EP1664156A1 - Stable emulsions which are used to lower the pour point of crude oils and to inhibit paraffin deposition - Google Patents

Stable emulsions which are used to lower the pour point of crude oils and to inhibit paraffin deposition

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Publication number
EP1664156A1
EP1664156A1 EP04786266A EP04786266A EP1664156A1 EP 1664156 A1 EP1664156 A1 EP 1664156A1 EP 04786266 A EP04786266 A EP 04786266A EP 04786266 A EP04786266 A EP 04786266A EP 1664156 A1 EP1664156 A1 EP 1664156A1
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EP
European Patent Office
Prior art keywords
water
weight
parts
polymers
solvent
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP04786266A
Other languages
German (de)
French (fr)
Inventor
Marie-France Delamotte
Didier Faure
Denis Tembou N'zudie
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Carbonisation et Charbons Actifs CECA SA
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Application filed by Carbonisation et Charbons Actifs CECA SA filed Critical Carbonisation et Charbons Actifs CECA SA
Publication of EP1664156A1 publication Critical patent/EP1664156A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C10L10/16—Pour-point depressants
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    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
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    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/192—Macromolecular compounds
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    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
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    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
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Definitions

  • compositions according to the invention which are in the form of stable emulsions provide a solution to this problem of phase shift which induces processing difficulties when using the combination of said polymers on petroleum fields.
  • Many crude petroleum oils contain significant fractions of paraffins, the amount and exact nature of which vary according to the fields of extraction. At the temperature of the well, the paraffins are liquid and dissolved in the crude oil. When the oil rises to the surface, its temperature drops and the paraffins, while crystallizing, form a three-dimensional network of needles and scales. This results in a loss of fluidity which makes the production, transport, storage and even processing of these oils very difficult.
  • n-alkyl (meth) acrylate monomers with n varying from 6 to 40 with optionally one or more comonomers such as vinylpiridines, fatty chain alpha olefin monomers (n-alkyl, with n varying from 6 to 40), and the monomers chosen from ethylenically unsaturated mono- and / or dicarboxylic acids or anhydrides, see for example US 6,218,490 from CECA, US 4,663,491 from STAUCHAUSEN,
  • the polymer compositions according to the invention comprise polymers derived from at least two of the three families: i) copolymers of ethylene and of at least one ethylenically unsaturated monomer, for example acetate of vinyl (EVA), ii) ethylene copolymers as defined under i) grafted with polymers such as fatty chain polyacrylates (eg.
  • EVA grafted n-alkyl polyacrylate and iii) (co) polymers of (meth ) acrylate of n-alkyl and of monomers chosen from the following group: fatty chain alpha olefins (n-alkyl, with n varying from 6 to 40), vinyl esters, aromatic vinyls, vinylpiridins and its derivatives, N-vinylpyrrolidone, (meth) acrylamides and their derivatives, ethylenically unsaturated mono- and / or dicarboxylic acids or anhydrides or ethylenically unsaturated mono- and / or dicarboxylic anhydrides and are in the form of a stable emulsion.
  • fatty chain alpha olefins n-alkyl, with n varying from 6 to 40
  • vinyl esters aromatic vinyls
  • vinylpiridins and its derivatives N-vinylpyrrolidone
  • compositions of the present invention preferably comprise at least 100 parts by weight of the following constituents 1 to 6: 1) 5 to 70, preferably 5 to 50 and advantageously 5 to 40 parts by weight of at least two (co) polymers belonging to at least two of the following families i) ii) and iii): i) copolymers of ethylene containing 50 to 90% and advantageously 60 to 80% by weight of ethylene and 10 to 50, advantageously 20 to 40% by weight of at least one ethylenically unsaturated monomer chosen from the following group: vinyl esters of C 2 to Ci ⁇ and preferably C 2 to C 5 monocarboxylic acids, alkyl esters thereof to C ⁇ 2 monocarboxylic acids C 3 C ⁇ 2, alpha and beta unsaturated dicarboxylic compounds as the diacid, diester of C1-C ⁇ 2, or anhydride.
  • vinyl esters vinyl acetate is advantageously used.
  • unsaturated mono carboxylic acid esters it is preferable to use the Ci to C acrylates and methacrylates
  • the unsaturated alpha, beta dicarboxylic compounds are preferably methyl, ethyl or propyl diesters of maleic acid, maleic alkyl, fumaric or alkyl fumaric acid.
  • ethylene copolymers described in i) grafted with polymers which are (co) polymers derived from 50 to 100%, preferably from 70 to 100%, by weight of one or more monomers of (meth) acrylate n-alkyl, with n varying from 6 to 40, preferably from 14 to 30 and optionally 0 to 50%, preferably from 0 to 30% of one or more monomers chosen from the following group: fatty chain alpha olefins (n-alkyl, with n varying from 6 to 40), vinyl esters, aromatic vinyls, vinylpiridins and its derivatives, N-vinylpyrrolidone, (meth) acrylamides and their derivatives, acids or anhydrides mono- and / or ethylenically unsaturated dicarboxyls or ethylenically unsaturated mono- and / or dicarboxylic anhydrides; the graft copolymers ii) comprise 5 to 95% and advantageously 40 to 75%
  • n-alkyl (meth) acrylate monomers derived from 50 to 100%, preferably from 70 to 100%, by weight of one or more n-alkyl (meth) acrylate monomers, with n varying from 6 to 40, preferably from 14 to 30 and optionally 0 to 50%, preferably from 0 to 30% of one or more monomers chosen from the following group: fatty chain alpha olefins (n-alkyl, with n varying from 6 to 40), esters vinyl, aromatic vinyl, vinylpiridins and its derivatives, N-vinylpyrrolidone, (meth) acrylamides and their derivatives, ethylenically unsaturated mono- and / or dicarboxylic acids or anhydrides or ethylenically unsaturated mono- and / or dicarboxylic anhydrides.
  • a solvent or mixture of solvents immiscible with water preferably chosen from aromatic solvents (toluene, xylene), alone or as a mixture
  • a co-solvent or a mixture of co-solvents miscible with water preferably from 5 to 25, and advantageously from 5 to 20 parts by weight, chosen from ketones such as methyl ethyl ketone or methylisobutyl ketone, alcohols such as butanol or isopropanol, glycols and polyglycol ethers such as ethylene or propylene glycol, diethylene glycol or dipropylene glycol;
  • the surfactants used for the emulsions to be mixed can be identical or different, 5) 0 to 2, preferably from 0.01 to 0.6 and advantageously from 0.02 to 0.2 parts by weight d '' one or more thickeners such as Xanthane ®, 6) water (qs 100: the sum of constituents 1) to 6) representing 100 parts by weight)
  • the invention also relates to the processes for preparing these compositions which can be obtained according to one of the following two processes : - by emulsification of the mixture of polymers from at least two of families i), ii) and iii) (process A) or - by mixture of emulsions of polymers of different families i), ii) and iii) (process B) Method A of emulsification of a mixture of polymers derived from at least two of the three families of polymers i), ii) and iii) mentioned above is characterized in that: A1- a solution of polymers from at least two
  • A5- optionally one or more surfactants are added which may or may not be identical to those of step A2 and / or one or more thickeners to improve the stability of the emulsion.
  • the phases A1, A2, and A3 are carried out with stirring at temperatures generally of at least 25 ° C.
  • the temperature is chosen such that the viscosity of the solutions of the polymers to be emulsified allows scraping, stirring and shearing by stirring the mixture using a stirring mobile.
  • the viscosity generally does not exceed 300 Pa.s (300,000 cp)
  • Phase A4 can be carried out at the same time as phase A3 or before phase A3.
  • Phase A5 can be carried out at the same time as phase A4, before or after phase A4.
  • the addition of water can be done in continuous, batch, semi-continuous or semi-batch mode.
  • the quantities of reagents used are as follows: A1- a solution of 10 to 70 parts by weight of polymers of at least two of the families i) to iii) described above is prepared in 10 to 60 parts by weight of at least one organic solvent or mixture of solvents ( s) immiscible with water, A2- 0.1 to 10 parts by weight of pure or diluted surfactant (s) are added to the solution obtained, A3- 10 to 80 are added parts by weight of water to form an emulsion, A4- 0 to 30 parts by weight of a solvent or mixture of solvents miscible with water are added, A5- 0 to 3 parts by weight of one or more surfactants and / or 0 to 2 parts by weight of one or more thickeners to improve the stability of the emulsion.
  • a variant of method A can be carried out as follows: Aa1- a solution of polymers of at least two of the families i) to iii) described above is prepared in at least one solvent or mixture of organic solvents (s) which are immiscible (s) with water, Aa2- one or more pure or diluted surfactants in water or in another solvent (miscible or immiscible with water) are put into water, Aa3- is added to l water containing the surfactant (s) prepared in Aa2) the polymer solution prepared in Aa1) to form an emulsion, Aa4- optionally adding a solvent or mixture of solvents miscible with water, Aa5- optionally adding one or more surfactants which may or may not be identical to those of step Aa2 and / or one or more thickeners to improve the stability of the emulsion.
  • the phases Aa1, Aa2, and Aa3 are carried out with stirring at temperatures generally of at least 25 ° C.
  • the temperature is chosen such that the viscosity of the solution of the polymers to be emulsified allows it to be poured and dispersed in water containing surfactant (s) prepared in Aa2.
  • surfactant s
  • the viscosity of the polymer solution generally does not exceed 150 Pa.s (150,000 cp)
  • Phase A4 can be conducted before phase Aa3.
  • the Aa5 phase can be carried out at the same time as the Aa4 phase, before or after the Aa4 phase.
  • the polymer solution can be added either in continuous, batch, semi-continuous or semi-batch mode.
  • the quantities of reagents used are in the same ranges as for process A: Aa1- a solution of 10 to 70 parts by weight of polymers of at least two of families i) to iii) described is prepared. above in 10 to 60 parts by weight of at least one solvent or mixture of organic solvents immiscible with water, Aa2- in 10 to 80 parts by weight of water, 0.1 to 10 parts by weight of surfactant (s) pure or diluted in water or in another solvent (miscible or immiscible with water), Aa3- is added to the water containing the (s) surfactant (s) prepared in Aa2) the polymer solution prepared in Aa1) to form an emulsion, Aa4- 0 to 30 parts by weight of a solvent or mixture of solvents miscible with water are added , Aa5- 0 to 3 parts by weight of one or more surfactants and / or 0 to 2 parts by weight of one or more thickeners are added.
  • the emulsion mixing process B is characterized in that: B1- at least two polymer emulsions belonging solely to at least two of the three families i), ii) or iii) described above are prepared separately (each emulsion obtained therefore contains only polymers belonging to a single family i), ii), or iii)) according to method A above, its variant Aa or, for the emulsion of polymer (s) from family iii), can also proceed by radical emulsion polymerization, carried out in a conventional manner in an apparatus known for emulsion polymerizations according to a batch, semi-batch, continuous or semi-continuous process.
  • the emulsions of polymers i) not containing any water-immiscible solvent according to the well-known method of emulsification using an extruder, B2- mixed (by addition, with stirring, of an emulsion in the other at a temperature in general of at least 10 ° C., the temperature being chosen such that it is greater than the freezing point of the emulsions) the polymer emulsions obtained in B1), it being understood that said emulsions have mix must come from at least two of families i), ii) and iii), B3- optionally one or more surfactants are added which may or may not be identical to those of steps A2 or Aa2 and / or one or more thickeners to improve the stability of the emulsion.
  • the organic solvents of each of the emulsions to be mixed can be identical or different.
  • compositions according to the invention comprising polymers of families i) and ii)
  • process A the process for emulsifying the mixture of polymers i) and ii) is preferred in order to avoid double emulsification followed by mixing .
  • the present invention also relates to the use of the compositions according to the invention as additives for lowering the pour point of crude oils and / or inhibiting the deposition of paraffins in crude oils.
  • the advantage of the compositions according to the invention lies in their excellent stability, which results in an easy implementation on the oil fields. Indeed, the presence of polymers from at least two of the three families i) to iii) in a single composition or single pot without their separating into several distinct phases makes it possible to avoid the use of several injection lines for different additives on the oil fields and / or to have a single tank for mixing several additives before injection into the crude oil.
  • the invention provides additives which allow them to avoid multiple point injections, tank agitation before injection as well as the management constraints of several "incompatible" products.
  • the performances of the compositions of Examples 1 to 3 were evaluated by measuring the pour point according to standard ASTM D97 which consists in adding the crude oil brought to a temperature above its pour point, with a defined amount of additive, then cool the crude in 3 ° C increments, the pour point representing the temperature from which the crude oil no longer flows.
  • ASTM D97 standard ASTM D97 which consists in adding the crude oil brought to a temperature above its pour point, with a defined amount of additive, then cool the crude in 3 ° C increments, the pour point representing the temperature from which the crude oil no longer flows.
  • a HERZOG MP852 device was used, the flow detection of which is ensured by an LCD camera. All the compositions were tested in an Egyptian crude oil whose pour point measured according to this method is 33 ° C.
  • EXAMPLE 1 75 g of a solution comprising 55% are introduced into a half-liter double-walled reactor equipped with stirring, a reflux condenser, a bath thermostatically controlled at 75 ° C. __ by weight of copolymer of alkyl acrylate, C 18 to 22 and 4-vinyl pyridine (5% by weight of 4-vinyl pyridine) in a mixture of aromatic solvents (SOLVESSO150) 2 was added 75 g of a solution comprising 49% of ethylene and vinyl acetate (28% vinyl acetate) grafted with an alkyl polyacrylate C ⁇ 8- 22 (the ratio of polyacrylate grafted alkyl / ethylene and vinyl acetate being 1) in a mixture of aromatic solvents (SOLVESSO150) 3- heating to 75 ° C, 4- introducing 20 g of nonionic surfactant (REMCOPAL 25 sold by CECA which is an ethoxylated fatty alcohol) 5- wait 30 min for the homogenization of the reaction mixture 6- introduce in
  • Example 2 (comparative) 75 g of a solution are introduced into a double-walled half-liter reactor equipped with stirring, a reflux condenser, a bath thermostatically controlled at 75 ° C.
  • Example 3 The compositions obtained in examples 1 and 2 are injected at the level of 1000 ppm into an Egyptian crude oil having a pour point of 33 ° C.
  • the polymer solution of Example 2 it is necessary to stir it for homogenization before the additivation of the oil or else to prepare separately two solutions each containing the polymers and to carry out a double injection.
  • Crude oils with additives have a pour point of 9 ° C.
  • the emulsion of Example 1 according to the invention has the advantage of being able to be injected into the oil without prior homogenization operation or double injection.

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Abstract

The invention relates to compositions which are based on olefinic copolymers and/or polyacrylate and which take the form of stable concentrated emulsions. Such compositions are particularly effective as additives which are used in order to lower the pour point of crude oils and/or to inhibit paraffin deposition in crude oils, for example in one pot form.

Description

EMULSIONS STABLES POUR L'ABAISSEMENT DU POINT D'ECOULEMENT DES HUILES BRUTES ET L'INHIBITION DU DEPOT DE PARAFFINES DOMAINE TECHNIQUE La présente invention concerne des compositions de polymères STABLE EMULSIONS FOR LOWERING THE FLOW POINT OF CRUDE OILS AND INHIBITING THE DEPOSITION OF PARAFFINS TECHNICAL FIELD The present invention relates to polymer compositions
« incompatibles en solution organique» c'est-à-dire se séparant en plusieurs phases distinctes lorsque les solutions des polymères sont mélangées et laissées au repos. Les compositions selon l'invention qui se présentent sous forme d'émulsions stables apportent une solution à ce problème de déphasage qui induit des difficultés de mise en œuvre lors de l'utilisation de la combinaison desdits polymères sur les champs de pétrole. De nombreuses huiles brutes de pétrole contiennent des fractions importantes de paraffines, dont la quantité et la nature exacte sont variables selon les champs d'extraction. A la température du puits, les paraffines sont liquides et dissoutes dans l'huile brute. Lors de la remontée de l'huile en surface, sa température s'abaisse et les paraffines en cristallisant forment un réseau tridimensionnel d'aiguilles et d'écaillés. Il en résulte une perte de fluidité qui rend la production, le transport, le stockage et même le traitement de ces huiles très difficiles. Les bouchages au niveau des pipelines et des appareils de traitement sont fréquents. TECHNIQUE ANTÉRIEURE On a proposé de nombreux procédés pour résoudre ce problème, comme le raclage mécanique ou bien le chauffage des parois. Ces procédés sont coûteux et leur mise en oeuvre n'est pas toujours possible. Pour améliorer la rhéologie des pétroles bruts, différentes familles de polymères ont été proposées : i) les copolymères de l'éthylène comme les copolymères d'éthylène et d'acétate de vinyle (EVA) décrits dans FR 2 184 522 (1972) ; RU 785.337 décrit des produits de copolymérisation entre l'éthylène, l'acétate de vinyle et l'anhydride maléique ; US 3.341.309 et US 3.304.261 de ESSO recommandent l'utilisation des produits de copolymérisation de l'éthylène, acétate de vinyle et du fumarate de dilauryl ou diisodecyl ; US 4.160.459 de TEXACO décrit des produits de copolymérisation entre l'éthylène, l'acétate de vinyle et les méthacrylates d'alkyle. ii) les copolymères d'éthylène greffés avec des polymères comme les poly(méth)acrylates de n-alkyle. US 4.608.411 de ELF décrit ce type de copolymères dont des exemples typiques sont les EVA greffés avec de chaînes polyacrylates de n-alkyle. iii) les (co) polymères d'un ou plusieurs monomères de (méth)acrylate de n-alkyle, avec n variant de 6 à 40 avec éventuellement un ou plusieurs comonomères tels que les vinylpiridines, les monomères d'alpha oléfine à chaîne grasse (n-alkyle, avec n variant de 6 à 40), et les monomères choisis parmi les acides ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés, voir par exemple US 6.218.490 de CECA, US 4.663.491 de STAUCHAUSEN,"Incompatible in organic solution" that is to say separating into several distinct phases when the solutions of the polymers are mixed and left to stand. The compositions according to the invention which are in the form of stable emulsions provide a solution to this problem of phase shift which induces processing difficulties when using the combination of said polymers on petroleum fields. Many crude petroleum oils contain significant fractions of paraffins, the amount and exact nature of which vary according to the fields of extraction. At the temperature of the well, the paraffins are liquid and dissolved in the crude oil. When the oil rises to the surface, its temperature drops and the paraffins, while crystallizing, form a three-dimensional network of needles and scales. This results in a loss of fluidity which makes the production, transport, storage and even processing of these oils very difficult. Blockages in pipelines and processing equipment are common. PRIOR ART Numerous methods have been proposed for solving this problem, such as mechanical scraping or even wall heating. These methods are expensive and their implementation is not always possible. To improve the rheology of crude oils, different families of polymers have been proposed: i) ethylene copolymers such as the ethylene and vinyl acetate (EVA) copolymers described in FR 2 184 522 (1972); RU 785.337 describes products of copolymerization between ethylene, vinyl acetate and maleic anhydride; US 3,341,309 and US 3,304,261 from ESSO recommend the use of copolymerization products of ethylene, vinyl acetate and dilauryl or diisodecyl fumarate; US 4,160,459 to TEXACO describes products of copolymerization between ethylene, vinyl acetate and alkyl methacrylates. ii) ethylene copolymers grafted with polymers such as n-alkyl poly (meth) acrylates. US 4,608,411 to ELF describes this type of copolymer typical examples of which are EVAs grafted with n-alkyl polyacrylate chains. iii) the (co) polymers of one or more n-alkyl (meth) acrylate monomers, with n varying from 6 to 40 with optionally one or more comonomers such as vinylpiridines, fatty chain alpha olefin monomers (n-alkyl, with n varying from 6 to 40), and the monomers chosen from ethylenically unsaturated mono- and / or dicarboxylic acids or anhydrides, see for example US 6,218,490 from CECA, US 4,663,491 from STAUCHAUSEN,
US 2.839.512 et FR 2.128.589 de SHELL. Ces polymères i) à iii) décrits ci-dessus sont en général proposés sous forme de solution organique pour le traitement des huiles brutes de pétrole. Cependant des polymères issus des familles i) ou iii) sous forme d'émulsion ou de dispersion ont fait l'objet de brevets : les polymères iii) en émulsion sont décrits dans WO03/014170 de CECA, US 4.110.283 de SERVO, EP 448.166 et WO 98/51731 de SHELL et WO 98/33846 de British Petroleum ; les polymères i) sous forme d'émulsion ont été recommandés dans CA986635 d'EXXON et EP46.190 de BASF. Pour ce qui concerne l'amélioration des propriétés des pétroles bruts par additivation de ces polymères, les familles de polymères i), ii) et iii) en solution ont souvent montré des limites d'efficacité pour certains bruts lorsqu'elles sont utilisées individuellement alors que l'association des différentes familles permet de dégager des synergies d'efficacité. C'est ainsi qu'une combinaison entre EVA et polyacrylates à longues chaîne alkyle [polymère i) + polymère iii)] a montré une amélioration des performances comparativement à chaque polymère pris séparément. De telles combinaisons sont décrites dans GB 1.112.803 de ESSO et US 4.153.423 de EXXON. Cependant, les mélanges des polymères en solution issus de la combinaison des familles i), ii) et iii) ont montré des limites en terme de stabilité liée à leur « incompatibilité ». L'homme de l'art doit ainsi faire face à ce problème « d'incompatibilité » des polymères et de stabilité de leurs solutions organiques, c'est à dire des polymères se séparant en plusieurs phases distinctes lorsque les solutions organiques sont mélangées et laissées au repos. Il en résulte une impossibilité de commercialiser une solution stable comprenant un mélange de ces polymères. Les fabricants d'additifs pétroliers doivent par conséquent proposer chaque famille de polymères [i), ii), ou iii)] séparément en laissant le soin aux opérateurs pétroliers de gérer la mise en œuvre de leur combinaison sur les champs de pétrole au moment de l'injection dans le pétrole brut. Il est bien connu dans le métier de la production pétrolière qu'on peut faire face à ce problème en utilisant : - soit une cuve agitée contenant la solution de mélange desdits polymères avant l'injection dans le pétrole brut. L'agitation, qui doit être maintenue en permanence, permet ainsi d'éviter la séparation des phases avant l'injection. - soit plusieurs lignes d'injection, chaque ligne étant dédiée à une famille de polymères. Dans ces deux cas de figure, l'opérateur pétrolier est emmené à faire face à un investissement en matériels ainsi qu'à des contraintes de gestion de plusieurs produits qui augmentent les difficultés de production mais aussi le coût de l'extraction. EXPOSE DE L'INVENTION Les compositions de polymères selon l'invention comprennent des polymères issus d'au moins deux des trois familles : i) copolymères de l'éthylène et d'au moins un monomère à insaturation éthylénique, par exemple l'acétate de vinyle (EVA), ii) copolymères de l'éthylène tels que définis sous i) greffés avec des polymères comme des polyacrylates à chaîne grasse (eg. EVA greffés polyacrylate de n-alkyle), et iii) (co)polymères de (méth)acrylate de n-alkyle et de monomères choisis parmi le groupe suivant : les alpha oléfines à chaîne grasse (n-alkyle, avec n variant de 6 à 40), les esters vinyliques, les vinyle aromatiques, les vinylpiridines et ses dérivés, la N-vinylpyrrolidone, les (méth)acrylamides et leurs dérivés, les acides ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés et se présentent sous forme d'émulsion stable. Les compositions de la présente invention comprennent de préférence au moins 100 parties en poids des constituants 1 à 6 suivants : 1) 5 à 70 , de préférence 5 à 50 et avantageusement 5 à 40 parties en poids d'au moins deux (co)polymères appartenant à au moins deux des familles i) ii) et iii) suivants : i) copolymères de l'éthylène contenant 50 à 90% et avantageusement 60 à 80% en poids d'éthylène et 10 à 50, avantageusement 20 à 40% en poids d'au moins un monomère à insaturation éthylénique choisi dans le groupe suivant : les esters vinyliques de C2 à Ciβ et avantageusement de C2 à C5, les acides monocarboxyliques, les esters d'alkyle en Ci à Cι2 d'acides mono carboxyliques en C3 à Cι2, les alpha et bêta de composés dicarboxyliques insaturés sous forme de diacide, de diester d'alkyle en C-i à Cι2, ou d'anhydride. Parmi les esters vinyliques l'acétate de vinyle est avantageusement utilisé. Parmi les esters d'acide mono carboxylique insaturé, il est préférable d'utiliser les acrylates et méthacrylates en C-i à C-|2 et avantageusement de Ci à C5. Les composés alpha, bêta dicarboxyliques insaturés sont préférentiellement les diesters de méthyle, éthyle ou propyle d'acide maléique, alkyle maléique, fumarique ou acide alkylfumarique. ii) copolymères de l'éthylène décrits en i) greffés avec des polymères qui sont des (co)polymères issus de 50 à 100 % de préférence de 70 à 100 %, en poids d'un ou plusieurs monomères de (méth)acrylate de n-alkyle, avec n variant de 6 à 40, de préférence de 14 à 30 et éventuellement 0 à 50 %, de préférence de 0 à 30 % d'un ou plusieurs monomères choisis parmi le groupe suivant : les alpha oléfines à chaîne grasse (n-alkyle, avec n variant de 6 à 40), les esters vinyliques, les vinyle aromatiques, les vinylpiridines et ses dérivés, la N-vinylpyrrolidone, les (méth)acrylamides et leurs dérivés, les acides ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés ; les copolymères greffés ii) comprennent 5 à 95% et avantageusement 40 à 75% en poids de copolymère de l'éthylène i) formant le tronc. iii) (co)polymères issus de 50 à 100 % de préférence de 70 à 100 %, en poids d'un ou plusieurs monomères de (méth)acrylate de n-alkyle, avec n variant de 6 à 40, de préférence de 14 à 30 et éventuellement 0 à 50 %, de préférence de 0 à 30 % d'un ou plusieurs monomères choisis parmi le groupe suivant : les alpha oléfines à chaîne grasse (n-alkyle, avec n variant de 6 à 40), les esters vinyliques, les vinyle aromatiques, les vinylpiridines et ses dérivés, la N-vinylpyrrolidone, les (méth)acrylamides et leurs dérivés, les acides ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés. 2) 0 à 60 parties en poids d'un solvant ou mélange de solvants non miscibles à l'eau, de préférence choisis parmi les solvants aromatiques (toluène, xylène), seuls ou en mélange 3) 0 à 30 parties en poids d'un co-solvant ou d'un mélange de co-solvants miscible(s) à l'eau de préférence de 5 à 25, et avantageusement de 5 à 20 parties en poids, choisi parmi les cétones telles que la méthyléthylcétone ou methylisobutylcetone, les alcools tels que le butanol ou l'isopropanol, les glycols et éthers de polyglycol tels que l'éthylène ou le propylène glycol, le diéthylène glycol ou le dipropylène glycol ; 4) 0,1 à 10, de préférence de 0,1 à 8 et avantageusement de 0,5 à 5 parties en poids d'un ou plusieurs tensioactifs (tensioactifs ioniques (cationiques ou anioniques) et/ou non-ioniques et/ou colloïdes protecteurs et/ou polymères amphiphiles; parmi les tensioactifs cationiques, on peut citer les sels d'ammonium quaternaires tels que les chlorures de diméthyldialkylammonium, les aminés grasses protonées ; parmi les tensioactifs non-ioniques, on peut citer les alcools gras polyethoxyles, les acides gras polyethoxyles, les alkylphénols polyethoxyles ; parmi les tensioactifs anioniques, on peut citer les alcools gras polyethoxyles sulfatés, les acides gras polyethoxyles sulfatés, les alkylphénols polyethoxyles sulfatés, les alkylbenzènes sulfonates et sulfosuccinates, les acides gras neutralisés ; parmi les colloïdes protecteurs on peut citer les alcools polyvinyliques ; parmi les polymères amphiphiles, on peut citer les copolymères de l'acide (méth)acrylique, les copolymères de l'anhydride maléique neutralisés par une base ou imidisés suivi d'une protonation ou d'une quaternisation ; dans le cas des compositions préparées par mélange d'au moins deux émulsions (procédé B), il convient d'éviter de mélanger des émulsions stabilisées par des tensioactifs de charges opposées et ce, afin d'éviter la floculation des particules. En dehors de cette restriction, les tensioactifs utilisés pour les émulsions à mélanger peuvent être identiques ou différents, 5) 0 à 2, de préférence de 0,01 à 0,6 et avantageusement de 0,02 à 0,2 parties en poids d'un ou plusieurs épaississants comme le Xanthane ®, 6) de l'eau (q s p 100: la somme des constituants 1) à 6) représentant 100 parties en poids) L'invention a trait également aux procédés de préparation de ces compositions qui peuvent être obtenues selon l'un des deux procédés suivants : - par émulsification du mélange de polymères issus d'au moins deux des familles i), ii) et iii) (procédé A) ou - par mélange d'émulsions de polymères de familles différentes i), ii) et iii) (procédé B) Le procédé A d'émulsification d'un mélange de polymères issus d'au moins deux des trois familles de polymères i), ii) et iii) cités ci-dessus est caractérisé en ce que : A1- on prépare une solution de polymères d'au moins deux des familles i) à iii) décrites ci-dessus dans au moins un solvant ou mélange de solvants organique(s) non miscible(s) à l'eau, A2- on ajoute à la solution obtenue un ou plusieurs tensioactifs purs ou dilués dans de l'eau ou dans un autre solvant (miscible ou non miscible avec l'eau), A3- on ajoute de l'eau pour former une émulsion, A4- on ajoute éventuellement un solvant ou mélange de solvants miscible(s) à l'eau. A5- on ajoute éventuellement un ou plusieurs tensioactifs qui peuvent être identiques ou non à ceux de l'étape A2 et/ou un ou plusieurs épaississants pour améliorer la stabilité de l'émulsion. Les phases A1 , A2, et A3 sont menées sous agitation à des températures en général d'au moins 25°C. La température est choisie telle que la viscosité des solutions des polymères à émulsionner permette raclage, brassage et cisaillement par agitation du mélange à l'aide d'un mobile d'agitation. Typiquement, la viscosité ne dépasse en général pas 300 Pa.s (300 000 cp) La phase A4 peut être menée en même temps que la phase A3 ou avant la phase A3. La phase A5 peut être menée en même temps que la phase A4, avant ou après la phase A4. L'ajout d'eau peut se faire soit en mode continu, batch, semi-continu ou semi-batch. De préférence les quantités des réactifs mis en œuvre sont les suivantes : A1- on prépare une solution de 10 à 70 parties en poids de polymères d'au moins deux des familles i) à iii) décrites ci-dessus dans 10 à 60 parties en poids d'au moins un solvant ou mélange de solvants organique(s) non miscible(s) à l'eau, A2- on ajoute à la solution obtenue 0,1 à 10 parties en poids de tensioactif(s) pur(s) ou dilué(s) , A3- on ajoute 10 à 80 parties en poids d'eau pour former une émulsion, A4- on ajoute 0 à 30 parties en poids d'un solvant ou mélange de solvants miscible(s) à l'eau, A5- on ajoute 0 à 3 parties en poids d'un ou plusieurs tensioactifs et/ou 0 à 2 parties en poids d'un ou plusieurs épaississants pour améliorer la stabilité de l'émulsion. Une variante du procédé A peut être conduite comme suit : Aa1- on prépare une solution de polymères d'au moins deux des familles i) à iii) décrites ci-dessus dans au moins un solvant ou mélange de solvants organique(s) non miscible(s) à l'eau, Aa2- on met dans l'eau un ou plusieurs tensioactifs purs ou dilués dans de l'eau ou dans un autre solvant (miscible ou non miscible avec l'eau), Aa3- on ajoute dans l'eau contenant le(s) tensioactif(s) préparée en Aa2) la solution de polymères préparée en Aa1) pour former une émulsion, Aa4- on ajoute éventuellement un solvant ou mélange de solvants miscible(s) à l'eau, Aa5- on ajoute éventuellement un ou plusieurs tensioactifs qui peuvent être identiques ou non à ceux de l'étape Aa2 et/ou un ou plusieurs épaississants pour améliorer la stabilité de l'émulsion. Les phases Aa1 , Aa2, et Aa3 sont menées sous agitation à des températures en général d'au moins 25°C. La température est choisie telle que la viscosité de la solution des polymères à émulsionner permette sa coulée et sa dispersion dans l'eau contenant du ou des tensioactifs préparée en Aa2. Typiquement, la viscosité de la solution des polymères ne dépasse en général pas 150 Pa.s (150.000 cp) La phase A4 peut être menée avant la phase Aa3. La phase Aa5 peut être menée en même temps que la phase Aa4, avant ou après la phase Aa4. L'ajout de la solution des polymères peut se faire soit en mode continu, batch, semi-continu ou semi-batch. De préférence les quantités des réactifs mis en œuvre sont dans les mêmes gammes que pour le procédé A : Aa1- on prépare une solution de 10 à 70 parties en poids de polymères d'au moins deux des familles i) à iii) décrites ci-dessus dans 10 à 60 parties en poids d'au moins un solvant ou mélange de solvants organique(s) non miscible(s) à l'eau, Aa2- dans 10 à 80 parties en poids d'eau, on met 0,1 à 10 parties en poids de tensioactif(s) pur(s) ou dilué(s) dans de l'eau ou dans un autre solvant (miscible ou non miscible avec l'eau), Aa3- on ajoute dans l'eau contenant le(s) tensioactif(s) préparée en Aa2) la solution de polymères préparée en Aa1) pour former une émulsion, Aa4- on ajoute 0 à 30 parties en poids d'un solvant ou mélange de solvants miscible(s) à l'eau, Aa5- on ajoute 0 à 3 parties en poids d'un ou plusieurs tensioactifs et/ou 0 à 2 parties en poids d'un ou plusieurs épaississants.US 2,839,512 and FR 2,128,589 from SHELL. These polymers i) to iii) described above are generally proposed in the form of an organic solution for the treatment of crude petroleum oils. However, polymers from families i) or iii) in the form of an emulsion or dispersion have been the subject of patents: the polymers iii) in emulsion are described in WO03 / 014170 by CECA, US 4,102,283 by SERVO, EP 448,166 and WO 98/51731 from SHELL and WO 98/33846 from British Petroleum; polymers i) in the form of an emulsion have been recommended in CA986635 by EXXXON and EP46.190 by BASF. With regard to the improvement of the properties of crude oils by additivation of these polymers, the families of polymers i), ii) and iii) in solution have often shown limits of effectiveness for certain crudes when they are used individually then that the association of the different families makes it possible to generate synergies of efficiency. A combination of EVA and long alkyl chain polyacrylates [polymer i) + polymer iii)] has shown an improvement in performance compared to each polymer taken separately. Such combinations are described in GB 1,112,803 from ESSO and US 4,153,423 from EXXON. However, mixtures of polymers in solution from the combination of families i), ii) and iii) have shown limits in terms of stability linked to their "incompatibility". Those skilled in the art must therefore face this problem of “incompatibility” of polymers and of stability of their organic solutions, ie polymers which separate in several distinct phases when the organic solutions are mixed and left resting. This results in an impossibility of marketing a stable solution comprising a mixture of these polymers. Petroleum additive manufacturers must therefore offer each family of polymers [i), ii), or iii)] separately, leaving it to the oil operators to manage the implementation of their combination on the oil fields at the time of injection into the crude oil. It is well known in the art of petroleum production that this problem can be overcome by using: - either a stirred tank containing the solution for mixing said polymers before injection into crude oil. Agitation, which must be maintained continuously, thus makes it possible to avoid the separation of the phases before injection. - or several injection lines, each line being dedicated to a family of polymers. In these two cases, the petroleum operator is led to face an investment in materials as well as constraints in the management of several products which increase production difficulties but also the cost of extraction. PRESENTATION OF THE INVENTION The polymer compositions according to the invention comprise polymers derived from at least two of the three families: i) copolymers of ethylene and of at least one ethylenically unsaturated monomer, for example acetate of vinyl (EVA), ii) ethylene copolymers as defined under i) grafted with polymers such as fatty chain polyacrylates (eg. EVA grafted n-alkyl polyacrylate), and iii) (co) polymers of (meth ) acrylate of n-alkyl and of monomers chosen from the following group: fatty chain alpha olefins (n-alkyl, with n varying from 6 to 40), vinyl esters, aromatic vinyls, vinylpiridins and its derivatives, N-vinylpyrrolidone, (meth) acrylamides and their derivatives, ethylenically unsaturated mono- and / or dicarboxylic acids or anhydrides or ethylenically unsaturated mono- and / or dicarboxylic anhydrides and are in the form of a stable emulsion. The compositions of the present invention preferably comprise at least 100 parts by weight of the following constituents 1 to 6: 1) 5 to 70, preferably 5 to 50 and advantageously 5 to 40 parts by weight of at least two (co) polymers belonging to at least two of the following families i) ii) and iii): i) copolymers of ethylene containing 50 to 90% and advantageously 60 to 80% by weight of ethylene and 10 to 50, advantageously 20 to 40% by weight of at least one ethylenically unsaturated monomer chosen from the following group: vinyl esters of C 2 to Ciβ and preferably C 2 to C 5 monocarboxylic acids, alkyl esters thereof to Cι 2 monocarboxylic acids C 3 Cι 2, alpha and beta unsaturated dicarboxylic compounds as the diacid, diester of C₁-Cι 2, or anhydride. Among vinyl esters, vinyl acetate is advantageously used. Among the unsaturated mono carboxylic acid esters, it is preferable to use the Ci to C acrylates and methacrylates | 2 and advantageously from Ci to C 5 . The unsaturated alpha, beta dicarboxylic compounds are preferably methyl, ethyl or propyl diesters of maleic acid, maleic alkyl, fumaric or alkyl fumaric acid. ii) ethylene copolymers described in i) grafted with polymers which are (co) polymers derived from 50 to 100%, preferably from 70 to 100%, by weight of one or more monomers of (meth) acrylate n-alkyl, with n varying from 6 to 40, preferably from 14 to 30 and optionally 0 to 50%, preferably from 0 to 30% of one or more monomers chosen from the following group: fatty chain alpha olefins (n-alkyl, with n varying from 6 to 40), vinyl esters, aromatic vinyls, vinylpiridins and its derivatives, N-vinylpyrrolidone, (meth) acrylamides and their derivatives, acids or anhydrides mono- and / or ethylenically unsaturated dicarboxyls or ethylenically unsaturated mono- and / or dicarboxylic anhydrides; the graft copolymers ii) comprise 5 to 95% and advantageously 40 to 75% by weight of ethylene copolymer i) forming the trunk. iii) (co) polymers derived from 50 to 100%, preferably from 70 to 100%, by weight of one or more n-alkyl (meth) acrylate monomers, with n varying from 6 to 40, preferably from 14 to 30 and optionally 0 to 50%, preferably from 0 to 30% of one or more monomers chosen from the following group: fatty chain alpha olefins (n-alkyl, with n varying from 6 to 40), esters vinyl, aromatic vinyl, vinylpiridins and its derivatives, N-vinylpyrrolidone, (meth) acrylamides and their derivatives, ethylenically unsaturated mono- and / or dicarboxylic acids or anhydrides or ethylenically unsaturated mono- and / or dicarboxylic anhydrides. 2) 0 to 60 parts by weight of a solvent or mixture of solvents immiscible with water, preferably chosen from aromatic solvents (toluene, xylene), alone or as a mixture 3) 0 to 30 parts by weight of a co-solvent or a mixture of co-solvents miscible with water, preferably from 5 to 25, and advantageously from 5 to 20 parts by weight, chosen from ketones such as methyl ethyl ketone or methylisobutyl ketone, alcohols such as butanol or isopropanol, glycols and polyglycol ethers such as ethylene or propylene glycol, diethylene glycol or dipropylene glycol; 4) 0.1 to 10, preferably 0.1 to 8 and advantageously 0.5 to 5 parts by weight of one or more surfactants (ionic (cationic or anionic) and / or nonionic surfactants and / or protective colloids and / or amphiphilic polymers; among the cationic surfactants, mention may be made of quaternary ammonium salts such as dimethyldialkylammonium chlorides, protonated fatty amines; among non-ionic surfactants, mention may be made of polyethoxy fatty alcohols, polyethoxylated fatty acids, polyethoxylated alkylphenols; among the anionic surfactants, mention may be made of sulfated polyethoxylated fatty alcohols, sulfated polyethoxylated fatty acids, sulfated polyethoxylated alkylphenols, alkylbenzene sulfonates and sulfosuccinates, neutralized fatty acids; protective colloids can be mention polyvinyl alcohols; among the amphiphilic polymers, mention may be made of (meth) acrylic acid copolymers, copo maleic anhydride lymers neutralized by a base or imidized followed by a protonation or a quaternization; in the case of compositions prepared by mixing at least two emulsions (method B), it is advisable to avoid mixing emulsions stabilized by surfactants of opposite charges, in order to avoid flocculation of the particles. Apart from this restriction, the surfactants used for the emulsions to be mixed can be identical or different, 5) 0 to 2, preferably from 0.01 to 0.6 and advantageously from 0.02 to 0.2 parts by weight d '' one or more thickeners such as Xanthane ®, 6) water (qs 100: the sum of constituents 1) to 6) representing 100 parts by weight) The invention also relates to the processes for preparing these compositions which can be obtained according to one of the following two processes : - by emulsification of the mixture of polymers from at least two of families i), ii) and iii) (process A) or - by mixture of emulsions of polymers of different families i), ii) and iii) (process B) Method A of emulsification of a mixture of polymers derived from at least two of the three families of polymers i), ii) and iii) mentioned above is characterized in that: A1- a solution of polymers from at least two of families i) to iii) described above in at least one organic solvent or mixture of organic solvents immiscible with water, A2- one or more are added to the solution obtained several surfactants pure or diluted in water or in another solvent (miscible or immiscible with water), A3- we add water to form an emulsion, A4- optionally adding a solvent or mixture of solvents miscible with water. A5- optionally one or more surfactants are added which may or may not be identical to those of step A2 and / or one or more thickeners to improve the stability of the emulsion. The phases A1, A2, and A3 are carried out with stirring at temperatures generally of at least 25 ° C. The temperature is chosen such that the viscosity of the solutions of the polymers to be emulsified allows scraping, stirring and shearing by stirring the mixture using a stirring mobile. Typically, the viscosity generally does not exceed 300 Pa.s (300,000 cp) Phase A4 can be carried out at the same time as phase A3 or before phase A3. Phase A5 can be carried out at the same time as phase A4, before or after phase A4. The addition of water can be done in continuous, batch, semi-continuous or semi-batch mode. Preferably, the quantities of reagents used are as follows: A1- a solution of 10 to 70 parts by weight of polymers of at least two of the families i) to iii) described above is prepared in 10 to 60 parts by weight of at least one organic solvent or mixture of solvents ( s) immiscible with water, A2- 0.1 to 10 parts by weight of pure or diluted surfactant (s) are added to the solution obtained, A3- 10 to 80 are added parts by weight of water to form an emulsion, A4- 0 to 30 parts by weight of a solvent or mixture of solvents miscible with water are added, A5- 0 to 3 parts by weight of one or more surfactants and / or 0 to 2 parts by weight of one or more thickeners to improve the stability of the emulsion. A variant of method A can be carried out as follows: Aa1- a solution of polymers of at least two of the families i) to iii) described above is prepared in at least one solvent or mixture of organic solvents (s) which are immiscible (s) with water, Aa2- one or more pure or diluted surfactants in water or in another solvent (miscible or immiscible with water) are put into water, Aa3- is added to l water containing the surfactant (s) prepared in Aa2) the polymer solution prepared in Aa1) to form an emulsion, Aa4- optionally adding a solvent or mixture of solvents miscible with water, Aa5- optionally adding one or more surfactants which may or may not be identical to those of step Aa2 and / or one or more thickeners to improve the stability of the emulsion. The phases Aa1, Aa2, and Aa3 are carried out with stirring at temperatures generally of at least 25 ° C. The temperature is chosen such that the viscosity of the solution of the polymers to be emulsified allows it to be poured and dispersed in water containing surfactant (s) prepared in Aa2. Typically, the viscosity of the polymer solution generally does not exceed 150 Pa.s (150,000 cp) Phase A4 can be conducted before phase Aa3. The Aa5 phase can be carried out at the same time as the Aa4 phase, before or after the Aa4 phase. The polymer solution can be added either in continuous, batch, semi-continuous or semi-batch mode. Preferably, the quantities of reagents used are in the same ranges as for process A: Aa1- a solution of 10 to 70 parts by weight of polymers of at least two of families i) to iii) described is prepared. above in 10 to 60 parts by weight of at least one solvent or mixture of organic solvents immiscible with water, Aa2- in 10 to 80 parts by weight of water, 0.1 to 10 parts by weight of surfactant (s) pure or diluted in water or in another solvent (miscible or immiscible with water), Aa3- is added to the water containing the (s) surfactant (s) prepared in Aa2) the polymer solution prepared in Aa1) to form an emulsion, Aa4- 0 to 30 parts by weight of a solvent or mixture of solvents miscible with water are added , Aa5- 0 to 3 parts by weight of one or more surfactants and / or 0 to 2 parts by weight of one or more thickeners are added.
Le procédé B de mélange d'émulsion est caractérisé en ce que : B1- on prépare séparément au moins deux émulsions de polymères appartenant uniquement à au moins deux des trois familles i), ii) ou iii) décrites ci- dessus (chaque émulsion obtenue contient donc uniquement des polymères appartenant à une seule famille i), ii), ou iii)) selon le procédé A ci-dessus, sa variante Aa ou, pour l'émulsion de polymère(s) issue de la famille iii), on peut également procéder par polymérisation radicalaire en émulsion, menée de manière classique dans un appareillage connu pour les polymérisations en émulsion selon un procédé batch, semi-batch, continu ou semi-continu. Il est également possible de préparer les émulsions de polymères i) ne contenant pas de solvant non miscible à l'eau selon le procédé bien connu de mise en émulsion utilisant une extrudeuse, B2- on mélange (par addition sous agitation d'une émulsion dans l'autre à une température en général d'au moins 10°C, la température étant choisie de telle sorte qu'elle soit supérieure au point de congélation des émulsions) les émulsions de polymères obtenues en B1), étant entendu que lesdites émulsions à mélanger doivent être issues d'au moins deux des familles i), ii) et iii), B3- on ajoute éventuellement un ou plusieurs tensioactifs qui peuvent être identiques ou non à ceux des étapes A2 ou Aa2 et/ou un ou plusieurs épaississants pour améliorer la stabilité de l'émulsion. Les solvants organiques de chacune des émulsions à mélanger peuvent être identiques ou différents.The emulsion mixing process B is characterized in that: B1- at least two polymer emulsions belonging solely to at least two of the three families i), ii) or iii) described above are prepared separately (each emulsion obtained therefore contains only polymers belonging to a single family i), ii), or iii)) according to method A above, its variant Aa or, for the emulsion of polymer (s) from family iii), can also proceed by radical emulsion polymerization, carried out in a conventional manner in an apparatus known for emulsion polymerizations according to a batch, semi-batch, continuous or semi-continuous process. It is also possible to prepare the emulsions of polymers i) not containing any water-immiscible solvent according to the well-known method of emulsification using an extruder, B2- mixed (by addition, with stirring, of an emulsion in the other at a temperature in general of at least 10 ° C., the temperature being chosen such that it is greater than the freezing point of the emulsions) the polymer emulsions obtained in B1), it being understood that said emulsions have mix must come from at least two of families i), ii) and iii), B3- optionally one or more surfactants are added which may or may not be identical to those of steps A2 or Aa2 and / or one or more thickeners to improve the stability of the emulsion. The organic solvents of each of the emulsions to be mixed can be identical or different.
Dans le cas de compositions selon l'invention comprenant des polymères des familles i) et ii), le procédé emulsification du mélange de polymères i) et ii) (procédé A) est préféré afin d'éviter une double emulsification suivie d'un mélange.In the case of compositions according to the invention comprising polymers of families i) and ii), the process for emulsifying the mixture of polymers i) and ii) (process A) is preferred in order to avoid double emulsification followed by mixing .
La présente invention concerne également l'utilisation des compositions selon l'invention comme additifs pour l'abaissement du point d'écoulement des pétroles bruts et/ou l'inhibition de dépôt de paraffines dans les pétroles bruts. L'avantage des compositions selon l'invention tient à leur excellente stabilité, ce qui se traduit par une mise en œuvre facile sur les champs de pétrole. En effet, la présence de polymères issus d'au moins deux des trois familles i) à iii) dans une seule et même composition ou pot unique sans qu'ils ne se séparent en plusieurs phases distinctes permet d'éviter l'utilisation de plusieurs lignes d'injection d'additifs différents sur les champs de pétrole et/ou de disposer d'une seule cuve de mélange de plusieurs additifs avant l'injection dans le pétrole brut. Pour les opérateurs pétroliers, l'invention propose des additifs qui leur permettent d'éviter les injections en points multiples, les agitations de cuve avant injection ainsi que les contraintes de gestion de plusieurs produits « incompatibles ». Les performances des compositions des exemples 1 à 3 ont été évaluées par mesure du point d'écoulement selon la norme ASTM D97 qui consiste à additionner l'huile brute portée à une température supérieure à son point d'écoulement, avec une quantité définie d'additif, puis à refroidir le brut par paliers de 3°C, le point d'écoulement représentant la température à partir de laquelle l'huile de brut ne s'écoule plus. Dans les exemples ci-dessous a été utilisé un appareil HERZOG MP852 dont la détection de l'écoulement est assurée par une caméra LCD. Toutes les compositions ont été testées dans une huile brute égyptienne dont le point d'écoulement mesuré selon cette méthode est de 33°C.The present invention also relates to the use of the compositions according to the invention as additives for lowering the pour point of crude oils and / or inhibiting the deposition of paraffins in crude oils. The advantage of the compositions according to the invention lies in their excellent stability, which results in an easy implementation on the oil fields. Indeed, the presence of polymers from at least two of the three families i) to iii) in a single composition or single pot without their separating into several distinct phases makes it possible to avoid the use of several injection lines for different additives on the oil fields and / or to have a single tank for mixing several additives before injection into the crude oil. For petroleum operators, the invention provides additives which allow them to avoid multiple point injections, tank agitation before injection as well as the management constraints of several "incompatible" products. The performances of the compositions of Examples 1 to 3 were evaluated by measuring the pour point according to standard ASTM D97 which consists in adding the crude oil brought to a temperature above its pour point, with a defined amount of additive, then cool the crude in 3 ° C increments, the pour point representing the temperature from which the crude oil no longer flows. In the examples below, a HERZOG MP852 device was used, the flow detection of which is ensured by an LCD camera. All the compositions were tested in an Egyptian crude oil whose pour point measured according to this method is 33 ° C.
Exemple 1 Dans un réacteur à double-paroi d'un demi litre équipé d'une agitation, d'un réfrigérant à reflux, d'un bain thermostaté à 75°C, 1- on introduit 75 g d'une solution comprenant 55 %__ en poids de copolymère d'acrylate d'alkyle en C18-22 et de 4-vinyl pyridine (5% en poids de 4-vinyl pyridine) dans un mélange de solvants aromatiques (SOLVESSO150) 2- on ajoute 75 g d'une solution comprenant 49% de copolymère d'éthylène et d'acétate de vinyle (28% acétate de vinyle) greffé avec un polyacrylate d'alkyle en Cι8-22 (le ratio polyacrylate d'alkyle greffé/copolymère d'éthylène et d'acétate de vinyle étant de 1) dans un mélange de solvants aromatiques (SOLVESSO150) 3- on chauffe à 75°C, 4- on introduit 20 g de tensioactif non-ionique (REMCOPAL 25 commercialisé par CECA qui est un alcool gras éthoxylé) 5- on attend 30 min pour l'homogénéisation du mélange réactionnel 6- on introduit en 2 h 23,1 g d'eau 7- on refroidit à 30°C et on vidange le réacteur. On obtient ainsi une émulsion contenant 40% de polymère et présentant une bonne stabilité c'est-à-dire qu'elle ne se sépare pas en plusieurs phases à 28°C et 50°C au bout d'une semaine. Exemple 2 (comparatif) Dans un réacteur à double-paroi d'un demi litre équipé d'une agitation, d'un réfrigérant à reflux, d'un bain thermostaté à 75°C, 1- on introduit 75 g d'une solution comprenant 55 % en poids de copolymère d'acrylate d'alkyle en C-I8-22 et de 4-vinyl pyridine (5% en poids de 4-vinyl pyridine) dans un mélange de solvants aromatiques (SOLVESSO150) 2- on ajoute 75 g d'une solution comprenant 49% de copolymère d'éthylène et d'acétate de vinyle (28% acétate de vinyle) greffé avec un polyacrylate d'alkyle en C18-22 (le ratio polyacrylate d'alkyle greffé/copolymère d'éthylène et d'acétate de vinyle étant de 1) dans un mélange de solvants aromatiques (SOLVESSO150), 3- on chauffe à 75°C, 4- on introduit 53,1 g de solvant aromatique (SOLVESSO 150) 5- on attend 30 min pour l'homogénéisation du mélange réactionnel 6- on refroidit à 30°C et on vidange le réacteur. La solution obtenue n'est pas stable : laissée au repos à 28°C ou à 50°C, elle se sépare au bout de 4 heures en deux phases distinctes rendant impossible la commercialisation et l'utilisation du mélange en pot unique pour l'additivation de fluides pétroliers.EXAMPLE 1 75 g of a solution comprising 55% are introduced into a half-liter double-walled reactor equipped with stirring, a reflux condenser, a bath thermostatically controlled at 75 ° C. __ by weight of copolymer of alkyl acrylate, C 18 to 22 and 4-vinyl pyridine (5% by weight of 4-vinyl pyridine) in a mixture of aromatic solvents (SOLVESSO150) 2 was added 75 g of a solution comprising 49% of ethylene and vinyl acetate (28% vinyl acetate) grafted with an alkyl polyacrylate Cι 8- 22 (the ratio of polyacrylate grafted alkyl / ethylene and vinyl acetate being 1) in a mixture of aromatic solvents (SOLVESSO150) 3- heating to 75 ° C, 4- introducing 20 g of nonionic surfactant (REMCOPAL 25 sold by CECA which is an ethoxylated fatty alcohol) 5- wait 30 min for the homogenization of the reaction mixture 6- introduce in 2 h 23.1 g of water 7- cool to 30 ° C and drain the re actor. An emulsion is thus obtained containing 40% of polymer and having good stability, that is to say that it does not separate into several phases at 28 ° C and 50 ° C after one week. Example 2 (comparative) 75 g of a solution are introduced into a double-walled half-liter reactor equipped with stirring, a reflux condenser, a bath thermostatically controlled at 75 ° C. comprising 55% by weight of copolymer of alkyl acrylate in CI 8 - 22 and of 4-vinyl pyridine (5% by weight of 4-vinyl pyridine) in a mixture of aromatic solvents (SOLVESSO150) 2- 75 g are added of a solution comprising 49% of copolymer of ethylene and vinyl acetate (28% vinyl acetate) grafted with a polyalkyl acrylate in C 18 - 22 (the ratio of grafted alkyl polyacrylate / copolymer of ethylene and vinyl acetate being 1) in a mixture of aromatic solvents (SOLVESSO150), 3- heating at 75 ° C, 4- introducing 53.1 g of aromatic solvent (SOLVESSO 150) 5- wait 30 min for the homogenization of the reaction mixture 6- cool to 30 ° C and drain the reactor. The solution obtained is not stable: left to stand at 28 ° C or 50 ° C, it separates after 4 hours into two distinct phases making it impossible to market and use the mixture in a single pot for additivation of petroleum fluids.
Exemple 3 Les compositions obtenues dans les exemples 1 et 2 sont injectées à hauteur de 1000 ppm dans une huile brute égyptienne ayant un point d'écoulement de 33°C. En ce qui concerne la solution de polymère de l'exemple 2, il est nécessaire de l'agiter pour homogénéisation avant l'additivation de l'huile ou bien de préparer séparément deux solutions contenant chacun des polymères et de procéder à une double injection. Les huiles brutes additivées ont un point d'écoulement de 9°C. On note que l'émulsion de l'exemple 1 selon l'invention présente l'avantage de pouvoir être injectée dans l'huile sans opération d'homogénéisation préalable ou de double injection. Example 3 The compositions obtained in examples 1 and 2 are injected at the level of 1000 ppm into an Egyptian crude oil having a pour point of 33 ° C. As regards the polymer solution of Example 2, it is necessary to stir it for homogenization before the additivation of the oil or else to prepare separately two solutions each containing the polymers and to carry out a double injection. Crude oils with additives have a pour point of 9 ° C. It should be noted that the emulsion of Example 1 according to the invention has the advantage of being able to be injected into the oil without prior homogenization operation or double injection.

Claims

REVENDICATIONS 1. Compositions de polymères selon l'invention comprenant des polymères issus d'au moins deux des trois familles : i)copolymères de l'éthylène et d'au moins un monomère à insaturation éthylénique, par exemple l'acétate de vinyle (EVA), ii) copolymères de l'éthylène tels que définis sous i) greffés avec des polymères des (co)polymères issus d'un ou plusieurs monomères de (méth)acrylate de n-alkyle, avec n variant de 6 à 40, de préférence de 14 à 30 et éventuellement d'un ou plusieurs monomères choisis parmi les alpha oléfines à chaîne grasse (n-alkyle, avec n variant de 6 à 40), les esters vinyliques, les vinyle aromatiques, les vinylpiridines et ses dérivés, la N-vinylpyrrolidone, les (méth)acrylamides et leurs dérivés, les acides ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés, et iii) (co)polymères de (méth)acrylate de n-alkyle et de monomères choisis parmi le groupe suivant : les alpha oléfines à chaîne grasse (n-alkyle, avec n variant de 6 àCLAIMS 1. Polymer compositions according to the invention comprising polymers from at least two of the three families: i) copolymers of ethylene and of at least one ethylenically unsaturated monomer, for example vinyl acetate (EVA) ), ii) ethylene copolymers as defined under i) grafted with polymers of (co) polymers derived from one or more n-alkyl (meth) acrylate monomers, with n varying from 6 to 40, preferably from 14 to 30 and optionally from one or more monomers chosen from fatty chain alpha olefins (n-alkyl, with n varying from 6 to 40), vinyl esters, vinyl aromatics, vinylpiridins and its derivatives, N-vinylpyrrolidone, (meth) acrylamides and their derivatives, ethylenically unsaturated mono- and / or dicarboxylic acids or anhydrides or ethylenically unsaturated mono- and / or dicarboxylic anhydrides, and iii) (co) polymers of n (meth) acrylate -alkyl and monomer res chosen from the following group: fatty chain alpha olefins (n-alkyl, with n varying from 6 to
40), les esters vinyliques, les vinyle aromatiques, les vinylpiridines et ses dérivés, la40), vinyl esters, aromatic vinyls, vinylpiridins and its derivatives,
N-vinylpyrrolidone, les (méth)acrylamides et leurs dérivés, les acides ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés ou anhydrides mono- et/ou dicarboxyliques éthyléniquement insaturés, caractérisées en ce qu'elles se présentent sous forme d'émulsion stable. 2. Compositions selon la revendication 1 caractérisées en ce que le monomère à insaturation éthylénique est choisi parmi les esters vinyliques de C2 à Cιβ et avantageusement deC2 à C5, les acides monocarboxyliques, les esters d'alkyle en Ci à Cι2 d'acides mono carboxyliques en C3 à C-ι2, les alpha et bêta de composés dicarboxyliques insaturés sous forme de diacide, de diester d'alkyle en Ci à C12, ou d'anhydride, de préférence parmi l'acétate de vinyle, les acrylates et méthacrylates en Ci à C12 et avantageusement de Ci à C5], les diesters de méthyle, éthyle ou propyle d'acide maléique, alkyle maléique, fumarique ou acide alkylfumarique. 3. Compositions selon la revendication 1 ou 2 caractérisées en ce qu'elles comprennent au moins 100 parties en poids des constituants 1 à 6 suivants : 1) 5 à 70 , de préférence 5 à 50 et avantageusement 5 à 40 parties en poids d'au moins deux (co)polymères appartenant à au moins deux des familles i) ii) et iii), 2) 0 à 60 parties en poids d'un solvant ou mélange de solvants non miscibles à l'eau, de préférence choisis parmi les solvants aromatiques (toluène, xylène), seuls ou en mélange, 3) 0 à 30 parties en poids d'un co-solvant ou d'un mélange de co-solvants miscible(s) à l'eau de préférence de 5 à 25, et avantageusement de 5 à 20 parties en poids, choisi parmi les cétones telles que la méthyléthylcétone ou methylisobutylcetone, les alcools tels que le butanol ou l'isopropanol, les glycols et éthers de polyglycol tels que l'éthylène ou le propylène glycol, le diéthylène glycol ou le dipropylène glycol , 4) 0,1 à 10, de préférence de 0,1 à 8 et avantageusement de 0,5 à 5 parties en poids d'un ou plusieurs tensioactifs ioniques et/ou non-ioniques et/ou colloïdes protecteurs et/ou polymères amphiphiles, 5) 0 à 2, de préférence de 0,01 à 0,6 et avantageusement de 0,02 à 0,2 parties en poids d'un ou plusieurs épaississants, 6) de l'eau (q s p 100: la somme des constituants 1) à 6) représentant 100 parties en poids) 4. Procédé de préparation des compositions telles que définies dans l'une quelconque des revendications 1 à 3, caractérisé en ce que soit A1- on prépare une solution de polymères d'au moins deux des familles i) à iii) dans au moins un solvant ou mélange de solvants organique(s) non miscible(s) à l'eau, A2- on ajoute à la solution obtenue un ou plusieurs tensioactifs purs ou dilués dans de l'eau ou dans un autre solvant (miscible ou non miscible avec l'eau), A3- on ajoute de l'eau pour former une émulsion, A4- on ajoute éventuellement un solvant ou mélange de solvants miscible(s) à l'eau, A5- on ajoute éventuellement un ou plusieurs tensioactifs et/ou un ou plusieurs, les phases A1 , A2, et A3 étant menées sous agitation, la phase A4 pouvant être menée en même temps ou avant la phase A3, la phase A5 pouvant être menée en même temps, avant ou après la phase A4, l'ajout d'eau pouvant se faire soit en mode continu, batch, semi-continu ou semi-batch, soit Aa1- on prépare une solution de polymères d'au moins deux des familles i) à iii) décrites ci-dessus dans au moins un solvant ou mélange de solvants organique(s) non miscible(s) à l'eau, Aa2- on ajoute dans l'eau un ou plusieurs tensioactifs purs ou dilués dans de l'eau ou dans un autre solvant (miscible ou non miscible avec l'eau), Aa3- on ajoute dans l'eau contenant le(s) tensioactif(s) préparée en Aa2) la solution de polymères préparée en Aa1) pour former une émulsion, Aa4- on ajoute éventuellement un solvant ou mélange de solvants miscible(s) à l'eau, Aa5- on ajoute éventuellement un ou plusieurs tensioactifs et/ou un ou plusieurs épaississants pour améliorer la stabilité de l'émulsion, les phases Aa1 , Aa2, et Aa3 étant menées sous agitation, la phase Aa4 pouvant être menée en même temps ou avant la phase A3, la phase Aa5 pouvant être menée en même temps, avant ou après la phase Aa4, l'ajout d'eau pouvant se faire soit en mode continu, batch, semi-continu ou semi-batch. 5. Procédé selon la revendication 4, caractérisé en ce que soit A1- on prépare une solution de 10 à 70 parties en poids de polymères d'au moins deux des familles i) à iii) dans 10 à 60 parties en poids d'au moins un solvant ou mélange de solvants organique(s) non miscible(s) à l'eau, A2- on ajoute à la solution obtenue 0,1 à 10 parties en poids de tensioactif(s) pur(s) ou dilué(s) , A3- on ajoute 10 à 80 parties en poids d'eau pour former une émulsion, A4- on ajoute éventuellement 0 à 30 parties en poids d'un solvant ou mélange de solvants miscible(s) à l'eau. A5- on ajoute éventuellement 0 à 3 parties en poids d'un ou plusieurs tensioactifs et/ou 0 à 2 parties en poids d'un ou plusieurs épaississant pour améliorer la stabilité de l'émulsion, soit Aa1- on prépare une solution de 10 à 70 parties en poids de polymères d'au moins deux des familles i) à iii) décrites ci-dessus dans 10 à 60 parties en poids d'au moins un solvant ou mélange de solvants organique(s) non miscible(s) à l'eau, Aa2- dans 10 à 80 parties en poids d'eau, on met 0,1 à 10 parties en poids de tensioactif(s) pur(s) ou dilué(s) dans de l'eau ou dans un autre solvant (miscible ou non miscible avec l'eau), Aa3- on ajoute dans l'eau contenant le(s) tensioactif(s) préparée en Aa2) la solution de polymères préparée en Aa1), Aa4- on ajoute éventuellement 0 à 30 parties en poids d'un solvant ou mélange de solvants miscible(s) à l'eau, Aa5- on ajoute éventuellement 0 à 3 parties en poids d'un ou plusieurs tensioactifs et/ou 0 à 2 parties en poids d'un ou plusieurs épaississants. 6. Procédé selon la revendication 4 ou 5 pour la préparation de compositions comprenant au moins un mélange de polymères i) et ii). 7. Procédé de préparation des compositions telles que définies dans l'une quelconque des revendications 1 à 3, caractérisé en ce que B1- on prépare séparément au moins deux émulsions de polymères appartenant uniquement à au moins deux des trois familles i), ii) ou iii) décrites ci- dessus (chaque émulsion obtenue contient donc uniquement des polymères appartenant à une seule famille i), ii), ou iii)) selon le procédé A ou Aa tel que défini dans l'une quelconque des revendications 4 à 6, ou, pour l'émulsion de polymère(s) issue de la famille iii), on peut également procéder par polymérisation radicalaire en émulsion, menée de manière classique dans un appareillage connu pour les polymérisations en émulsion selon un procédé batch, semi-batch ou continu ou semi- continu, ou pour les émulsions de polymères i) ne contenant pas de solvant non miscible à l'eau, on peut procéder par mise en émulsion au moyen d'une extrudeuse, B2- on mélange (par addition sous agitation d'une émulsion dans l'autre à une température qui ne soit supérieure au point de congélation des émulsions) les émulsions de polymères obtenues en B1), étant entendu que lesdites émulsions à mélanger doivent être issues d'au moins deux des familles i), ii) et iii). B3- on ajoute éventuellement sous agitation un ou plusieurs tensioactifs et/ou un ou plusieurs épaississants. 8. Utilisation des compositions telles que définies dans l'une quelconque des revendications 1 à 3 comme additifs pour abaisser pour l'abaissement de point d'écoulement des pétroles bruts et/ou l'inhibition de dépôt de paraffines dans les pétroles bruts. N-vinylpyrrolidone, (meth) acrylamides and their derivatives, ethylenically unsaturated mono- and / or dicarboxylic acids or anhydrides or ethylenically unsaturated mono- and / or dicarboxylic anhydrides, characterized in that they are in the form of a stable emulsion . 2. Compositions according to claim 1 characterized in that the ethylenically unsaturated monomer is chosen from vinyl esters from C 2 to Cιβ and advantageously from C 2 to C 5 , monocarboxylic acids, alkyl esters from C1 to Cι 2 d 'mono carboxylic acids C 3 to C-ι 2 , alpha and beta of unsaturated dicarboxylic compounds in the form of diacid, of C 1 -C 12 alkyl diester, or of anhydride, preferably from vinyl acetate , acrylates and methacrylates, C1 to C12 and advantageously from C1 to C 5] , methyl, ethyl or propyl diesters of maleic acid, maleic alkyl, fumaric or alkyl fumaric acid. 3. Compositions according to claim 1 or 2 characterized in that they comprise at least 100 parts by weight of the following constituents 1 to 6: 1) 5 to 70, preferably 5 to 50 and advantageously 5 to 40 parts by weight of at least two (co) polymers belonging to at least two of the families i) ii) and iii), 2) 0 to 60 parts in weight of a solvent or mixture of solvents immiscible with water, preferably chosen from aromatic solvents (toluene, xylene), alone or as a mixture, 3) 0 to 30 parts by weight of a co-solvent or d '' a mixture of co-solvents miscible with water, preferably from 5 to 25, and advantageously from 5 to 20 parts by weight, chosen from ketones such as methyl ethyl ketone or methyl isobutyl ketone, alcohols such as butanol or isopropanol, glycols and polyglycol ethers such as ethylene or propylene glycol, diethylene glycol or dipropylene glycol, 4) 0.1 to 10, preferably from 0.1 to 8 and advantageously from 0.5 5 parts by weight of one or more ionic and / or nonionic surfactants and / or protective colloids and / or amph polymers iphiles, 5) 0 to 2, preferably from 0.01 to 0.6 and advantageously from 0.02 to 0.2 parts by weight of one or more thickeners, 6) of water (qs 100: the sum constituents 1) to 6) representing 100 parts by weight) 4. Process for the preparation of the compositions as defined in any one of Claims 1 to 3, characterized in that either A1- a solution of polymers of at least is prepared at least two of families i) to iii) in at least one organic solvent or mixture of organic solvents immiscible with water, A2- one or more surfactants, pure or diluted in l, are added to the solution obtained water or in another solvent (miscible or immiscible with water), A3- water is added to form an emulsion, A4- optionally a solvent or mixture of solvents is miscible with water , A5- one or more surfactants and / or one or more are optionally added, the phases A1, A2 and A3 being carried out with stirring, the phase A4 possibly be conducted at the same time or before phase A3, phase A5 can be carried out at the same time, before or after phase A4, the addition of water can be done either in continuous, batch, semi-continuous or semi-batch mode, or Aa1- a solution of polymers from at least two of the families is prepared i) to iii) described above in at least one solvent or mixture of organic solvents immiscible with water, Aa2- one or more surfactants, pure or diluted in l, are added to the water water or in another solvent (miscible or immiscible with water), Aa3- is added to the water containing the surfactant (s) prepared in Aa2) the polymer solution prepared in Aa1) to form a emulsion, Aa4- optionally adding a solvent or mixture of solvents miscible with water, Aa5- optionally adding one or more surfactants and / or one or more thickeners to improve the stability of the emulsion, the phases Aa1 , Aa2, and Aa3 being carried out with stirring, phase Aa4 can be carried out at the same time or before phase A3, phase Aa5 p opening being carried out at the same time, before or after the Aa4 phase, the addition of water can be done either in continuous, batch, semi-continuous or semi-batch mode. 5. Method according to claim 4, characterized in that either A1- a solution of 10 to 70 parts by weight of polymers of at least two of families i) to iii) is prepared in 10 to 60 parts by weight of minus one solvent or mixture of organic solvents immiscible with water, A2- 0.1 to 10 parts by weight of pure or diluted surfactant (s) are added to the solution obtained ), A3- 10 to 80 parts by weight of water are added to form an emulsion, A4- optionally 0 to 30 parts by weight of a solvent or mixture of solvents miscible with water is added. A5- optionally 0 to 3 parts by weight of one or more surfactants and / or 0 to 2 parts by weight of one or more thickeners are added to improve the stability of the emulsion, or Aa1- a solution of 10 is prepared to 70 parts by weight of polymers from at least two of the families i) to iii) described above in 10 to 60 parts by weight of at least one solvent or mixture of organic solvents immiscible with the water, Aa2- in 10 to 80 parts by weight of water, 0.1 to 10 parts by weight of surfactant (s) pure or diluted in water or in another solvent (miscible or immiscible with water), Aa3- is added to the water containing the surfactant (s) prepared in Aa2) the polymer solution prepared in Aa1), Aa4- optionally 0 to 30 parts by weight d 'a solvent or mixture of solvents miscible with water, Aa5- optionally 0 to 3 parts by weight of one or more surfactants and / or 0 to 2 parts by weight of one or more thickeners are added. 6. Method according to claim 4 or 5 for the preparation of compositions comprising at least one mixture of polymers i) and ii). 7. Process for the preparation of the compositions as defined in any one of claims 1 to 3, characterized in that B1- at least two emulsions of polymers belonging only to at least two of the three families i), ii) are prepared separately or iii) described above (each emulsion obtained therefore contains only polymers belonging to a single family i), ii), or iii)) according to method A or Aa as defined in any one of claims 4 to 6 , or, for the emulsion of polymer (s) from family iii), it is also possible to proceed by radical emulsion polymerization, carried out conventionally in an apparatus known for emulsion polymerizations according to a batch, semi-batch process or continuous or semi-continuous, or for polymer emulsions i) containing no water-immiscible solvent, it can be carried out by emulsion using an extruder, B2- mixed (by addition with stirring of one emulsion in the other at a temperature which is not higher than the freezing point of the emulsions) the polymer emulsions obtained in B1), it being understood that said emulsions to be mixed must come from at least two of the families i), ii) and iii). B3- one or more surfactants and / or one or more thickeners are optionally added with stirring. 8. Use of the compositions as defined in any one of claims 1 to 3 as additives for lowering for the lowering of pour point of crude oils and / or the inhibition of paraffin deposition in crude oils.
EP04786266A 2003-08-28 2004-08-05 Stable emulsions which are used to lower the pour point of crude oils and to inhibit paraffin deposition Withdrawn EP1664156A1 (en)

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FR0310242A FR2859211B1 (en) 2003-08-28 2003-08-28 COMPOSITIONS IN THE FORM OF STABLE EMULSIONS, PREPARATIONS THEREOF AND THEIR USE FOR REDUCING THE FLOW POINT OF RAW OILS AND INHIBITING DEPOSITION OF PARAFFINS
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