EP2922945B1 - Kontinuierliches verfahren zur herstellung von flüssigen wasch- oder reinigungsmitteln - Google Patents

Kontinuierliches verfahren zur herstellung von flüssigen wasch- oder reinigungsmitteln Download PDF

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Publication number
EP2922945B1
EP2922945B1 EP13788766.7A EP13788766A EP2922945B1 EP 2922945 B1 EP2922945 B1 EP 2922945B1 EP 13788766 A EP13788766 A EP 13788766A EP 2922945 B1 EP2922945 B1 EP 2922945B1
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EP
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Prior art keywords
agent
acid
mixer
cleaning
dynamic
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EP13788766.7A
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German (de)
English (en)
French (fr)
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EP2922945A1 (de
Inventor
Thomas Holderbaum
Bernd Richter
Berthold Schreck
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL13788766T priority Critical patent/PL2922945T3/pl
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising

Definitions

  • the present invention relates to a continuous process for the preparation of liquid detergents using a special device.
  • the anionic surfactants are predominantly provided as the corresponding acid precursor compounds (acid precursors) and produced in the process by neutralization of the precursor.
  • acid precursors of certain anionic surfactants for example, linear alkyl benzene sulfonates
  • the anionic surfactants are formed in these cases in the preparation of detergents or cleaners by neutralization with a suitable neutralizing agent.
  • the reaction is usually carried out in a non-continuous or so-called “batch process", usually in a mixer, in which the starting materials are introduced and the intermediate or end product is removed after a certain reaction time.
  • the "batch process” has a number of disadvantages. On the one hand, the required long times lead to increased production costs. Furthermore, there is the risk of contamination, which are registered by the fact that the corresponding systems for the "batch process" must always be emptied and filled. Also undesirable is that often larger amounts of air are entered into the system, resulting in turbidity.
  • loop reactors which circulate a large portion of the reaction mixture and wherein only a small portion of the mixture is discharged.
  • These are lines that lead the reaction mixture in a circle, with possibly one or more liquid mixers and various inlets and outlets are interposed.
  • the disadvantage of such loop reactors is that they require very large volumes and powerful pumps and the backmixing effect is often unsatisfactory.
  • the object of the present invention was therefore to provide continuous processes for the preparation of detergents or cleaners which are improved over the processes used hitherto and, in particular, can also be used for the neutralization of acid precursors of anionic surfactants.
  • a continuous process for the preparation of a liquid detergent or cleaning agent which process comprises the mixing of continuous separate volume flows of at least two liquid detergent or cleaning agent components and is characterized in that a dynamic loop mixer is used as the reaction volume in the process and that the at least two liquid detergent or cleaning agent components react chemically with one another, in particular via a neutralization reaction.
  • the reaction volume preferably has a size of from 50 to 1000 L, in particular from 100 to 400 L.
  • the reaction volume is preferably closed to the atmosphere, which has as an advantage an improvement in hygiene, a lower air intake into the product and the fact that only one pump is necessary for passage through a closed to the atmosphere reaction volume, while filling and emptying, for example of an unlocked tank two pumps are needed.
  • the dynamic loop mixer used is preferably a closed loop in-line mixer, characterized in that it comprises a cylindrical housing with an inlet and an outlet for the volume flows to be mixed, wherein in the housing a cylindrical guide tube with internal Conveyor is arranged such that between this and the housing a ring-cylindrical outer space and in the housing with the guide tube a mixing loop is formed, wherein the mixing of the product is effected in that the conveyed by the inner conveyor volume is a multiple of that fed through the inlet Volume is and so a forced circulation outside the guide tube against the conveying direction within the guide tube is formed.
  • the guide tube in the outlet region on an end face and at least one radial opening to the annular cylindrical outer space, wherein in the interior of the guide tube, a rotating displacer, in particular a screw conveyor, preferably a multi-start screw conveyor, for transporting the volume flow to the radial Opening is arranged.
  • a rotating displacer in particular a screw conveyor, preferably a multi-start screw conveyor
  • guide structures can be provided for guiding part of the volume flows from the annular-cylindrical outer space to the outlet.
  • the dynamic loop mixer can have in the region of the radial opening a rotating tool such as a rotor and optionally also a stator, the rotor having in different embodiments at least one axially extending wall section. With the help of such rotors / stators foaming or emulsifying tasks can be performed in addition to pure mixing operation.
  • Such dynamic loop mixers are also known as Burdosa loop mixers and are used, for example, as dmt loop mixers (for example MD series) from BIS E.M.S. GmbH (Buseck, Germany). These mixers allow a very variable adaptation of the process parameters to the requirements. So can be emulsified or foamed in addition to pure mixer operation.
  • the invention relates to the use of a dynamic loop mixer in the manufacture of liquid detergents or cleaners by means of a continuous process.
  • At least as used herein in combination with a numerical value means that the numerical value given represents a lower limit and any larger numerical values are recorded.
  • at least two means, for example, 2 or more, especially 2, 3, 4, 5, 6, 7, 8, 9, 10 or more.
  • fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
  • the former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them.
  • the oxo alcohols or their derivatives which are obtainable, for example, by the RoELEN's oxo synthesis, can also be used correspondingly.
  • alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
  • the method is characterized in that the continuous separate volume flows of the at least two liquid washing or cleaning agent components are introduced successively or simultaneously into a water-bearing main strand.
  • the water-bearing main branch is a water volume flow in which the volume flows of the individual detergent or cleaning agent components are introduced.
  • "Separate" as used herein in connection with Volume flows of the components used means that the components of the detergent or cleaning agent are introduced individually and not pre-mixed in the main strand.
  • also volume flows of individual components can be introduced directly into a mixer used in the process and combined there / mixed with the main strand.
  • the detergent or cleaner components are liquid in the sense that they are either themselves liquid or are used in the form of a liquid solution or dispersion (emulsion).
  • the at least two liquid detergent or detergent components may preferably comprise at least one acid precursor of an anionic surfactant and at least one neutralizer for the acid precursor.
  • the detergent or cleaning agent produced is therefore preferably a washing or cleaning agent containing an anionic surfactant.
  • the acid precursor reacts with the neutralizing agent in a neutralization step to obtain an anionic surfactant.
  • a dynamic loop mixer makes it possible to drain the neutralization reaction as completely as possible by the circulation of the reaction mixture in the mixing loop before the mixture leaves the dynamic loop mixer.
  • the neutralization therefore proceeds at least partially in the dynamic loop mixer.
  • "Partial" here means that the neutralization reaction has already begun before the introduction of the mixture into the dynamic loop mixer, or may not be completely completed at the exit from the dynamic loop mixer.
  • the acid precursors (acid precursors) of the anionic surfactant are the free acids of anionic surfactants, especially those containing sulfate or sulfonate groups.
  • anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • acylaminoalkanesulfonates fatty acid taurides
  • fatty acid sarcosinates fatty acid sarcosinates
  • ethercarboxylic acids and alkyl (ether) phosphates and also ⁇ -sulfofatty acid salts
  • acylglutamates monoglyceride disulfates and alkyl ethers of glyceryl disulfate.
  • Preferred in the context of the present invention are the linear alkylbenzenesulfonates, fatty alcohol sulfates and / or fatty alcohol ether sulfates, in particular the linear alkylbenzenesulfonates.
  • Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols
  • fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • the person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, for the purposes of the present invention preferably with longer-chain alcohols.
  • a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions.
  • Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • Preferred fatty alcohol ether sulfates are the sulfates of lower ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.
  • alkylbenzenesulfonates preference is given in particular to those having about 12 C atoms in the alkyl moiety, for example linear sodium C 10-18 -alkylbenzenesulfonate.
  • Preferred olefin sulfonates have a carbon chain length of 14 to 16.
  • anionic surfactants are usually used as sodium salts, but can also be used as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts.
  • the acid precursors are preferably the free acids of the above-described fatty alcohol sulfates, fatty alcohol ether sulfates and linear alkylbenzenesulfonates, most preferably the free acids of linear alkylbenzenesulfonates. That In various embodiments of the invention, the acid precursor is an alkylsulfuric acid, alkylalkoxysulfuric acid or a linear alkylbenzenesulfonic acid, especially a linear alkylbenzenesulfonic acid, preferably a C10-C18 linear alkylbenzenesulfonic acid, such as dodecylbenzenesulfonic acid.
  • the neutralizing agent is an aqueous solution of an inorganic alkali or alkaline earth metal salt, in particular an alkali metal salt.
  • an inorganic alkali or alkaline earth metal salt Preference is given to sodium salts, such as, for example, sodium hydroxide or sodium carbonate.
  • the neutralizing agent may contain a concentration of the inorganic alkali metal or alkaline earth metal salt of 1 to 90 wt .-%, preferably 10 to 80 wt .-%, for example 20, 30, 40, 50 or 60 wt .-%.
  • more than one acid precursor and / or more than one neutralizing agent may also be used.
  • more than one anionic surfactant may be formed in the process by neutralization.
  • several acid precursors or neutralizing agents are used, in certain embodiments they can also be used as mixtures of several acid precursors or mixtures of several neutralizing agents.
  • the at least two liquid washing or cleaning agent components at least one acid precursor of an anionic surfactant, in particular an alkyl sulfuric acid or an alkylbenzenesulfonic acid, and at least one neutralizing agent for the acid precursor, in particular an aqueous solution of an inorganic alkali metal salt, preferably a sodium hydroxide or sodium carbonate solution, and the process includes a neutralization step of the acid precursor with the neutralizing agent to obtain an anionic surfactant, wherein the neutralization is carried out at least partially in the reaction volume.
  • an anionic surfactant in particular an alkyl sulfuric acid or an alkylbenzenesulfonic acid
  • neutralizing agent for the acid precursor in particular an aqueous solution of an inorganic alkali metal salt, preferably a sodium hydroxide or sodium carbonate solution
  • the amount of neutralizing agent used in the process can be controlled by controlling the volume flow of neutralizing agent introduced.
  • the amount is preferably controlled by controlling the pH of the mixture leaving the dynamic loop mixer. If the pH of the mixture after the neutralization reaction in the dynamic loop mixer deviate from the desired value, the volume flow of the neutralizing agent can be readjusted accordingly.
  • the amount of the at least one neutralizing agent is such that substantially complete neutralization of the at least one acid precursor occurs. "Substantially” in this context means that more than 90, preferably more than 95% of the acid precursor are neutralized.
  • the at least two liquid detergent or cleaner components may further comprise at least one co-surfactant.
  • a cosurfactant may be advantageous for improving the solubility of the acid precursor in the aqueous phase and thus favoring neutralization.
  • Such a cosurfactant is therefore preferably added to the reaction mixture prior to introduction into the dynamic loop mixer.
  • the co-surfactant can be combined, for example, in the form of a separate continuous volume flow with the volume flows of the other constituents or introduced into the main water supply after or before this.
  • the cosurfactant after the acid precursor and the neutralizer is introduced directly into a liquid mixer upstream of the dynamic loop mixer and mixed there with the remaining ingredients before the reaction mixture, which is preferably homogeneous, containing acid precursors, neutralizing agents and cosurfactant , is introduced into the dynamic loop mixer.
  • the co-surfactant may be, for example, an anionic or nonionic surfactant.
  • the anionic surfactants may be selected from the surfactants described above in connection with the acid precursors.
  • the co-surfactant may in particular be a fatty alcohol ether sulfate, preferably with 2 to 4 EO, more preferably 2 EO.
  • An example of a suitable surfactant is, but is not limited to, sodium dodecylpoly (oxyethylene) sulfate having 2 EO.
  • Nonionic surfactants in the invention may be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also useful are ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers.
  • Another important class of nonionic surfactants which can be used according to the invention are the polyol surfactants, in particular the glycerides, such as alkyl polyglycosides and fatty acid glucamides.
  • the alkylpolyglycosides in particular the alkylpolyglucosides, the alcohol particularly preferably being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C 8 - to C 18 -alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, especially 1.1 to 3, most preferably 1.1 to 1.7, for example, C 8-10 alkyl-1.5-glucoside (DP of 1.5).
  • DP degree of oligomerization
  • fatty alcohol alkoxylates are also preferred, especially with ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C 8-22 -alcohols having a degree of alkoxylation up to 30, preferably ethoxylated C 12- 22 fatty alcohols having a degree of ethoxylation of less than 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example C 16-18 fatty alcohol ethoxylates with 25 EO.
  • EO ethylene oxide
  • PO propylene oxide
  • the volume of the dynamic loop mixer and the continuous separate volume flows of the at least two liquid detergent or detergent components are such that the residence time of the combined volume flow in the dynamic loop mixer is sufficient to neutralize the neutralization reaction by at least 80%, preferably at least 90%, in particular 99% complete. It is advantageous to keep the residence time as short as possible, for example ⁇ 1 minute, preferably 45 seconds or less, in order to make the process as economical as possible. For a production of detergents or cleaning agents of 25 t / h, volumes of the dynamic loop mixer in the range of approximately 200-300 l are required.
  • the continuous separate volume streams of the at least two liquid detergent components may be directed into at least one static or dynamic liquid mixer upstream of the dynamic loop mixer to produce a homogeneous mixture.
  • the homogeneous mixture produced by the at least one static or dynamic liquid mixer is then introduced into the dynamic loop mixer where the neutralization reaction occurs.
  • the at least one static or dynamic liquid mixer has no recycle and is, in various embodiments, a high performance emulsifier.
  • it is a dynamic liquid mixer, more preferably a dynamic multi-frequency Liquid mixer.
  • Such mixers are available, for example, under the name PENTAX from Bran + Luebbe (SPX Process Equipment, Norderstedt, Germany).
  • volume flows of the individual components can already be combined prior to introduction into the mixer, for example introduced into the water-bearing main branch, or volume flows of individual components can be combined and mixed only in the mixer with the remaining volume flows of the other components.
  • the volume flows of the acid precursor and of the neutralizing agent are combined before the mixer and / or the cosurfactant is first mixed in the mixer with the other constituents.
  • additional additional static or dynamic liquid mixers upstream of, for example, the first dynamic liquid mixer may be used. These may be used, for example, to mix together various components of the detergents or cleaners in a predetermined order.
  • the individual constituents of the washing or cleaning agent are mixed in such a way that undesirable side reactions are avoided as far as possible.
  • compounds which are sensitive to acidic / basic degradation are supplied only after neutralization, ie, first to the volume flow exiting from the dynamic loop mixer.
  • At least one further continuous volume flow of at least one detergent or cleaning agent component in particular selected from acids, fragrances, dyes, bitter substances, and adjusting agents for regulating the viscosity, can be supplied to the continuous volume flow emerging from the dynamic loop mixer.
  • All constituents of the washing or cleaning agent which are used in the process according to the invention can be used as pure substances or as aqueous or organic solutions.
  • the neutralizing agent for example an aqueous NaOH solution
  • a buffer acid such as phosphoric acid
  • the acid precursor of the anionic surfactant for example an acid precursor of a linear alkylbenzenesulfonate
  • the mixture is introduced into a dynamic liquid mixer, into which a volumetric flow of a cosurfactant, such as, for example, an alkanesulfate, is introduced simultaneously.
  • the metering of the acid precursor directly in front of the dynamic liquid mixer ensures that the corrosive effect of the concentrated acid precursor on the plants is minimized. Further, direct dosing of the cosurfactant into the liquid mixture ensures that viscosity maxima that are passed through during mixing are eliminated quickly and effectively.
  • the volumetric flow exiting the dynamic liquid mixer is then introduced into the dynamic loop mixer to complete the neutralization reaction.
  • the volumetric flow leaving the dynamic liquid mixer is then fed with further constituents, such as acids, in particular ascorbic acid, bitter substances, fragrances, dyes and thickeners, and then mixed in a further static liquid mixer. The mixture exiting from this mixer is then the finished, ready for bottling detergent or cleaning product.
  • the volume flow exiting from the last mixer can pass through a pH sensor, which then regulates the addition of the neutralizing agent via the specific pH value. It is advantageous in various embodiments to first introduce low viscosity ingredients, such as ethanol, as well as preservatives into the continuous process. Thickeners, such as sodium chloride solution (20% wt .-%), however, should only be added at the end of the process.
  • heat exchangers can be used at any point in order to regulate the temperature of the mixture.
  • the invention also relates to the use of a dynamic loop mixer in a continuous process for the preparation of liquid detergents or cleaners.
  • the continuous process is a manufacturing process as described above. Therefore, the features disclosed above in connection with the method according to the invention are analogously transferable to the use according to the invention and it is intended that such embodiments of use fall within the scope of the present invention.
  • the washing or cleaning agent produced according to the invention is a liquid washing or cleaning agent, "liquid” in this context also including higher-viscosity gels or pastes.
  • the preparations produced may be liquid detergents or liquid hard surface cleaners, such as liquid dishwashing detergents, for example hand dishwashing detergents, or even glass cleaners, bathroom cleaners and the like.
  • the anionic surfactant i. the acid precursor and the neutralizing agent, and optionally the co-surfactant
  • other components in the process are added at different locations.
  • These components are ingredients commonly found in detergents or cleaners. This group of other possible ingredients includes, but is not limited to, acids, bases, salts, chelants, polymers, fillers, builders, bleaches, and mixtures thereof.
  • the washing or cleaning agent produced according to the invention may contain one or more water-soluble salts in a total amount of from 0.1 to 75% by weight.
  • These may be inorganic and / or organic salts, in a preferred embodiment it is at least one inorganic salt.
  • Inorganic salts which can be used according to the invention are preferably selected from the group comprising colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used. Particularly preferred are halides and sulfates of the alkali metals; Preferably, the at least one inorganic salt is therefore selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof. In a preferred embodiment, sodium chloride and / or sodium sulfate is used.
  • the organic salts which can be used according to the invention are, in particular, colorless water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and / or transition metal salts of the carboxylic acids.
  • the salts are selected from the A group comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.
  • inorganic salts are used, very particularly preferably sodium chloride and / or sodium sulfate. These salts may be present in an amount of up to 75 wt .-%, preferably 0.01 to 60 wt .-%, particularly preferably 20 to 60 wt .-%, in particular 35 to 60 wt .-%.
  • washing or cleaning agent produced according to the invention may contain all builders (builders) customarily used in detergents or cleaners, in particular silicates, carbonates, organic cobuilders and also the phosphates.
  • builders customarily used in detergents or cleaners, in particular silicates, carbonates, organic cobuilders and also the phosphates.
  • amorphous sodium silicates with a Na 2 O: SiO 2 module of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, to which also water glass is to be counted.
  • the term "amorphous" is also understood to mean "X-ray amorphous”.
  • zeolites can be used as builders, preferably zeolite A and / or P.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • alkali metal ions are sodium and / or potassium ions, particularly preferred are soda (sodium carbonate) and potash (potassium carbonate).
  • alkali metal phosphates are the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • Suitable phosphates are the sodium dihydrogen phosphate, NaH 2 PO 4 , the Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , the trisodium phosphate, sodium tertiary phosphate, Na 3 PO 4 , the tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , and those by condensation of NaH 2 PO 4 and KH 2 PO, respectively 4 arise higher molecular weight sodium and potassium phosphates, in which cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or Kaliumpolyphosphate can distinguish.
  • organic cobuilders it is possible in particular to include polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • NTA nitrilotriacetic acid
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.
  • the acids can also be used per se.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their molecular weight, relative to free acids is generally 2000 to 100000 g / mol.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursors, in particular polyaspartic acids or salts and derivatives thereof, besides polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, and dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • these are hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • Oxydisuccinates and other derivatives of disuccinates are further suitable co-builders, preferably in the form of their sodium or magnesium salts, furthermore iminodisuccinates (IDS) and their derivatives, for example hydroxyiminodisuccinates (HDIS), and acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • IDS iminodisuccinates
  • HDIS hydroxyiminodisuccinates
  • HDIS hydroxyiminodisuccinates
  • acetylated hydroxycarboxylic acids or their salts which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, it may be preferred Aminoalkanphosphonate, in particular DTPMP use, or to use mixtures of said phosphonates.
  • all compounds capable of forming complexes with alkaline earth ions may be included as co-builders in the particulate agents.
  • the acids are preferably produced from renewable raw materials. Suitable acids are therefore in particular organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and mixtures thereof. In addition, however, it is also possible to use the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or else sulfamic acid or mixtures thereof.
  • the acids and / or their salts are particularly preferably selected from the group comprising citric acid, lactic acid, formic acid, their salts and mixtures thereof. They are preferably used in amounts of 0.01 to 10 wt .-%, particularly preferably 0.2 to 5 wt .-%.
  • Acids can also be used as buffer substances, for example to reduce pH fluctuations.
  • Phosphoric acid H 3 PO 4 is particularly suitable for this purpose in the process according to the invention.
  • the detergents or cleaners prepared according to the invention may furthermore contain alkalis.
  • Suitable bases in agents according to the invention are preferably those from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide.
  • ammonia and / or alkanolamines having up to 9 C atoms in the molecule preferably the ethanolamines, in particular monoethanolamine.
  • Chelating agents also called sequestering agents, are ingredients capable of complexing and inactivating metal ions to prevent their detrimental effects on the stability or appearance of the detergents or cleaners of the invention, for example clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents. In addition, the complexing agents support the cleaning effect.
  • the following complexing agents designated as INCI are suitable: aminotrimethylene phosphonic acid, beta-alanines diacetic acid, calcium disodium EDTA, citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin , Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate
  • the washing or cleaning agent produced according to the invention may further contain polymers. These can be used, for example, to reduce calcification and the tendency to re-soiling.
  • Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol.
  • bleaching agents can be added to the washing or cleaning agent.
  • Suitable bleaching agents include peroxides, peracids and / or perborates, more preferably sodium percarbonate or phthalimidoperoxyhexanoic acid.
  • chlorine-containing bleaching agents such as trichloroisocyanuric acid or sodium dichloroisocyanurate, are less suitable for acidic detergents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents.
  • a bleach activator may be required in addition to the bleaching agent.
  • the washing or cleaning agent produced according to the invention may contain one or more further auxiliary agents and additives customary in hand dishwashing detergents and hard surface cleaners.
  • auxiliary agents and additives customary in hand dishwashing detergents and hard surface cleaners.
  • organic propellants especially sugars, sugar alcohols, glycerol, glycols and polymers thereof
  • hydrophobicity mediators such as paraffin
  • UV stabilizers such as paraffin
  • perfume oils such as paraffin
  • pearlescing agents ICI Opacifying Agents, for example glycol distearate, eg
  • opacifiers for example the technical 2-bromo-2-nitropropane, also referred to as bronopol.
  • 1,3-diol (CAS 52-51-7), which is commercially available, for example, as Myacide® BT or Boots Bronopol BT from Boots, or also Bronopol-containing mixtures such as Preventol® (ex Lanxess) or Parmetol® ( ex Schülke & Mayr)), disinfectants, enzymes, pH adjusters, fragrances and skin feel-improving or skin-care additives (eg dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericin, Collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, Ha mamelsextracts, algae extracts, etc., allantoin, AHA complexes, glycerol, urea,
  • the washing or cleaning agent produced according to the invention may comprise one or more fragrances, preferably in an amount of from 0.01 to 10% by weight, in particular from 0.05 to 8% by weight, particularly preferably from 0.1 to 5% by weight. %.
  • a perfume component d-limonene may be contained.
  • the detergent block according to the invention thereby contains a perfume of essential oils (also referred to as essential oils). Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil, for example, can be used as such in the context of this invention.
  • fragrances usually used in detergents or cleaning agents are likewise suitable for use in the washing or cleaning agent prepared according to the invention, for example further essential oils, esters, alcohols, aldehydes or terpenes.
  • the washing or cleaning agent according to the invention therefore contains one or more antimicrobial agents, preferably in an amount of from 0.01 to 1% by weight. preferably 0.02 to 0.8 wt .-%, in particular 0.05 to 0.5 wt .-%, particularly preferably 0.1 to 0.3 wt .-%, most preferably 0.2 wt .-%.
  • disinfection, sanitation, antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention.
  • the killing of - in theory all - infectious germs means under sanitation the greatest possible elimination of all - including the usually harmless to humans saprophytic - germs to understand.
  • the extent of disinfection or sanitation depends on the antimicrobial effect of the applied agent, which decreases with decreasing content of antimicrobial agent or increasing dilution of the agent for use.
  • antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention
  • Derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores, active chlorine-releasing Compounds and peroxides.
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2 Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13
  • Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, it is also possible to use antimicrobial-effective essential oils which at the same time ensure scenting of the washing / cleaning product.
  • particularly preferred antimicrobial agents are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite, sodium dichloroisocyanurate and mixtures thereof.
  • Preservatives may also be included in detergents or cleaners according to the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.
  • the washing or cleaning agent prepared according to the invention may contain one or more dyes ( INCI Colorants).
  • dyes both water-soluble and oil-soluble dyes can be used, on the one hand, the compatibility with other ingredients, such as bleaching agents, is observed and on the other hand, the used dye against the objects to be cleaned / washed should not be substantive even with prolonged exposure.
  • the dyes are preferably present in an amount of 0.0001 to 0.1 wt .-%, in particular 0.0005 to 0.05 wt .-%, particularly preferably 0.001 to 0.01 wt .-%, contained.
  • Suitable corrosion inhibitors are, for example, the following named according to INCI : Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphates, Nitromethanes, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.
  • Suitable regulators are preferably solid long-chain fatty acids, such as stearic acid, but also salts of such fatty acids, fatty acid ethanolamides, such as coconut fatty acid monoethanolamide, or solid polyethylene glycols, such as those having molecular weights between 10,000 and 50,000.
  • the washing or cleaning agent prepared according to the invention may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They can be added to the composition according to the invention in any form established according to the prior art. These include solutions of the enzymes, preferably concentrated as possible, low in water and / or added with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in core-shelled form.
  • enzymes preferably proteases, lipases, amylases, hydrolases and / or cellulases.
  • an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • enzyme stabilizers may be present in enzyme-containing cleaning products in order to prevent an enzyme contained in a WC cleaning product according to the invention from damage such as, for example, inactivation, denaturation or decomposition physical influences, oxidation or proteolytic cleavage.
  • Suitable enzyme stabilizers are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, for example substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars.
  • benzamidine hydrochloride borax, boric acids, boronic acids or their salts or esters, especially derivatives with
  • stabilizers for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the pH sensor indicated that in this procedure, the neutralization reaction was not complete and resulted in a pH variation of ⁇ 2.5 per fill.
  • Mixture E1 was subsequently produced in a continuous process with buffer vessel (volume 18 liters) scale 800 kg / h or with dynamic loop mixer (BIS EMS MD 100 with single rotor / stator, volume 12.5 liters) scale 1150 kg / h.
  • the measurement with pH sensor 2 gave a relatively constant signal in both cases.
  • the residence time in the buffer vessel was 81 seconds, that in the dynamic loop mixer 39 seconds.
  • a disadvantage was also here that air is introduced into the product through the buffer vessel, which becomes noticeable as turbidity during filling, whereas the use of the closed dynamic loop mixer avoids this problem.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP13788766.7A 2012-11-22 2013-11-08 Kontinuierliches verfahren zur herstellung von flüssigen wasch- oder reinigungsmitteln Not-in-force EP2922945B1 (de)

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DE102012221360.0A DE102012221360A1 (de) 2012-11-22 2012-11-22 Kontinuierliches Verfahren zur Herstellung von flüssigen Wasch- oder Reinigungsmitteln
PCT/EP2013/073364 WO2014079702A1 (de) 2012-11-22 2013-11-08 Kontinuierliches verfahren zur herstellung von flüssigen wasch- oder reinigungsmitteln

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WO2024235669A1 (en) 2023-05-12 2024-11-21 Basf Se Process for preparing chemical formulations comprising a neutralized component

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DE102015212131A1 (de) * 2015-06-30 2017-01-05 Henkel Ag & Co. Kgaa Verfahren zur Herstellung einer flüssigen, Tensid enthaltenden Zusammensetzung

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GB8506025D0 (en) * 1985-03-08 1985-04-11 Unilever Plc Chemical reactions
GB9107092D0 (en) 1991-04-04 1991-05-22 Unilever Plc Process for preparing detergent compositions
US6657071B1 (en) * 1999-06-25 2003-12-02 Lion Corporation Process for producing α-sulfo-fatty acid alkyl ester salt
DE10208265A1 (de) * 2002-02-26 2003-09-11 Beiersdorf Ag Verfahren zur Herstellung von Emulsionen

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