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    • 专利摘要:
    The present invention relates to the use of at least one alkane-sulphonic acid of formula R-SO3H, where R represents a linear or branched, saturated hydrocarbon-based chain containing from 1 to 4 carbon atoms, for cleaning solid deposits comprising at least one salt of aconitic acid. The invention also relates to a method for cleaning solid deposits comprising at least one salt of aconitic acid, using at least one alkanesulfonic acid.
    公开号:FR3035403A1
    申请号:FR1553575
    申请日:2015-04-21
    公开日:2016-10-28
    发明作者:Jean-Alex Laffitte；Bernard Monguillon
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of sugar industries, and more particularly to the cleaning of installations, comprising reactors, evaporators, containers, valves, pipes, pipes and the like, used in the field of sugar industries. in the manufacture of sugar from natural plant materials, such as for example sugar cane or sugar beet.  During the preparation of sugar from plants, the sugar industry uses evaporators to concentrate the juice.  During these concentrations of deposits appear over time.  The accumulation of these deposits can cause disruptions in heat exchanges or even prevent some heat exchanges, which can lead to very significant economic consequences.  Also it is necessary to clean such deposits, when they become too large and they finally hinder the manufacturing yields.  These cleaning phases require manufacturing stops, and must therefore last as short as possible, while of course being as effective as possible.  Today, the cleaning of these deposits takes place most often chemically, with chelating agents, such as sodium salt of EDTA, as described for example in application WO2003 / 106735, or in the middle acid, for example using hydrochloric acid, but also sulfamic acid or sulfuric, as described for example in "Chemical cleaning of sugar mill evaporators", W. O. S.  Doherty, Proc.  Aust.  Soc.  Sugar Cane Technol. , (2000), 22, 341-346.  These deposits encountered in the sugar industry are generally made of a type of scale composed of various elements including salts, such as calcium carbonate, calcium oxalate, iron oxides, calcium phosphate, hydroxyapatite and aconitate, most often calcium and / or magnesium, as described in "Development of descriptor tools for the characterization of Australian sugar mill evaporator scale", D. W.  Rackemann et al. , Proc.  Int.  Soc.  Sugar Cane Technol. , (2010), 27, 1-12.  The problem encountered in the cleaning of this type of pie is the great difficulty of solubilizing aconitates, or salts of aconitic acid.  Aconitic acid is equivalent to dehydrated citric acid and is predominantly in trans form in cane and beet sugar.  Aconitic acid is found mainly in the form of tri-calcium salts and di-calcium and magnesium mixed salts, which are unavailable commercially.  However, even today, the literature hardly describes the problem related to the difficulty of solubilizing aconitates, an example being the elimination of these salts by washing with chelating agent solution such as EDTA salts. as previously indicated (cf.  W02003 / 106735 or "Development of descriptor tools for the characterization of Australian sugar mill evaporator scale", D. W.  Rackemann et al. , ibid. so that the person skilled in the art knows today only the effectiveness of EDTA salts for the removal of deposits in the sugar industry.  However, EDTA is today considered to be potentially hazardous to the environment, especially the aquatic environment, when it is used as a raw material for detergent products.  In addition, the biodegradability of EDTA is less than 10% (cf.  European Union Risk Assessment Report, edetic acid (EDTA), PL-1, 49, (2004)).  According to the work reported in "Chemical cleaning of sugar mill evaporators", 20 W. O. S.  Doherty, Proc.  Aust.  Soc.  Suger Cane Technol. (2000), 22, 341-346, it is learned, however, that dilute acids, such as sulfamic acid, hydrochloric acid and sulfuric acid, allow slow attack of the aconitic acid salts.  In spite of its effectiveness, hydrochloric acid (HCl) has numerous disadvantages, among which mention may be made of the release of toxic, nauseating, irritating and tear vapors, as well as the problems of effluents due to the large quantities chlorides released into the environment.  Moreover, because of its chemical nature, the concentration of HCl is limited to about 37%, whereas it could be advantageous, even desirable to have much higher acid concentrations to eliminate in particular all of the deposits that accumulate during the preparation of sugar.  Sulfuric acid is little used industrially, especially because of its corrosive nature.  Similarly, sulphamic acid, the releases of which are considered harmful to the environment, in particular for aquatic organisms, is not an acid that can be widely used on an industrial scale.  Still other acids could be used, such as, for example, phosphoric acid, the release of phosphates, however, a major problem for the environment.  Indeed, the use of phosphoric acid is today more than disputed, because of the releases of phosphates that it generates.  It has also been envisaged to use organic acids, such as, for example, acetic acid, citric acid, oxalic acid, glycolic acid, lactic acid, formic acid, etc.  However, their acidity being lower than the aforementioned mineral acids, their effectiveness is lower and requires the use of larger quantities of products.  In addition, some of the above acids are in solid form, which leads to handling difficulties and formulation (powdered powders), and therefore are not preferred acids for the use of the present invention .  In addition some of these organic acids are considered harmful.  This is particularly the case of oxalic acid and glycolic acid.  The work of D. W.  Rackemann et al.  (International Sugar Journal, (2008), 1/0, 344-349) teach that sodium hydroxide is ineffective in dissolving calcium salts. including calcium aconitate.  In addition, the washing with sodium hydroxide must be followed by an acid wash (phosphoric acid, formic acid, sulphamic acid, sulfuric acid, hydrochloric acid).  However, this process is inefficient because sodium hydroxide residues neutralize the acid and it is advisable to replace the acid with EDTA.  [0017] Thus, a suitable formulation appears to be a formulation containing 13% sodium hydroxide, 10% EDTA and 2% sodium gluconate.  EDTA, however, is not a product that can continue to be used, especially for the reasons mentioned above.  There remains therefore a need for products, formulations and processes making it possible to overcome the disadvantages previously listed, in particular a need for acids which make it possible to effectively remove the deposits observed in the installations used for the manufacture of sugar. , in particular from raw materials of plant origin and especially from sugar cane and sugar beet, and more generally in installations used for processes employing at least one step evaporation of water from a mixture comprising at least one salt of aconitic acid capable of depositing.  In particular, there remains a particular need for products, formulations and methods for rapidly and effectively solubilizing the salts of aconitic acid, and in particular the magnesium and / or calcium salts of aconitic acid, while preserving the environment, that is to say, products, formulations and processes that comply with environmental and labor standards in force, and that do not have the disadvantages associated in particular with gaseous releases irritants related to the use of hydrochloric acid, or related to corrosive effects, including sulfuric acid.  Thus, a first object of the present invention is to provide products and formulations effective for the dissolution of salts of aconitic acid in particular, and more generally cleaning processes of deposits encountered in manufacturing facilities. of sugar, especially in the sugar industries.  Another object of the present invention is to provide an effective alternative to acids commonly used in this application while avoiding discharges and effluents harmful to the environment, as well as toxic and nauseating gaseous releases.  Other objectives and advantages will become apparent from the description of the present invention which follows, invention that achieves the above objectives in whole or at least in part.  Indeed, the Applicant has now discovered that it is possible to effectively clean the solid deposits comprising at least one salt of aconitic acid, and this without the need to use EDTA, the salts of EDTA or the strong organic acids known from the prior art.  In the description of the invention which follows, the term "cleaning" is understood to mean the elimination and / or dissolution of deposits comprising at least one salt of aconitic acid, preferably a calcium salt and and / or magnesium, this elimination may be partial or total, preferably total, without the aforementioned drawbacks, in particular the disadvantages on the environment, the disadvantages related to gassing and other, as will be described now.  It has thus been discovered that it is possible to effectively clean solid deposits comprising at least one salt of aconitic acid and which are usually encountered in industries employing at least one evaporation step. water of a mixture comprising at least one salt of aconitic acid capable of depositing, using a formulation based on at least one alkanesulphonic acid.  The formulations based on at least one alkane-sulphonic acid have in particular an efficiency at least equal to or even improved with respect to the hydrochloric acid which is the acid usually used in this field, or even with respect to the salts. ethylenediaminetetraacetic acid (EDTA).  The alkanesulfonic acids have the advantage of being less corrosive than hydrochloric acid, of not generating chlorides, of being biodegradable and of not giving off toxic or foul-smelling products. and to be less polluting than phosphoric acid, because of the phosphates released into the environment.  In addition, the alkanesulphonic acids can be used in a more concentrated form than hydrochloric acid.  As already indicated, the use of the present invention finds quite interesting applications in industries employing at least one step of evaporation of water from a mixture comprising at least one acid salt. aconitic depositable, and in particular during the manufacture of sugar from natural plant materials, such as for example sugar cane or sugar beet.  Indeed, the formulations based on (s) alkane-sulfonic acid (s) have in particular greater ease of use and handling compared to the products and formulations usually used for cleaning solid deposits 25 comprising aconitic acid salts.  Indeed, the use of formulations based on alkane-sulfonic acid (s) produces no or few toxic, irritating or tear gas emissions.  Thus, and according to a first aspect, the present invention relates to the use of at least one alkane-sulphonic acid of formula R-S03H, where R represents a linear or branched saturated hydrocarbon chain containing from 1 to 4 carbon atoms, for cleaning solid deposits comprising at least one salt of aconitic acid.  As indicated previously, this type of solid deposition is usually encountered in industries employing at least one step of evaporation of water from a mixture comprising at least one aconitic acid salt capable of to deposit, and in particular during the manufacture of sugar from natural plant materials, such as for example sugar cane or sugar beet.  Thus, the invention relates to the use of at least one alkane-sulphonic acid as active compound for cleaning solid deposits comprising at least one aconitic acid salt, said solid deposits being usually encountered in industries with at least one step of evaporation of the water of a mixture comprising at least one salt of aconitic acid capable of depositing, and in particular during the production of sugar from natural plant materials, such as by sugar cane or sugar beet.  More particularly the invention relates to the use of at least one alkane-sulfonic acid for cleaning surfaces soiled by solid deposits comprising at least one aconitic acid salt, on all types of surfaces.  More specifically, the present invention provides a formulation, particularly suitable for replacing the use of hydrochloric acid, for cleaning deposits comprising at least one aconitic acid salt, or more simply "aconitates" in the As a result of the present disclosure, said formulation comprising at least one alkane-sulphonic acid which is a biodegradable, low-toxicity acid, which does not release little or no irritating or lachrymatory gases, does not generate effluents which are harmful to the environment and which can be used in more concentrated form than hydrochloric acid.  Aconitates, and in particular the aconitates encountered in the sugar industry, are well known to those skilled in the art and lead, especially after numerous cycles of evaporation of aqueous sugar solutions, to solid deposits, especially or less compact.  The aconitates encountered are mainly aconitates of calcium and / or magnesium, and may be present in solid deposits in combination with other salts.  Illustrative and non-limiting examples of other salts that may be present in the solid deposits include carbonates, such as calcium carbonate, phosphates, such as tricalcium phosphate, hydroxyapatite, oxalates, and the like. such as calcium oxalate, sulphates, such as calcium sulphate, iron oxides, and others.  The use of the present invention allows the cleaning of aconitates, and more generally deposits comprising at least one aconitate, and which may be present on all types of surfaces, in particular hard surfaces, especially metallic surfaces (iron, aluminum). , steels and others), of wood, polymers (plastics, paints, lacquers, varnishes), glasses, stones, ceramics, porcelains, terracotta, and others.  For the purposes of the present invention, "cleaning" is understood to mean cleaning, stripping, of all types of surfaces, as indicated above, soiled, coated, covered, in whole or in part by residues. , scales, deposits, whether dry or still wet, generated during the preparation of products obtained from plants and in particular from sugar cane or sugar beet, by elimination, dissolution, of said residues, scales and deposits in general.  As previously indicated, the term "cleaning" also encompasses the partial or total removal of solid deposits, comprising at least one aconitate, and which may have taken up in bulk, unexpectedly, undesirably or undesirably. in installations comprising reactors, evaporators, containers, valves, pipes, pipes and the like, used in the manufacture of sugar from natural plant materials, such as, for example, sugar cane or sugar beet, and which are usually removed / removed by other chemical and / or mechanical means, such as brushes, trowels, shovels, pickaxes, hammers, jackhammers and others.  In the present invention, the term "alkane-sulphonic acid" is understood to mean alkane-sulphonic acids of formula R-S03H, where R represents a linear or branched saturated hydrocarbon-based chain containing from 1 to 4 carbon atoms.  The alkane-sulphonic acids that can be used in the context of the present invention are preferably chosen from methanesulfonic acid, ethanesulphonic acid, n-propanesulphonic acid and isopropane sulphonic acid. n-butanesulfonic acid, isobutanesulfonic acid, sec-butanesulphonic acid, tert-butanesulphonic acid, and mixtures of two or more of them in all proportions.  According to a preferred embodiment, the alkane-sulphonic acid used in the context of the present invention is methanesulfonic acid or ethanesulphonic acid, very preferably the acid. used is methanesulfonic acid.  Thus, the use according to the present invention uses at least one alkane-sulphonic acid chosen from linear or branched chain alkane-sulphonic acids containing from 1 to 4 carbon atoms, and preferably from at least methanesulfonic acid (AMS).  Said at least one alkane-sulphonic acid that can be used in the context of the present invention may be used as such, or in combination with one or more other components, that is to say in formulation.  Any type of formulation comprising at least one alkanesulphonic acid may be suitable.  As a rule, the formulation comprises from 0.01% to 100% by weight of alkanesulfonic acid, more generally from 0.05% to 90% by weight, in particular from 0.5% to 75% by weight, inclusive limits, of alkane-sulfonic acid (s), relative to the total weight of said formulation.  The formulation is for example an aqueous, organic, or even hydro-organic formulation.  The formulation may be prepared as a concentrated mixture, wherein the concentrated mixture may be diluted by the end user.  Alternatively, the formulation may also be a ready-to-use formulation, i.e., it does not need to be diluted.  Finally, within the meaning of the present invention, the formulation may be a pure alkanesulfonic acid, or a mixture of pure alkanesulphonic acids, that is, the formulation may contain only one or more acidulphonic acid, without other formulation additives or other solvents or diluents.  The concentration of alkane-sulfonic acid (s) in the formulation depends on many factors, among which mention may be made of the quantity of deposits to be cleaned, the nature and the shape of the surface to be cleaned, the temperature to which the formulation is applied, and others.  Those skilled in the art will be able to adapt, without undue effort, the appropriate concentration of acid in the formulation.  Concentrated solutions, for example from 60% to 100%, preferably from approximately 70% to 100% by weight of alkane-sulphonic acid (s), are thus preferred, relative to the total weight of said formulation, when it is desired to remove large amounts of deposits, or on the surface of materials that are not very sensitive to acid attack.  Less concentrated solutions of from 0.01% to 60%, preferably from 0.05% to 50% are preferred for smaller amounts of deposits to be removed, or for cleaning of still wet deposits, and or on surfaces sensitive to acid attacks.  For example, it is possible to use methanesulphonic acid in aqueous solution sold by Arkema under the name Scaleva, or else under the name Lutropur marketed by the company B. AT. S. F. , ready for use or diluted with water in the proportions indicated above.  In addition to the alkane-sulfonic acid or acids, the formulation used in the present invention may optionally comprise one or more additives well known to those skilled in the art, such as those chosen from: solvents, hydrotropic agents or solubilizing agents ( for example alcohols, esters, ketones, amides, and others), biocides, disinfectants (bromoacetic acid, peracetic acid, hydrogen peroxide, and the like), rheological or texturizing agents or thickeners or gelling agents (sugars, polysaccharides, alginates, silica, amorphous silica, gums and others), - organic or inorganic acids (for example sulfuric, phosphoric, nitric, sulphamic, acetic, citric, formic, lactic, glycolic, oxalic and other), - alkali salts, d alkaline earth metals, in particular fluorides, chlorides, iodides, bromides of alkalis and / or alkaline earths, preferably chlorides and fluorides, more preferably fluorides, especially sodium or calcium fluorides, flame retardants, preservatives, anionic, cationic, nonionic or amphoteric surfactants (such as alcohols and / or ethoxylated amines, alkyl and / or aryl sulfonates); emulsifiers, detergents, soaps, and others; foaming agents, anti-foaming agents, anti-gels (for example ethylene glycol, propylene glycol, and others); dyes, corrosion inhibitors, perfumes, odorants, and other additives known to those skilled in the art.  The formulation in aqueous form is particularly advantageous in the so-called "cleaning in place" (or "cleaning in place" or "CIP" in English language) processes.  In addition, the use of alkane sulphonic acid (s), in particular of methane sulphonic acid, makes it possible to control the acid content, in order to be able to adjust the acidity of the solution as well as possible. cleaning agent for optimal cleaning of reactors, pipes, evaporators. . . .  This control of the acid content can be carried out according to any method known per se, and for example by conductivity.  According to one variant, the formulation is a formulation in the form of a gel.  It has indeed been observed that the formulations in the form of alkane-sulfonic acid (s) gel (s) are very effective for the removal of deposits comprising aconitates, as described above, not only because of the gel itself which allows a longer action of the active ingredient acid (the gel "adheres" longer on the surfaces, compared to an aqueous formulation), but also has an improved cleaning power, compared to other formulations- gels.  Thus, according to another aspect, the present invention relates to the use of a formulation in gel form comprising: from 0.01% to 97% by weight, preferably from 0.05% to 75% by weight; weight and more particularly from 0.5% to 70% by weight of at least one alkanesulfonic acid, preferably methanesulfonic acid; from 0.1% to 30% by weight, preferably from 0.5% to 15% by weight and more particularly from 1% to 10% by weight, of at least one gelling agent; from 0.1% to 30% by weight, preferably from 0.5% to 15% by weight, of at least one additive chosen from those mentioned above; and the 100% complement of water and / or organic solvent, for cleaning solid deposits comprising at least one aconitic acid salt.  The gelling agents and the surfactants that can be used in the formulations in the form of a gel can be of any type.  Those skilled in the art will know, without particular difficulty and drawing inspiration from the examples which follow, to choose and adapt the nature of the gelling agents and the appropriate surfactants.  According to another aspect, the present invention relates to the use of a formulation in the form of a foaming gel.  Foaming gels are in fact of particular interest because they produce a sticky foam, that is, a foam adhering to soiled surfaces, while generally requiring a lower consumption of cleaning acid active ingredient, advantage of being rinsed quite effectively, that is to say to be able to be removed in a simpler and more efficient way, while requiring a smaller amount of water.  Thus, the present invention also relates to the use of a formulation in the form of a foaming gel comprising: from 0.01% to 97% by weight, preferably from 0.05% to 75% by weight and more Especially from 0.5% to 70% by weight of at least one alkanesulfonic acid, preferably methanesulfonic acid; from 0.1% to 30% by weight, preferably from 0.5% to 15% by weight and more particularly from 1% to 10% by weight, of at least one foaming agent; from 0 to 30% by weight, preferably from 0.5 to 15% by weight, and more preferably from 1 to 10% by weight, of at least one gelling agent; from 0 to 30% by weight, preferably from 0.5% to 15% by weight, of at least one additive chosen from those mentioned above, preferably from 0 to 10% by weight, preferably from 0.1 to 5% by weight, of a solubilizing or hydrotropic agent, and 0 to 20% by weight, preferably 0.5 to 10% by weight, of at least one surfactant; and the 100% complement of water and / or organic solvent for cleaning solid deposits comprising at least one aconitic acid salt.  Depending on the field and the method of application, the formulation may be prepared as a concentrate, and then diluted before use until the expected efficiency, as for the viscosity and the foaming power.  In the foaming gel formulation above, the foaming agent may be selected from foaming agents commonly used by those skilled in the art, and preferably from amine oxides, for example: dimethylalkylamine oxides, the alkyl chain being a "fatty" chain, for example containing from 10 to 30 carbon atoms, preferably from 12 to 22 carbon atoms; ethoxylated amine oxides; and - mixtures of two or more of them.  The use of at least one ethoxylated amine oxide, such as, without limitation, Cecajel ° 0X100 from CECA, or Aromoe T12 from Akzo alone or combination with at least one dimethylalkylamine oxide provides stability to the foaming gel.  Foaming agents, and in particular those described above, generally form gels when mixed with water, i.e., they increase the viscosity of the formulation, it is necessary to add a gelling agent.  However, the addition of such a gelling agent is not excluded from the present invention.  Among the solubilizing or hydrotropic agents that can be used in the formulations 10 according to the invention, mention may be made, by way of example and in a nonlimiting manner, of sodium xylene- or cumene-sulfonates.  Such agents are however not essential in the acidic formulations according to the invention.  An aqueous, organic or hydro-organic formulation, in the form of a solution, a gel or in the form of a foaming gel, which is particularly preferred, is a formulation comprising from 0.01% to 95%, preferably 0.05%. % to 75%, more preferably 0.5% to 50% by weight of methanesulfonic acid.  The formulations used according to the present invention, whether in liquid form, gels or foaming gels, concentrated or diluted, may be applied according to any method known to those skilled in the art, and in particular under pressure. , or using a spray gun.  The concentration of alkane-sulfonic acid (s) can thus vary in very large proportions, depending on the nature and quantity of the residues to be removed, but also depending on the nature of the surfaces to be cleaned.  The invention also relates to a solid deposit cleaning process comprising at least one salt of aconitic acid, which deposit of aconitate can be encountered in all types of industries employing at least one step of evaporation of water from a mixture comprising at least one salt of aconitic acid capable of depositing, and in particular in the sugar-making industries from natural plant materials, such as, for example, sugar cane or sugar cane; sugar beet.  The present invention relates to a cleaning method (i. e.  solubilization and / or elimination), at least partial and preferably total solid deposition comprising at least one aconitic acid salt, whether in wet or dried form, for example taken in bulk, and present on all types of surfaces, particularly hard surfaces, especially metal (iron, aluminum, steel and others), wood, polymers (plastics, paints, lacquers, varnishes), glasses, stones, ceramics, porcelains, terracotta, and others.  Thus, the present invention relates to a process for removing deposits comprising at least one aconitic acid salt, as defined above, present for example on all types of surfaces, as indicated above, soiled, coated, covered in whole or in part by residues, scales, deposits, dry or still wet, generated during the preparation of products obtained from plants and in particular from sugar cane or sugar beet.  More particularly, the process of the present invention comprises at least one step of contacting an effective amount of at least one alkanesulfonic acid, as defined above, preferably methanesulfonic acid, in the form of of aqueous, organic or hydro-organic formulation, in the form of a solution, gel or foaming gel, as just described, with a solid deposit comprising at least aconitic acid to be removed, by contact, immersion spraying, spraying, application of a more or less thick layer, possibly using appropriate tools known to those skilled in the art (brushes, brushes, spatulas, and the like), said contacting step being optionally followed by one or more rinsing and / or drying steps.  The temperature at which the process is carried out, and in particular the contacting step, may vary in large proportions and is generally between -20 ° C. and + 150 ° C., preferably between 0 ° C. and 80 ° C, more preferably between 10 ° C and 80 ° C.  According to a preferred embodiment, the use temperature is the ambient temperature or a temperature between room temperature and about 80 ° C.  It may thus be envisaged to heat the alkane-sulphonic acid and the surface to be treated, this temperature may be identical or different, or to bring to temperature either the alkane-sulphonic acid or the surface. treat.  It is thus possible to treat surfaces soiled with solid deposits at ambient temperature (for example 10 ° C.) with the aid of an alkane-sulfonic acid (s) formulation (s). ) raised to 70 ° C, or treat surfaces soiled by solid deposits at a high temperature (for example about 100 ° C) using a formulation of alkane-sulfonic acid (s) to room temperature (eg 20 ° C).  It may also be envisaged to completely immerse the surfaces to be treated in a formulation of alkane-sulfonic acid (s), for example at a temperature of about 60.degree. C., for example to remove solid deposits present. in valves, pipes, and others.  In the process of the invention, it should be understood that it is possible to use at least one alkane-sulfonic acid or any formulation comprising at least one alkane sulfonic acid, as described above.  Finally, after the treatment step (s), by contacting, and optionally rinsing (s), the cleaned surface can be, if necessary and if necessary, dried, according to any known method those skilled in the art, for example in air, under a current of air more or less hot, in an oven, by heating (electric, heat lamps), wiping (paper or absorbent textiles), and others.  As indicated above, the alkanesulphonic acid is advantageously used in the form of a formulation, for example an aqueous, organic or hydro-organic formulation, in liquid form, as a gel or as a foaming gel, as defined above. .  In the process of the invention as described above, the term "effective amount" is understood to mean an amount allowing the cleaning of residues, scales, and in general of solid deposits comprising at least one acid salt. aconitic.  This amount may vary in large proportions, depending on the surfaces to be treated and the amount of solid deposits, the temperature and pressure of the formulation used, the desired duration of the cleaning process, and the like.  Thus, the amount of acid will advantageously be established to allow a complete cleaning, or as complete as possible, solid deposits of aconitates, while using a minimum amount of acid (s), mainly for economic reasons .  This cleaning operation of the solid deposits of aconitates can be repeated one or more times according to the quantity and the nature of the solid deposits, and their degree of incrustation on the surfaces to be treated.  The contacting of an effective amount of at least one alkanesulfonic acid is followed by a reaction time necessary for the dissolution of the solid deposits which it is desired to eliminate, this reaction time being able to vary from a few seconds to a few hours, or even a few days, depending on the temperature at which the cleaning is carried out, the application pressure of the alkane-sulfonic acid (s), the nature of the formulation comprising said less an alkane-sulfonic acid, the amount of deposits to eliminate, their degree of encrustation, and the nature of the surfaces to be treated.  The treatment with at least one alkane-sulphonic acid as defined above may optionally be accompanied and / or preceded, and / or followed by one or more washes, and preferably preceded by or several prewashes, if necessary, using a basic formulation comprising at least one mineral or organic base, preferably a mineral base, for example an alkali or alkaline earth metal hydroxide, for example hydroxide hydroxide. sodium, in all concentrations.  These basic washes are most preferably carried out before, or after, or before and after, but preferably not simultaneously with cleaning with said at least one alkane sulfonic acid, in order to avoid acid neutralization reactions. / base that could affect the quality of the cleaning sought.  The treatment with at least one alkane-sulphonic acid as defined above may optionally be accompanied and / or followed by one or more mechanical operations (stirring, scraping, brushing, and the like), in order to to improve the acidic chemical action, if necessary.  As indicated above, the treatment may be followed by one or more rinsing operations, for example with clear water, solvent (s) or mixture (s) water / solvent (s).  In the process of the invention as just described, the term "effective amount" means an amount allowing the dissolution and elimination of all or part of dirt, residue, scales, dry or not. solid deposits comprising at least one aconitic acid salt.  This amount can vary in large proportions, depending on the surfaces to be treated and the amount of solid deposits, the temperature, the pressure of the formulation used, the nature of the formulation used, the the desired duration of the removal process and others.  Thus, the amount of acid will advantageously be adjusted to allow a total or at least partial elimination, preferably total, of residues, scales, dried or not, of said solid deposits of aconitates, while observing a minimum amount. acid (s), mainly for economic reasons.  The alkane-sulphonic acids, in particular methanesulfonic acid, have proved effective for cleaning the solid deposits of aconitates, and especially the solid deposits encountered in the sugar preparation industry, in particular from sugar cane or sugar beet, without generating irritating and tear gas emissions.  Furthermore, the use of at least one alkane-sulfonic acid according to the present invention has the advantage of generating little or no corrosion, especially when cleaning metal surfaces (many in particular in 15 sugar industries), which is frequently observed on said metal surfaces when using more or less concentrated solutions of acids.  The alkane-sulphonic acids can also be used at high concentrations, in order to increase their effectiveness, which concentrations can be 50%, 70% or even 100% by weight, while the maximum concentration of hydrochloric acid can not be more than 37%, due to the intrinsic chemical nature of this acid.  In addition, the alkane-sulphonic acids used in the present invention have, compared with arylsulfonic acids, the advantage of generating a lower chemical oxygen demand (COD) at the effluent treatment stations, and consequently allow a higher concentration of organic discharges in these stations.  The formulations which can be used in the context of the present invention may contain phosphorus compounds, such as, for example, phosphates, originating, for example, from phosphoric acid, but in small proportions, for example less than 10% by weight. preferably less than 5% by weight, more preferably less than 1% by weight, relative to the total weight of the formulation, always with the aim of minimizing as much as possible the releases harmful to the environment.  In addition, the formulations that may be used in the context of the present invention may contain sulfur-containing compounds, such as for example sulphates, originating, for example, from sulfuric acid, but in small proportions, for example lower, 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, relative to the total weight of the formulation.  The formulations that may be used in the context of the present invention may contain chlorinated compounds, such as, for example, chlorides, originating, for example, from hydrochloric acid, but in small proportions, for example less than 10% by weight, of Preferably less than 5% by weight, more preferably less than 1% by weight, based on the total weight of the formulation.  The formulations that may be used in the context of the present invention may contain nitrogen compounds, such as, for example, nitrates, originating for example from nitric acid, but in small proportions, for example less than 10% by weight, of Preferably less than 5% by weight, more preferably less than 1% by weight, based on the total weight of the formulation.  The present invention described above shows that it is possible to remove solid deposits of aconitates on all types of surfaces, such as, and without limitation, metal surfaces (iron, steel, copper, alloys). and others), concretes, cements, tiles, porcelain, wood, paper, cardboard, textiles, polymers (plastics, varnishes, paints, lacquers), glasses, and others.  The present invention also shows that it is possible to clean the said surfaces of residues, dried or not, undesirable, but also to eliminate solid deposits that may have accumulated in various containers, evaporators, ducts, valves, and others, which are usually removed by acids which are poor in respect of the environment and / or which are corrosive to the surfaces to be treated.  Thus, the alkane-sulphonic acids can advantageously be used as a replacement for the acids that are commonly known and used by those skilled in the art for the removal of solid deposits of aconitates, in a large number of fields of application, among which include, but are not limited to, the sugar industries.  It should be understood that the use according to the present invention not only allows the cleaning of solid deposits of aconitates, but also and concomitantly, the cleaning of other type (s) soil that may be present on the surfaces to be treated, due to the acidic nature of the alkane-sulphonic acids used.  For example, the alkane sulphonic acids used in the context of the present invention may prove effective in cleaning any type of soil, such as rust, scale, but also any type of organic soiling inherent in the manufacture of, inter alia, sugar from plants as indicated previously.  The present invention is now illustrated by means of the examples which follow, without being limiting in nature, and which can not therefore be understood as being capable of restricting the scope of the invention as claimed.  To assess the effectiveness of the alkanesulphonic acids in the cleaning of deposits comprising salts of aconitic acid, a calcium salt of aconitic acid is first prepared and then dissolution tests are carried out.
    [0002] Example 1 Preparation of tricalcium aconitate trihydrate: Ca3 (C6H306) 2 - 3H20 [0099] This preparation is described in the thesis of Niconor Niconey Reece, University of Louisiana; December 2003, "Optimizing aconitate removal during clarification". In a quadricol of 500 mL provided with a magnetic bar, a water cooler, a temperature probe and a pH probe, 8 g of aconitic transacid (0.0457 moles, molecular weight = 174.). It is then added to 133 g with ultrapure water. The solution is then neutralized with 0.2M potassium hydroxide (NaOH) to pH 11.3, then the pH is adjusted to 6 with 1N hydrochloric acid (HCl) solution. The solution is then heated to 85 ° C., and then 228.5 ml of a 0.3M calcium chloride solution whose pH has been adjusted beforehand to 6 with 1N HCl is added. [0102] The reaction medium is heated for 3 hours at 85 ° C. and a precipitate then appears, the medium is then filtered while hot. 10.6 g of a solid which is washed 3 times with 30 ml of hot water are recovered. After drying in a 50 mbar vacuum oven for 48 hours at room temperature, 7.4 g of a white solid are obtained, which is characterized by analyzes of its carbon, hydrogen and carbon content. calcium, and which comply with the formula Ca3 (C6H306) 2 - 3 (H20).
    [0003] Measurement of the solubility of the tricalcium aconitate trihydrate [0104] In a 50 ml three-necked flask equipped with a magnetic stirrer, a condenser and a temperature probe, 30 g of aqueous 1-acid solution are introduced. M. The salt prepared as indicated above (tricalcium aconitate trihydrate) is then added in portions of about 0.1 g, until undissolved crystals appear (saturation of the medium). The percentage of dissolved salt is calculated according to the following formula:% dissolved salt = m / (M + m) where M represents the mass of acid solution, and m represents the mass of salt introduced. Table 1 below summarizes the dissolution results of tricalcium aconitate trihydrate at 20 ° C. Table 1 - acid tested% by weight of tricalcium aconitate trihydrate dissolved at room temperature (20 ° C) methanesulfonic acid 12.1% hydrochloric acid 12.1% sulfamic acid 11.9% sulfuric acid "2.2 % [0107] Sulfuric acid is very poorly effective with respect to the solubility of the aconitic acid salts. Methane sulfonic acid surprisingly has an efficiency comparable to that of hydrochloric acid and slightly higher than that of sulfamic acid. However, methanesulfonic acid is much less corrosive than hydrochloric acid, whose vapors are irritating and toxic to the user. In addition, methanesulfonic acid is biodegradable. Finally, sulphamic acid, whose discharges are also considered harmful to the environment, in particular for aquatic organisms, is not an acid that can be widely used on an industrial scale.
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. Use of at least one alkane-sulphonic acid of formula R-S03H, in which R represents a linear or branched, saturated hydrocarbon-based chain containing from 1 to 4 carbon atoms, for cleaning solid deposits comprising at least one salt of aconitic acid.
    [0002]
    2. Use according to claim 1, wherein the alkanesulfonic acid is selected from methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, isopropane sulfonic acid, n-butanesulfonic acid, isobutanesulfonic acid, sec-butanesulphonic acid, tert-butanesulphonic acid, and mixtures of two or more of them in all proportions.
    [0003]
    3. Use according to claim 1 or claim 2, wherein the alkanesulfonic acid is methanesulfonic acid or ethanesulfonic acid, preferably methanesulfonic acid.
    [0004]
    4. Use according to any one of the preceding claims, wherein said at least one alkanesulfonic acid is used in form of formulation, the amount of alkane-sulfonic acid (s) being from 0.01% to 100%, more generally from 0.05% to 90%, in particular from 0.5% to 75%, by weight, limits included, relative to the total weight of said formulation.
    [0005]
    5. Use according to any one of the preceding claims, wherein said at least one alkanesulfonic acid is present in an aqueous, organic, or hydro-organic, concentrated, ready-to-use or dilute formulation before use. 3035403 3035403 21- -21-
    [0006]
    6. Use according to any preceding claim, wherein at least one alkanesulfonic acid is used in combination with one or more additives selected from: - solvents, hydrotropic agents or solubilizers or gelling agents (eg alcohols, esters, ketones, amides, and others), - biocides, disinfectants (bromoacetic acid, peracetic acid, hydrogen peroxide, and others), - rheological or texturizing agents or thickeners (sugars, polysaccharides, alginates, silica, amorphous silica, gums and other), 10 - organic or inorganic acids (eg sulfuric, phosphoric, nitric, sulfamic, acetic, citric, formic, lactic, glycolic, oxalic and others), - flame retardants, - preservatives, - anionic surfactants, cationic nonionic or amphoteric (such as ethoxylated alcohols and / or amines, alkyl- and / or aryl-sulfonates), emulsifiers, detergents, soaps, and the like; foaming agents, anti-foaming agents, anti-gels (for example ethylene glycol, propylene glycol, and others); corrosion inhibitors, dyes, perfumes, odorants, and other additives known to those skilled in the art.
    [0007]
    7. Use according to any one of the preceding claims, wherein at least one alkanesulphonic acid is used in liquid formulation, gel or foaming gel.
    [0008]
    8. A method for cleaning solid deposits comprising at least one salt of aconitic acid, comprising at least one step of contacting an effective amount of at least one alkanesulphonic acid of formula R-S03H, where R represents a linear or branched, saturated hydrocarbon-based chain containing from 1 to 4 carbon atoms, preferably methanesulfonic acid, with said solid deposits to be removed by contact, immersion, spraying; spraying, applying a more or less thick layer, possibly using appropriate tools known to those skilled in the art (brushes, brushes, spatulas, and others), said contacting step possibly being followed by one or more rinsing and / or drying steps. 5
    [0009]
    9. Process according to claim 8, characterized in that it is carried out at a temperature of between -20 ° C and + 150 ° C, preferably between 0 ° C and 80 ° C, more preferably between 10 ° C and 80 ° C, preferably at room temperature or at a temperature between room temperature and about 80 ° C. 10
    [0010]
    10. Use according to any one of claims 1 to 7, for cleaning solid deposits comprising at least one salt of aconitic acid, on all types of surfaces, in particular metal surfaces, concretes, cements, tiles, tile , stone, porcelain, wood, paper, cardboard, textiles, polymers (plastics, varnishes, paints, lacquers), glasses, and others.
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    同族专利:
    公开号 | 公开日
    HRP20191362T1|2019-11-01|
    CA2983047C|2019-10-08|
    MX2017013143A|2018-02-21|
    EP3286354A1|2018-02-28|
    US20180093305A1|2018-04-05|
    CA2983047A1|2016-10-27|
    CN107438659A|2017-12-05|
    AU2016252084B2|2019-08-29|
    EP3286354B1|2019-05-22|
    DK3286354T3|2019-08-05|
    FR3035403B1|2017-05-19|
    CN107438659B|2020-08-14|
    RU2695848C2|2019-07-29|
    RU2017134350A3|2019-04-04|
    AR104324A1|2017-07-12|
    BR112017022480A2|2018-07-10|
    RU2017134350A|2019-04-04|
    WO2016170245A1|2016-10-27|
    PL3286354T3|2020-01-31|
    AU2016252084A1|2017-11-16|
    ES2738698T3|2020-01-24|
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    FR2923735A1|2007-11-15|2009-05-22|Arkema France|PROCESS FOR ACID CLEANING IN THE BRASSICOLE INDUSTRY|
    US20090288683A1|2008-05-21|2009-11-26|Ecolab Inc.|Alkaline peroxygen food soil cleaner|
    EP2336282B1|2009-12-17|2014-07-30|The Procter and Gamble Company|Liquid acidic hard surface cleaning composition|
    ES2819029T3|2010-01-12|2021-04-14|Arkema Inc|Hydrogen Peroxide Compositions and Their Uses|
    FR2961803B1|2010-06-29|2013-02-22|Arkema France|ACID COMPOSITIONS FOR THE REMOVAL OF OXALATES|CN108130194A|2017-12-26|2018-06-08|郑州佰沃生物质材料有限公司|A kind of stainless steel hot press formwork cleanser|
    WO2020126855A1|2018-12-21|2020-06-25|Basf Se|Mixture comprising methanesulfonic acid and sulfuric acid|
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    法律状态:
    2016-03-09| PLFP| Fee payment|Year of fee payment: 2 |
    2016-10-28| PLSC| Search report ready|Effective date: 20161028 |
    2017-03-13| PLFP| Fee payment|Year of fee payment: 3 |
    2018-03-15| PLFP| Fee payment|Year of fee payment: 4 |
    2020-03-12| PLFP| Fee payment|Year of fee payment: 6 |
    2021-03-10| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1553575A|FR3035403B1|2015-04-21|2015-04-21|USE OF ALKANE SULFONIC ACID FOR CLEANING IN SUGAR INDUSTRIES|FR1553575A| FR3035403B1|2015-04-21|2015-04-21|USE OF ALKANE SULFONIC ACID FOR CLEANING IN SUGAR INDUSTRIES|
    BR112017022480-1A| BR112017022480A2|2015-04-21|2016-04-08|use of alkanesulfonic acid for cleaning in the sugar industry|
    US15/567,385| US20180093305A1|2015-04-21|2016-04-08|Use of alkane sulfonic acid for cleaning in the sugar industries|
    CN201680023090.3A| CN107438659B|2015-04-21|2016-04-08|Use of alkanesulfonic acids for cleaning in the sugar industry|
    PL16733125T| PL3286354T3|2015-04-21|2016-04-08|Use of alkane sulfonic acid for cleaning in the sugar industries|
    RU2017134350A| RU2695848C2|2015-04-21|2016-04-08|Use of alkanesulphonic acid for cleaning in sugar industry|
    PCT/FR2016/050812| WO2016170245A1|2015-04-21|2016-04-08|Use of alkane sulfonic acid for cleaning in the sugar industries|
    CA2983047A| CA2983047C|2015-04-21|2016-04-08|Use of alkane sulfonic acid for cleaning in the sugar industries|
    DK16733125.5T| DK3286354T3|2015-04-21|2016-04-08|APPLICATION OF ALKANSULPHONIC ACID FOR CLEANING IN THE SUGAR INDUSTRY|
    EP16733125.5A| EP3286354B1|2015-04-21|2016-04-08|Use of alkane sulfonic acid for cleaning in the sugar industries|
    AU2016252084A| AU2016252084B2|2015-04-21|2016-04-08|Use of alkane sulfonic acid for cleaning in the sugar industries|
    ES16733125T| ES2738698T3|2015-04-21|2016-04-08|Use of alkanesulfonic acid for cleaning in the sugar industries|
    MX2017013143A| MX2017013143A|2015-04-21|2016-04-08|Use of alkane sulfonic acid for cleaning in the sugar industries.|
    ARP160101078A| AR104324A1|2015-04-21|2016-04-20|USE OF ALCANOSULPHONIC ACID FOR CLEANING IN THE SUGAR INDUSTRIES|
    HRP20191362| HRP20191362T1|2015-04-21|2019-07-29|Use of alkane sulfonic acid for cleaning in the sugar industries|
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