401 -1.1 347 47.8

427 -3.8 411 49.1

476 -1.4 584 53.1

546 0.1 651 54.1

657 -3.5 672 55.0

660 -4.3 701 55.0

697 -1.6 712 56.0

719 -4.4 717 55.6

771 -3.8 756 56.0

813 -5.7 786 56.1

861 -3.7 823 56.8

908 -2.1 913 57.0

951 -4.5 998 57.8

1001 -2.8 1,112 59.9

1,224 -3.3 1,381 60.9

1,351 -5.3 1,398 60.4

1366 -5.8 1453 60.4

1,423 -4.3 1,504 61.0

1,476 -5.6 1,509 62.6

Furthermore, the performance of the inhibitory agents X alone at the same concentration as that achieved during the tests combining the two products are:

(cm3 / s) DR%

X50

330 41.4

437 47.2

545 47.7

649 48.6 657 50.0

692 49.4

703 50.6

714 50.6

789 51.1

793 50.8

800 51.8

950 54.0

1008 52.5

1148 54.0

1,296 54.4

1356 55.1

1451 56.7

1,510 57.4

1,511 58.1

In view of the results obtained, it appears that the biocidal product Y does not have the ability to reduce hydrodynamic friction and in certain cases contributes to increasing hydrodynamic friction. On the other hand, the addition of the biocidal compound Y to friction inhibiting agents X, namely (X + Y) makes it possible to achieve performances in friction reduction comparable or superior to those measured when the latter are used alone in dilute solution, while retaining the biocidal performance, namely CE ₅₀ (24h) = 25%.

Claims

CLAIMS 1. Process for treating flowing water and surfaces in contact with said flowing water, characterized in that it is introduced together into said water, preferably near said surface, more preferably in the internal area of the boundary layer:

2. Method according to claim 1, characterized in that said macromolecular friction reducing compound comprises water-soluble polymers of molecular weight preferably greater than 5x10 ⁵ Dalton, more preferably still 5x10 ⁶ Dalton.

3. Method according to one of claims 1 or 2, characterized in that said friction reducing compound is chosen from the following polymers of the polyacrylamide, poly (ethylene oxide) and polysaccharide type extracted from plants or produced by algae, marine microorganisms or bacteria.

4. Method according to one of claims 1 to 3, characterized in that said biocidal compound is chosen from a polyamine of formula (I)

in which Ri is a C ₈ -C ₂₂ alkyl or alkenyl radical and 'n' is an integer from 0 to 3, and / or at least one monoamine of formula (II)

(II) R ₂ NH ₂ in which R ₂ is a C ₈ -C ₂₂ alkyl or alkenyl radical.

5. Method according to claim 4, characterized in that said biocidal compounds comprise a mixture containing on the one hand at least one polyamine of formula (I) in which the radical R 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.

6. Method according to one of claims 1 to 5, characterized in that said biocidal compounds comprise a mixture of polyamines derived from tallow and / or polyamines derived from a vegetable or animal oil containing olein with at least one polyamine derived from coconut.

7. Method according to one of claims 1 to 6, characterized in that the ratio of the concentrations in water of the said biocidal compound (s) to (x) said (s) compound (s) reducing friction (s) is understood between 10 ^"6 and 10 ⁺⁴ , and preferably between 0 ^{" 2} and 1.

8. Method according to one of claims 1 to 7, characterized in that the concentration of said biocidal compounds is from 0.01 to 100 ppm, preferably from 0.05 to 10 ppm, more preferably from 0.1 to 2 ppm.

9. Method according to one of claims 1 to 8, characterized in that the concentration of said friction-reducing polymer compounds is from 0.01 to 7500 ppm, preferably from 0.1 to 2500 ppm, more preferably from 1 at 500 ppm.

10. Method according to one of claims 1 to 9, characterized in that at least one of said biocidal compound and friction reducing compound is introduced into the water, intermittently, preferably near said surfaces, preferably still in the internal zone of the boundary layer.

11. Method according to one of claims 1 to 9, characterized in that at least one of said biocidal compound and friction reducing compound is introduced into the water continuously, preferably near said surfaces, preferably still in the inner area of the boundary layer.

12. Method according to one of claims 1 to 11, characterized in that said biocidal compound is introduced in the form of an emulsion in a continuous aqueous phase.

13. Method according to one of claims 1 to 12, characterized in that said friction-reducing compound is introduced in the form of a powder to be disseminated, or an aqueous solution, or a suspension, or an oily phase emulsion continues to inject.

14. Method according to one of claims 1 to 11, characterized in that the two said biocidal and friction-reducing compounds are formulated in the same composition.

15. Composition useful for the implementation of a method according to claim 14, characterized in that it comprises: - at least one said biocidal compound as defined in claims 1 to 9, and

- at least one said friction reducing compound as defined in claims 1 to 9.

16. Composition according to claim 14, characterized in that it is formulated in the form of a powder to be disseminated or in the form of an injectable liquid, in particular an emulsion, or in the form of a gel to be allowed to diffuse.

17. Composition according to one of claims 15 to 16, characterized in that said composition is in the form of an emulsion, said biocidal compound being contained in an oily phase and said friction reducing compound being contained in an aqueous phase.

18. Composition according to claim 15 to 17, characterized in that it is formulated in the form of a coating intended to be applied to said surface in contact with water, preferably a paint, said formulation being such that it gradually releases at least said friction reducing polymer compound in said water in contact with said surface.

19. Composition according to one of claims 15 to 18, characterized in that the weight ratio of said biocidal compounds to said friction reducing compound in said composition is from 1/100 to 1.