CN1046312C - A new powdered or granular non-dust surfactant concentrate of water-solubility improved - Google Patents
A new powdered or granular non-dust surfactant concentrate of water-solubility improved Download PDFInfo
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- CN1046312C CN1046312C CN93101455A CN93101455A CN1046312C CN 1046312 C CN1046312 C CN 1046312C CN 93101455 A CN93101455 A CN 93101455A CN 93101455 A CN93101455 A CN 93101455A CN 1046312 C CN1046312 C CN 1046312C
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Abstract
The invention relates to a solid, free flowable, powdered and/or granular anionic surfactant concentrate, the power or granule can also be compounded with other assistants and/or useful materials suitable as detergent and/or cleaning product that have been dried from the corresponding water preparation thereof. The invention is characterized in that the anionic surfactant concentrate shows washing state and/or cleaning salts state, has apparent density of at least 150 g/L, preferably over 200 g/L, more preferably at least about 300 g/L, and is prepared by drying the superheated steam. In addition, the surfactant concentrate can be in dust-free state by adding dust-binding assistant and/or useful materials and/or adjusting residual water amount.
Description
The present invention relates to novel solid-state loose powdery or granular detergent and/or clean the anion surfactant enriched material; therefore the present invention seeks to propose washing and/or clean anionic surfactant compound; this compound has the integrated materials performance that can't reach in the prior art; special fine-grannular powder and/or grain are especially proposed; its anion surfactant amount is adjustable arbitrarily; in fact can reach pure tensio-active agent or its mixture; this powder or grain dust are few or dustless; its bulk density is also high thereby adjustable, and this apparent density can be much higher than 150g/l and can keep the optimization solvability again in washing and/or scavenging solution simultaneously.
Such anion surfactant and/or its mixture are proposed in important embodiment of the present invention, in fact its amount has any adjustability, therefore its production cost can reduce, and can preferentially satisfy at present and also can make major contribution based on the anion surfactant of alkylbenzene sulfonate to the replacement of making every effort at present reach especially to the tensio-active agent that allows on the ecology or an urgent demand of its component.
In specific embodiments, the problem paid attention to of the present invention is with plant and/or the zoogenous initial material manufacturing known anionic tensio-active agent as new dustless anion surfactant enriched material main component.But the present invention is not limited to these plants and/or the initial material of animal source.The synthetic surfactant compound, the especially ecological synthetic compound of going up safety is preferred main component and/or blending ingredients in the present invention's explanation.
Solve the difficulty that the present invention proposes this problem and be found in following situation as an example: from oleophylic organic composition vitriol and/or sulfonate field can capacity and/or several ecologies of obtaining of reasonable price on the anion surfactant component of safety, as lipid acid, Fatty Alcohol(C12-C14 and C12-C18), sufficiently long alkene and/or alkane etc. are known for washing composition and/or cleaning products field professional, exemplary is sulfuric acid and Fatty Alcohol(C12-C14 and C12-C18), the half ester class of especially relative long-chain saturated fatty alcohol, this is the pure sulfonation gained fatty alcohol sulfate (FAS) that forms after Fatty Alcohol(C12-C14 and C12-C18) alkoxide, especially titanium dioxide and/or third oxidation and the important part in the fatty alcohol ether sulfate (FAES).
Other important example of typical anionic surfactants is alpha-sulfonated fatty acids and detergent active salt thereof and in conjunction with sulfonated fatty acid ester, wherein known have alpha-sulfo fatty acid methyl ester and salt (MES) and a α-sulfonation carboxylic acid, this be by the ester cracking of the detergent active salt (being called " disalt ") of lipid acid and these lipid acid and/or directly α-sulfonation obtain.Above-mentioned all anionic surfactant compounds of sheerly giving an example contain the organic residue of relative long-chain, as C
8-24, C especially
12-18, be the known blending ingredients of washing composition, wherein with other tensio-active agent, especially nonionogenic tenside, organic and/or inorganic builders or help and wash component and other typical hybrid component and use.
At present, difficult point is to make above-mentioned anion surfactant enriched material, is also referred to as ABS class synthetic anion surface active agent, but can obtain by solid-state free-flowing form, especially make dustless powder and/or grain, and have the height performance density of actual requirement and reach water-soluble at high proportion at a high speed.Make dustless, but dumpable and unrestricted flow and can dissolve fine powder rapidly or grain is the ideal solution can be widely used in plant and/or animal source vitriol and/or sulphonate-base anion surfactant field.Moisture paste as the principal reaction product when making above-mentioned anionic surfactant compound is having many problems aspect the industrial processes, for example stability and difficult treatment.On the other hand, the alkyl-sulphate facile hydrolysis, and also the solids content relation of all anion surfactants paste viscosity and concrete moisture paste is very big, and can reach moisture paste can not and manage the degree of transporting and can not measure with pump always.
Understood this technical background, just be not difficult to find out that many methods all are conceived to anion surfactant involved in the present invention is changed into the solid reason, as proposing to contain the compound and the dispersion agent of anion surfactant, solvating agent and/or easy water-soluble salt are also used.This auxiliary agent must be used for dryed product production in the prior art, because can only obtain being worth limited anion surfactant product based on the common dry technology of heated drying in the spray-drying tower and/or in the fluidized-bed.Difficulty specifically is following situation: the poorly soluble and possibility gelling of significant surfaces active agent component, even if be converted into the dried state of particulate and like this, just the dry powder dissolving is very slow for this.Carry out the dry powder that dry powder can only obtain for example containing in some cases high Dust Capacity of making in this spray-drying tower, even only have the anion surfactant of moderate content also like this in the initial material.This can cause second problem to a great extent, as producing and must being with respirator when handling these dry powder.
In addition, concrete difficulty is following phenomenon: this anionic surfactant compound can only be processed into the low bulk density powder-like product with hot waste gas by present known hot-air dry technology or by modern spray drying technology.Even if use these auxiliary agents, make wetting agent as inorganic salt, dried tensio-active agent powder apparent density is suitably increased.In many cases, apparent density is lower than g/l.In this method of optimizing, as under dry powder situation, being adjusted to the apparent density of about 130g/l at the most based on TAS.Even mix with auxiliary agent, this disalt also can not be made the dry powder that reaches this apparent density certainly.In this case, the accessible apparent density of technical scale generally is lower than 100g/l.
In its early stage patent application DE-A4030688, the applicant has illustrated that can be used for passing through steam with its aqueous compositions makes the dry heat air-flow and make wetting agent, the particulate of washing composition and/or cleaning products is solid-state, but the recovery method of the useful material of dumpable or unrestricted flow or its mixture, the drying of granulated material promptly stopped before heat damage.But add long-term pourability or free-flowing property that the mixing element that can be combined with the water of limiting the quantity of can guarantee such part exsiccant material in case of necessity.
Be used for superheat steam drying washing composition and/or cleaning products useful material simplification and improve early stage German patent application DE-A4204035 and the DE-A4204090 that technology has seen the applicant.Back of the present invention is described promptly based on these early stage German Patent examinations.Because of than, these early stage patent applications also are incorporated in this especially.As a part disclosed by the invention.
The present invention relates to the back but solid-state free flowing powder and/or granular anionic surfactant enriched material are described in detail in detail, these materials can be compound states of matter, wherein also comprise auxiliary agent and/or useful materials that other should be used for washing composition and/or cleaning products, the dry corresponding water-base preparation of its method for making forms powder and/or grain.
Anion surfactant enriched material feature of the present invention is that its apparent density is 150g/l at least comprising the anionic surfactant compound that is its washing and/or cleaning salt attitude to small part, and available superheated vapour is made dry gas heated drying aqueous compositions and made.About the preferred apparent density 200g/l of this anion surfactant enriched material or higher, preferred 300g/l or higher, more preferably 350g/l or higher at least.
In addition, anion surfactant enriched material difference of the present invention is that particularly its dustiness is very low at least, and is in preferred version, almost completely dustless.In a preferred version, this class enriched material is characterised in that, for reaching these performances, even if in the superfine particle material, also contains in conjunction with the auxiliary agent of dust and/or useful material as mixing element.Except this measure and, but also can regulate the quantity of residual in the dumpable and free-flowing materials and reach dustless state by the present invention.
In another program, the present invention relates to have the anion surfactant enriched material production method of above-mentioned requirements performance combination.At last, in another program, the present invention relates to dry state anion surfactant enriched material is used for washing composition and/or cleaning products, at first is water base class safety product, in particular for replace ABS base anion surfactant to small part.
But the preparation method of the dried enriched material of purpose mat powder of the present invention and/or granular detergent and/or cleaning active anionic surfactant compound reaches to realize, wherein by use the hot gas flow drying in spraying area or fluidized-bed
(a) washing and/or the cleaning active anionic surfactant compound, its also can with
(b) at room temperature be solid, from the commonly used organic and/or inorganic mixture component in washing composition and detergent mixture field, mix and exist, the content of component (a) is at least 30 weight % in the wherein this mixture,
Free flowable aqueous preparation be prepared, it is characterized in that, superheated vapour is used as hot gas flow in drying zone, be at least the solid that 150 grams per liters and residual moisture content are lower than 5 weight % with the preparation tap density, dumpable and free-pouring, dustless powder and/or particle, drying is carried out in the normal pressure scope, superheated vapour is supplied with drying zone with the temperature more than 150 ℃ and is followed with being removed from drying zone in the drying zone moisture evaporated, in the system of sealing, operate with the described flow of superheated steam of round-robin, remove from the moisture evaporated in the feed material from described cyclical superheating vapour stream, the energy that loses in the drying step is joined again as cycling stream and is recycled in the superheated vapour part of drying zone simultaneously.
Shockingly see existing, can make each composition of definition keep making solid-state anion surfactant and respective anionic surfactant concentrate by the present invention in conjunction with also considering following other composition in case of necessity, its performance reaches the requirement combination, though a little aspect those skilled in the art made great efforts several years, always also fail to reach this specific performance combination.The sprayable drying of these anion surfactants is made superfine powdery.Gained powder and tensio-active agent grain are dustless equally, and grain is considered to unique solutions basically at present, and wherein the manufacturing process of being undertaken by existing way with the powder of making also comprises an other step.Anion surfactant powder difference of the present invention also shows as high apparent density, can carry out material processing, packing and the transportation of this specific form by suitable mode and less expensive ground like this.Simultaneously, the high apparent density that reaches is for the washing composition of producing the form attitude on request and cleaning products, and it is very important making it become the used direct application mix component of so-called heavy powder.But the experience that prior art obtains shows, resembles this form of anion surfactant solid and usually is accompanied by in the water liquid complicated or be slow dissolved shortcoming at least.And among the present invention, this shortcoming has not existed or has dropped to the degree that there are not any restriction in actual treatment and application facet to anion surfactant enriched material of the present invention at least.
In a preferred version, washing or cleaning active amount of surfactant 20wt% at least in the anion surfactant enriched material of the present invention, preferably (in fine-grained solids) about 30wt% at least.Basically say that Duo solid surfactant can form powder or grain like this.But in fact, importantly should remember, in general, limited amount residual component (inorganic salt, non-sulfonation resistates etc.) can be in industrial-scale production anion surfactant gained solid surfactant as acceptable or even can be described as incoherent impurity and exist.Therefore in the present invention, especially preferably the active component content with anion surfactant is the tensio-active agent grain of about 35-95wt%.In this scope, preferably surface active agent composition reaches those materials or its mixture of 50wt% above (equally in fine-grained solids).In the special mixture of the useful material of gained, the preferred upper limit of anion surfactant amount is roughly 75-95wt%, for example promptly have roughly 80,85 or the anion surfactant of 90wt%.Other determinative of this respect may be to carry out the exsiccant ultimate principle with superheated vapour as dry gas, and this illustrates in the early stage patent application of above-mentioned application, especially sees DE-A4030688, below simply repeats so that the present invention is easier to understand.
Known when making drying medium with superheated vapour, temperature distribution in the material dropping process that is dried is different from the common drying means that carries out with warm air and/or hot fuel gas, be in particular in: by dry material with 100 ℃ following temperature introduce in the superheated vapour atmosphere, moisture whereabouts material is heated to the water boiling temperature simultaneously under operational condition, wherein superheated vapour condensation and heat of condensation discharged to the material that is dried on cold relatively initial material.Therefore, when normal pressure carried out drying, this referred to be heated in the material dropping process about 100 ℃.In whole time of drying in the material dropping process this boiling temperature remain minimum temperature.According to the melt temperature of used granular anionic surfactant or its mixture, but use 100 ℃ down for solid-state auxiliary agent and thereby the long-term pourability of the particulate materials that guarantees to be dried and free-flowing property may be effectively or or even necessary.As described below, these auxiliary agents may be again to reach selected useful material of application purpose or inert material, based on organic and/or inorganic blending ingredients, dissolve in and/or water insoluble.In spraying drying, this can guarantee to reach the result who reaches in the common spraying drying, be that the wet initial material of fluidised form can drying become the particulate attitude, particle can obviously not adhere to mutually or be adjusted particle diameter to a great extent at least simultaneously, even also like this during as dry gas at superheated vapour.
The anion surfactant component that exists in these solids can contain the useful material of above-mentioned some discrete, also can become any basically mixture of the useful material that is selected from described tensio-active agent certainly." surfactant mixture " should be understood by several modes: even in selection type, do not have individual substance as aliphatic alcohol sulfate and/or fatty acid sulfonate are on selected compound meaning.The processing of initial material processing of plant and/or animal source and corresponding synthetic original chemical product can obtain the useful material of described type, and it can fall in a certain scope on forming, as the carbonatoms in Fatty Alcohol(C12-C14 and C12-C18) and/or the fatty acid component.
But " surfactant mixture " of the present invention's definition also comprises the anion surfactant particular combinations of different structure in essence.Therefore, can be effectively with common detergent active TAS base anion surfactant for example with for example based on the anion surface activity dispersant of suitable short chain sulfuric ester and/or sulphonate.Other example of at least two kinds of different anion surfactants is a disalt on the one hand, and promptly the alpha-sulfo aliphatic salt is as having C
14-20The salt of chain length and on the other hand based on TAS and/or the alkylether sulfonate especially mixture of the anion surfactant of methyl ester sulfonate (MES).
The invention solves the problem that dustless powder and/or grain are provided, dual mode is arranged, and even the use that can mutually combine.First method according to the amount of concrete solid materials, can reach dustless based on the be dried scheme of material content of residual water of concrete application by the water-content of regulating dry material at least to a great extent.
This respect is relevant be that this paper begins to quote and at this at DE-A4030688 institute column data as a part disclosed by the invention.The about 1-20wt% of preferably water content, more preferably about at the most 10wt%, especially 5-7wt%, specially suitable is about 3 or the residual amount of 4wt%, and the quantity of residual of about 1-3wt% generally can reach gratifying result.But as described in example, also can reach the residual moisture content that is lower than 1wt%.
And in the present invention's one important aspect, the anion surfactant enriched material can contain the component that adds with the difference amount, and it is overriding concern that this amount reaches dustless purpose aspect in the present invention, and promptly this material is as the auxiliary agent in conjunction with dust.In this scheme, the present invention is particularly including adding these auxiliary agents, and this can be used as with concrete anion surfactant component and combines the useful material that is used for washing composition and/or cleaning products.
In this scheme, particulate of the present invention is dumpable and but unrestricted flow anion surfactant feature is wherein to contain blending ingredients (being preferably the uniform mixing states of matter) as auxiliary agent and/or useful material in conjunction with dust, this at room temperature is liquid and/or is viscosity at least, have the residuary water of limiting the quantity of in case of necessity, and the amount that adds surfactant concentrate is preferably the necessary dustless amount that guarantees, but can not bring disadvantageous effect to pourability and free-flowing property for a long time again simultaneously.
Suitable dust particularly can be water-soluble especially under the room temperature in conjunction with auxiliary agent, water-emulsifiabl and/or swollen monomeric compound.The blending ingredients of oligomer compounds and/or the suitable superpolymer compound form of selecting.Before the specific examples of discussing as these auxiliary agents of blending ingredients or useful material, this respect notion as basis of the present invention should be explained at this: but by its solvability in water and emulsifying property and swellable in any case, these auxiliary agents can evenly add the active material admixture based on the anion surfactant that is dried.If in the drying step that superheated vapour described in the early stage patent application of the follow-up applicant who begins to mention with this paper carries out and for just the present invention, disclose complete, with moisture initial thing section with granular, particularly the exsiccant form is dispersed in the superheated vapour under fine-grannular and the superheated vapour effect, then dust can add reliably and equably in conjunction with auxiliary agent, and is evenly distributed in each particle.Because auxiliary agent be a liquid state, viscosity or be toughness at least, so additive show the upper layer of utmost point dried particles in conjunction with the dust effect.On the other hand, by the amount of suitable selection active substance in mixture, still can keep through very long period of storage even can guarantee not have sticking dumpable or free flowable claimed condition.The ratio of mixture of setting up under each special situation is easy to determine considering under the relevant professional knowledge situation by simple experiment.
Be suitable for the representative example that combines auxiliary agent or useful material with anion surfactant component blended dust as follows:
Suitable water soluble ingredient fluid under the normal condition is low volatility polyvalent alcohol or its oligopolymer.Only consider that for the minimizing expense it is particularly important to levy this respect glycerine and its oligopolymer.But these component of mixture as ethylene glycol and/or propylene glycol oligopolymer and/or superpolymer are unrestricted flow and/or can reach enough further examples of close-burning respective compound at least under the residuary water effects.More particularly, molecular weight is as the highest by about 10000, be limited to the corresponding oligopolymer of about 500-1000 on the highest preferred about 7000 polyoxyethylene glycol and the molecular weight and especially can be useful material in the technology of the present invention, object lesson as above-mentioned relevant glycerine and/or its oligopolymer, these materials not only have the dust associativity of requirement, and can be used as solvating agent and/or useful material is used for washing composition and cleaning products.But, other typical object lesson of suitable auxiliary agent also comprises monomer and/or oligomeric glycosides, as glucose, glucose oligosaccharide, sugar, as sucrose, or one or more sugar compounds accordingly, comprising a large amount of rings, also comprise the corresponding superpolymer of starch and/or part degraded starch and starch derivative.The characteristics of all these compounds are more or less to have tangible viscosity, and are particularly like this in the presence of less water.In washing composition and cleaning products practical application, deposit that these components of levying are directly absorbed by aqueous cleaning solution and washing and cleaning that can interference requirement with extremely low concentration.
In this respect, note that the another kind of appearance form possibility of above-mentioned anionic surfactant compound: selected glycoside derivates is subject to people's attention just day by day as detergent-active compounds, and its distinguishing characteristics especially shows as its natural material matrix.These compounds belong to alkylpolyglycosides compound (APG) and glycosides, sugar etc. and the preferred quite ester or the part ester classification of longer chain fatty acid.Above-mentioned glycoside compound has outstanding nonionogenic tenside characteristic.Its difference also shows as itself and anion surfactant and time spent and has outstanding raising performance synergy.Although washing or cleaning active alkyl wherein can be arranged, as C
8-20, C especially
10-18Alkyl replaces, but this glycoside compound generally is moisture absorption as solid, and it has reliably the function in conjunction with the powdery composition in addition during evenly adding the useful material of anion surfactant and at corresponding aqueous slurry dry epoch chien shih.This situation that improves the value of corresponding anion surfactant/non-ionic surfactant mixture just need not to add to have explained.
Other suitable component of mixture of removing dust reliably preferably can water-solublely at least expand and/or water-soluble oligomeric and/or high poly-component of mixture for itself.In this case, the representative example that a large amount of this components is also arranged, these examples are very attractive at common washing composition and cleaning products field, comprise Polyvinylpyrolidone (PVP) (PVP), polyvinyl alcohol (PVA), polycarboxylate compound, special sintetics, can be for example with (methyl) vinylformic acid and toxilic acid or maleic anhydride polymerization or copolymerization and get, this plays an important role as so-called building component in modern washing powder.Another important example of the above-mentioned type compound is the oligomeric or high poly-dextrose of carboxyl group functional, and this can obtain by 6 introducing carboxyls at glucose ring by selective oxidation starch.Same available corresponding water-soluble and/or water-swellable fiber rope derivative, as methylcellulose gum, carboxymethyl cellulose, hydroxy alkyl cellulose is as Natvosol etc.
Above-mentioned non-limitative example also can obtain replenishing and/or replacement, can consider that any other has the component of mixture of identical performance, the non-volatility under the operational condition in suitable solvability in water or swelling property and the hot steam of going on a punitive expedition particularly, this respect can be used relevant professional knowledge.
The auxiliary agent of some other type below is discussed respectively: other suitable blending ingredients is specially nonionogenic tenside, but the also unrestricted flow or levy and have enough viscosity under the normal temperature conditions of these preparations, but can not be included into above-mentioned nonionogenic tenside based on glycosides, ether or ester.Purely as an example, can list this class fatty alcohol ethoxylate, contain for example 2-40EO unit in its molecule, preferred 2-20EO unit, and corresponding lipid acid, aliphatic amine, the corresponding ethoxylate of carboxylic acid amides and/or alkyl sulfonamide.Many important subclass and particular type have specifically been listed among the applicant's that this paper begins to mention the DE4030688 as the non-ionic surfactant component example that relates in the drying means that wherein carries out with superheated vapour.The technology of the present invention has surpassed this early stage patent application disclosure, wherein use the suitable nonionic surfactants component, it is deposited free-flowing property under levying or viscosity in residuary water and is not wished the dust that exists in being enough to safely in conjunction with the finished product, and the anion surfactant that simultaneously again can be just only obtains with the high dust formulations of powder-form at present becomes the high solid enriched material.
Suitable anionic surfactant compound is washing and/or the cleaning active product example that existing market can extensively obtain.As mentioned above, material and the corresponding sintetics based on crude substance is suitable equally.Preferred anionic tensio-active agent distinguishing characteristics is that its ecological security increases and suitable especially stem portion and/or replace the basic anion surfactant component of ABS-fully.
The anionic surfactant compound aliphatic alcohol sulfate of the used particularly important of the present invention (saturated and/or unsaturated), fatty alcohol ether sulphate, alkene and/or alkane sulfonate, fatty sulfonate, alpha-sulfonated fatty acid triglyceride level and/or glycerin fatty acid moieties ester vitriol.Another important anion surfactant example in the scope of the invention is a succinic acid half-ester sulfonate, and its ester group contains enough oleophylic residues, as C
0-20, C particularly
10-16The fat alcohol radical.The fatty sulfonate example of particularly important is the known anionic tensio-active agent based on alpha-sulfo-fatty acid lower alkyl esters or its salt, and wherein most important example still is an alpha-sulfo fatty acid methyl ester (MES).The specific examples of fatty acid sulfonate is alpha-sulfo-fatty acid and its washing or cleaning active salt, and this is called " disalt " in those skilled in the art.Can make with free fatty acids and/or corresponding alpha-sulfo fatty acid ester by ester cracking way.Known alpha-sulfonated fatty acid triglyceride level is natural fat and/or oil and particularly SO
3Reaction product.Can sulfuric ester and the multicomponent mixture form of sulphonate obtain and seen for example applicant's German patent application DE3936001 and 3941365.
Washing and/or clean anion surfactant and generally exist with its basic metal and/or ammonium salt or with the soluble salt of organic bases.An alkali metal salt of particularly important is sodium salt and corresponding sylvite.The amount of auxiliary of Shi Yonging is generally 2-3wt% at least in case of necessity, and preferred 5-10wt% at least is in multicomponent mixture.
The mixture that the present invention also comprises anion surfactant with and with above-listed blending ingredients, particularly organic constituent, even with the mixture of inorganic blending ingredients.These components are preferably the washing composition that is selected from even adding powder and/or the grain and/or the respective components of the typical composition of cleaning products.This class water-soluble inorganic blending ingredients example is a water-soluble salt, and as yellow soda ash, sodium bicarbonate and/or sodium sulfate, and water-soluble metasilicate are particularly for washing composition and the typical water glass of cleaning products.Except these water-soluble inorganic components and, also the water-insoluble blending ingredients can be added in the powdery anion surfactant granule.The example of water-insoluble blending ingredients is the synthetic zeolite compound, the zeolite NaA of washing composition quality-class particularly, and its calcium-binding capacity is 100-200mgCaO/9, presses DE2412387 and measures.The very special quality of the anion surfactant enriched material that constitutes by the present invention can specify with these insoluble inorganic componentss: if for example TAS carries out conventional drying process with atomizing with zeolite NaA, then detergent active TAS component can be on the zeolite granular surface firmly be skim being absorbed into, and washability can expand to no longer that it can reach Anywhere in the washing lotion in this continuous after an action of the bowels application.In the present invention's definition and the anion surfactant enriched material by the present invention's production, this disadvantageous effect that adds zeolite no longer exists or reduces at least greatly.Other example of available water-insoluble blending ingredients is that particulate swelling sex cords takes off stone class leaf silicate, as wilkinite.Total principle is applicable to used useful material of the present invention and auxiliary agent certainly equally basically described in the above-mentioned DE-A4030688 that quotes again and again of this paper, in the document, be exposed to can be obviously not impaired under 100-110 ℃ water or the steam useful material or the mixture of itself and auxiliary agent be suitable.Expose in the said temperature scope under the operational condition that this not impaired class component was specially suitable useful material at least about 0.5-1 minute.For example, the surfactant compounds of facile hydrolysis also can pass through the residence time of several minutes safely under these working conditions in essence, notices that just some critical condition that those skilled in the art know gets final product.Therefore, the anion surfactant of facile hydrolysis in essence can be processed into dustless dry powder by the inventive method as the aqueous compositions of FAS and/or MES.
The details of each possibility scheme of superheat steam drying technology is found in applicant's above-mentioned early stage German patent application, particularly P4204035.3 and P4204090.6.Complete for the present invention is disclosed, existing processing parameter selections with particularly important in these early stage patent applications are described as follows:
Can use high temperature mutually to cyclic steam at the drying step of drying process with atomizing in the operational condition of technology of the present invention.Used steam operation temperature is generally in the gas phase more than 150 ℃, preferably at least about 200 ℃.250 ℃ and higher service temperature particularly advantageous, even available at least 300 ℃, especially 300-380 ℃ temperature.In many cases, about 270-350 ℃ service temperature is suitable especially in the vapor phase.All these temperature values relate to be sent into following current or counter current drying district and is heated to the vapor temperature of optimizing temperature.At steam and wet stock period of contact, its temperature is pressed currently known methods and is descended.Mainly consider capacity factor, comprise the steam that subsequent applications is removed from the loop, just can quantitatively determine evaporated water and the superheated vapour amount sent between ratio.Drop to the scheme of about 190-250 ℃ value with can realizing only will leaving vapor temperature fidelity behind the spraying drying district in this respect, and in other scheme, steam thermal energy can further be used for vapor temperature is dropped to about condensing temperature under the processing condition (100-110 ℃).More particularly, these details can solve by the design of full cycle technology.Corresponding consideration also is applicable to uses superheated vapour post-processing stages where necessary as hot gas, as follow-up fluidized-bed process or any granulating technology that other is united in case of necessity of carrying out.In this case, above-mentioned numerical value is suitable equally.
In essence, in the factor of above-mentioned consideration as can be seen, this technology is carried out in the closed system that is provided with the water vapor cycling stream, and the water from initial material evaporation in steam cycle stream is removed, and the energy that particularly discharges in drying step directly or is preferably got back to this cycling stream indirectly.In an important aspect, but from the loop, removed at the following current of spraying drying district or counter-current operation and free-flowing materials, and removed steam diversion preferably uses it for anything else as process steam after carrying out the useful material that purifying carries secretly with removal in addition, uses after its pressure and temperature is transferred to requirement condition in case of necessity.In another embodiment of technology of the present invention, can be condensed and be recycled in the drying process to the steam diversion of this removal of small part with the wherein contained any useful material of from the loop, removing.In this respect, as using the gas phase of from circulation, removing steam aqueous liquid phase is concentrated.Can directly deliver to the spraying drying district or can mix with the fresh aqueous preparation earlier with the useful material round-robin liquid that wherein exists and then send into the spraying drying district and carry out drying with this form.
In the particularly advantageous scheme of the present invention, remove the heat of condensation of steam from the loop and recycled.The useful thing section that adopts adequate measure even can superheated vapour circulate and leave main steam-return line a small amount of the sixth of the twelve Earthly Branches through removing from the loop.In this respect, as adopting utilization to remove the following method of the heat of condensation of steam from the loop:
The heat of condensation of the air-flow that application is removed from the loop can concentrate steam condensate preferred multistep flash evaporation transmitting apparatus.The residual enriched material of accumulative returns the main technique loop.More particularly, this residual enriched material can add with superheated vapour and carries out in the useful material slurry of the exsiccant section.
In case of necessity, the uncooled residual gas phase that might assemble and contain minimum useful material from main loop in the superheated vapour condensation process of removing can be sent to further processing in condensation process, as calcining or in biological filter or washing device, handling.
Under operational condition of the present invention, also can be undertaken by spray-drying process on the other hand and/or be undertaken by fluid-bed drying with the drying that superheated vapour carries out.For example, the initial material of high water content is made also sprayable be dried useful material or its mixture aqueous solution, emulsion and/or the suspension that can flow relatively.In an important embodiment, this initial material carries out spraying drying by currently known methods, wherein can be in the spray-drying tower of arrange accordingly following current or adverse current carry out.In general, advantageous applications counter-current process in the inventive method.On the other hand, when carrying out with fluid-bed drying, then also can adopt known particle amplifieroperation principle in this case as if drying process of the present invention.
Under the spraying drying condition, preferably at least mainly will evaporate institute's energy requirement introduces steam-return line indirectly in addition from drying zone in the present invention.This can guarantee that fluidised form is moistened initial material can the fine-grained form drying, and simultaneously not just particle obviously adhere to mutually or controllable adjustment particle diameter at least.Introduce the energy of steam-return line in addition introduces by known any indirect heat transfer mode from drying zone.Example can be enumerated the hot gas that application wherein has any source on the one hand, and the tube bundle system of the steam flow of being heated is arranged on the other hand.
In the embodiment of particularly important of the present invention, thisly indirectly introduce energy and can carry out for the way of steam with the burner indirect heat transfer of one or more connection to steam-return line.Hot burning gas is directly introduced interchanger, and this interchanger is linked steam-return line in the burner side.This burning gas temperature can be for example about 400-1000 ℃, particularly about 650-960 ℃.From optimizing heat utilization efficiency and therefore reduce the expense of whole technology, but at waste gas also part, preferably basically fully loop condition assign may be very effective.For example, 30vol% at least, the above hot waste gas of preferred 40vol% can circulate after leaving the interchanger of linking and remove further to utilize energy.The exhausted air quantity of preferred cycle can reach more than the 60vol% that introduces burning gas, reaches about 70vol% usually.Burner can be with any universal fuel gas, particularly Sweet natural gas or comparable lower hydrocarbon or its mixture and/or steam operation.
If on the one hand, drying principles of the present invention is applied to fluidised bed drying, then steam can carry out outside drying zone for necessity heating of the dry gas on basis, and the also available device of linking the interchanger of fluidized-bed carries out.These two kinds heating principles also can mutually combine.
The preferred embodiment of the invention is carried out under normal pressure, also only needs suitable simple operation even if then reach necessary high unit time quantum of output in industrial equipments.The measure of being undertaken by preferred version of the present invention that improves interior pressure a little can stop external gas, particularly air unnecessarily to enter the loop that is full of steam reliably, thereby prevents the infringement once more to the high product quality that requires to reach reliably.Suitable working pressure is as being up to about 150mbar, preferably the highest about 75mbar, the more preferably superpressure of the superpressure of not enough 50mbar, particularly about 5-15mbar.Certainly, with superheated vapour by drying of the present invention also can levy in principle the decompression under carry out, particularly under medium decompression, carry out, must have the equipment size of increasing could guarantee not exist in the loop failure area that can cause unnecessary air to infiltrate certainly in this case.Therefore, above-mentioned numerical value has been represented preferred decompression.
Embodiment 1
In the test spray-drying tower of the pilot scale of Niro-Atomizer " small-scale production " type, with the C of dry matter content 36.5%
16/
18Alpha-sulfo-fatty acid sodium salt slurry is introduced in the tensio-active agent powder of apparent density 370g/l.Initial pulp property data are as follows:
Detergent active thing (Epton) 26.3% is in slurry
Unsulfonated lipid acid 2.09%
Sodium sulfate 3.1%
Sodium-chlor 2.2%
Sulfonation degree 89.6%
Regulate following operating parameters:
Rotating disk atomizer rotating speed 25000rpm
About 300 ℃ of steam-in temperature
About 200 ℃ of steam exit temperature
16mbar reduces pressure in the tower
Charging pump pressure 0.2bar
80 ℃ of feeding temperatures
Input speed increases to 18kg/h from 8 during levying spraying drying
The about 500m of vapour volume
3/ h
Products obtained therefrom dry matter content 99.8%, apparent density 370g/l, solvability excellence when adding entry.
Embodiment 2
Operation is with example 1, and the slurry that is dried is the slurry of solids content 36%, wherein contains above-mentioned C
16/
18The polyoxyethylene glycol of sodium salt of alpha-sulfo-fatty acid (impure) and molecular weight 2000, ratio are dry matter weight 9: 1.300 ℃ of tower temperature ins, 210 ℃ of temperature outs, all other parameter comparabilities.Product amount of dry matter 99wt%, apparent density 290g/l.
Embodiment 3
In the test spray-drying tower of the pilot scale of Niro-Atomizer " small-scale production " type, with C
16/
18The fatty alcohol sulphuric acid ester sodium salt changes in the free flowable tensio-active agent powder, adds yellow soda ash.Anion surfactant and yellow soda ash ratio of mixture 4: 1 are in dry-matter.
Aliphatic alcohol sulfate aqueous slurry white is to light yellow dense and burned, and its characteristic is as follows:
Detergent active thing (Epton) 54-58wt%
Aliphatic alcohol sulfate 53-55wt%
Unsulfonated 1-3wt%
NaCl amount＜=1wt%
Na
2SO
4Amount＜=2wt%
PH value (3% aqueous compositions) 10-11.5
After adding natron liquid, slurry reaches the dry matter content of 47.7wt%.
Following operating parameters is adjusted to uses superheat steam drying:
250 ℃ of steam-in temperature
Steam exit temperature 175-180 ℃
16mbar reduces pressure in the tower
Fresh feed pump pressure 5.5 crust
80 ℃ of feeding temperatures
Input speed 12kg/h
The about 350m of vapour volume
3/ h
The propulsive gas speed 3.3m of two composition nozzles
3/ h
Pressure 0.2bar
Products obtained therefrom amount of dry matter 99.2%, apparent density 293g/l, 20 ℃ of solubleness 90% in the water after 40 seconds.
Embodiment 4
Operational example 1, the slurry solids that is dried amount 53.3wt% is comprising C
16/
18The sodium salt of example 1 described fatty alcohol sulfate and fine grain silicon sodium aluminate (washing quality zeolite NaA), form is 48% suspension, has used 1.5wt% ox alcohol polyglycol ether stabilization.Ratio of mixture between anion surfactant and silicate (dry weight) 2: 1.Dry-matter apparent density 316g/l, solubleness 90% in the time of 10 seconds.
Embodiment 5
Operation is with example 3 and 4, and the slurry of solids content 24.1% is dry in mutually at superheated vapour.The original mixture solids component is example 3 described C
16/
18The fatty alcohol sulphuric acid ester sodium salt, C
16/
18The disodium salt of alpha-sulfo-fatty acid and yellow soda ash, ratio of mixture 4: 1: 1.Dried carrier powder apparent density 220g/l, solubleness 90% in the time of 20 seconds.
Embodiment 6
The various mixtures of the tensio-active agent of aqueous compositions attitude and water-soluble inorganic auxiliary agent are adverse current with example 3 usefulness two-component nozzle (propulsive gas is a nitrogen) and superheated vapour and carry out spraying drying.
Used mixture, the ratio of mixture of actual mixt (in dry-matter), the apparent density g/l that dryed product reaches, quantity of residual wt% and standard water (20 ℃) solubleness (90%) are shown in following table, wherein:
Sulfopon T55 (Henkel KGaA) is the anion surfactant based on aliphatic alcohol sulfate,
Disalt is C
16/
18The Na disalt of alpha-sulfo-fatty acid mixture,
Dehydrol TA40 is an ox alcohol b-oxide, average 40EO,
Water glass A is the washing quality water-soluble metasilicate,
APG is C
12/
14Alkylglycoside (DP about 1.4).
Following table has been summed up above-mentioned dry each data of mixture that form the porous support bead.Can know and find out, all quite high with the dissolution rate of solubleness (90%) expression, even also like this when having the apparent active agent component of the negatively charged ion that is insoluble in cold water in essence of a great deal of in all cases in the actual mixt.
Embodiment 7
Pilot scale in Niro-Atomizer " small-scale production " type is implemented in the spray-drying tower of chamber C
16/
18But the sodium salt slurry of fatty alcohol sulfate changes in the unrestricted flow tensio-active agent powder, adds yellow soda ash and sucrose.Anion surfactant, ratio of mixture is counted 80: 17: 3 with dry-matter between yellow soda ash and sucrose.
The aqueous slurry of fatty alcohol sulfate is that white is extremely light yellow dense and burned, and its characteristic is as follows:
Hydrous matter (Epton) 54-58%
Fatty alcohol sulfate 53-55%
Unsulfonated 1-3%
NaCl amount≤1%
Na
2SO
4Amount≤2%
PH value (3% aqueous compositions) 10-11.5
Behind the aqueous solution with soda and the sucrose liquid, reach the slurry amount of dry matter of 47.7wt%.
Regulate following parameter, it is suitable for superheated vapour carries out drying.
340 ℃ of steam-in temperature
Steam exit temperature 160-180 ℃
16mbar reduces pressure in the tower
Charging pump pressure 7.5bar
80 ℃ of feeding temperatures
Input speed 21kg/h
Vapour volume 350m
3/ h
The propelling tolerance 2.2m of two composition nozzles
3/ h
Pressure 0.3bar
Products obtained therefrom apparent density 310g/l is middle nature and flavor white powder, and amount of dry matter 99.2% demonstrates fabulous wettability and solubility in cold water.
Embodiment 8
Operation is with example 7, and the slurry that is dried is above-mentioned C
16/
18Fatty alcohol sulfate, yellow soda ash, the aqueous compositions of the polyoxyethylene glycol of sucrose and molecular-weight average 400, with dry material than ratio of mixture 80: 14: 3: 3, solid wherein, yellow soda ash and sucrose have been dissolved in 3 parts of water and with slurry and have mixed, fresh feed pump pressure 4.3-4.6bar, the propelling tolerance 3.8m of two composition nozzles
3/ h, all other parameters can compare the product amount of dry matter 99.3wt% that obtains, apparent density 280g/l and soluble in water with example 7.
Embodiment 9
Operation is with example 7 and 8, and the slurry that is dried is above-mentioned C
16/
18Fatty alcohol sulfate, yellow soda ash, sucrose and the beef fat alcohol that contains about 40molEo, ratio of mixture 80: 14: 3: 3, in dry-matter.It is water-soluble before yellow soda ash and sucrose mix with slurry with 1: 3 ratio.Beef fat alcohol/Eo
40Before adding, it melts (fusing point 42-47 ℃).Fresh feed pump pressure 3.2-3.3bar, two composition nozzles advance tolerance 3.7m
3/ h, all other parameters and example 7 are comparable.Product amount of dry matter 99.2wt%, apparent density 270g/l, easy-to-use water-wet and very high dissolution rate is arranged.
Table 1
Test-results, wt%
| Form | MR | AD g/l | RM ％ | L90 min/s |
| Sulfopon T 55+water glass A | 50∶50 | 267 | 1.46 | 1/01 |
| Sulfopon T 55+water glass A | 70∶30 | 209 | 1.52 | 0/27 |
| Sulfopon T 55+water glass A | 80∶20 | 251 | 0.81 | 1/00 |
| Sulfopon T 55+soda disalt | 90∶10 - | 285 187 | 4.02 1.25 | 2/14 0/22 |
| Sulfopon T 55+disalt | 2∶1 | 230 | 0.92 | 0/32 |
| Sulfopon T 55+disalt+soda | 4∶1∶1 | 220 | 1.07 | 0/20 |
| Sulfopon T 55+soda | 70∶30 | 198 | n.d | 0/22 |
| Sulfopon T 55+soda+Dehydol TA40 | 70∶20∶10 | 218 | n.d. | 0/16 |
| Sulfopon T 55+soda+Dehydol TA40 | 75∶20∶5 | 143 | n.d. | 0/18 |
| Sulfopon T 55+disalt+APG | 50∶48∶2 | 354 | n.d. | 0/16 |
MR=ratio of mixture (in dry-matter)
The AD=apparent density
The RM=residuary water
The L90=solvability
The n.d.=undetermined
Claims (15)
1. the preparation method of the dried enriched material of powder and/or granular detergent and/or cleaning active anionic surfactant compound wherein passes through to use the hot gas flow drying in spraying area or fluidized-bed
(a) washing and/or the cleaning active anionic surfactant compound, its also can with
(b) at room temperature be solid, from the commonly used organic and/or inorganic mixture component in washing composition and detergent mixture field, mix and exist, the content of component (a) is at least 30 weight % in the wherein this mixture,
Free flowable aqueous preparation be prepared, it is characterized in that, superheated vapour is used as hot gas flow in drying zone, be at least the solid that 150 grams per liters and residual moisture content are lower than 5 weight % with the preparation tap density, dumpable and free-pouring, dustless powder and/or particle, drying is carried out in the normal pressure scope, superheated vapour is supplied with drying zone with the temperature more than 150 ℃ and is followed with being removed from drying zone in the drying zone moisture evaporated, in the system of sealing, operate with the described flow of superheated steam of round-robin, remove from the moisture evaporated in the feed material from described cyclical superheating vapour stream, the energy that loses in the drying step is joined again as cycling stream and is recycled in the superheated vapour part of drying zone simultaneously.
2. method as claimed in claim 1, wherein said washing and/or cleaning active anion surfactant are the vitriol of the long-chain organic compound of organic moiety with 8 to 24 carbon atoms and/or the washing and/or the cleaning active salt of sulfonate.
3. method as claimed in claim 1, it is characterized in that, the aqueous compositions of applied component (a) or component (a) and mixture (b), this component (a) used with dosage form or component (a) and mixture (b) can not be adversely affected because of the water of 100-110 ℃ of temperature range or the effect of steam in 0.5 to 1 minute time.
4. method as claimed in claim 1 is characterized in that, in spraying drying, the use temperature in is at least 200 ℃ superheated vapour as hot gas flow.
5. method as claimed in claim 1 is characterized in that, in spraying drying, the use temperature in is at least 250 ℃ superheated vapour as hot gas flow, and the residual amount in the material that is dried is reduced to 1-3 weight %.
6. method as claimed in claim 1, it is characterized in that, but from the loop, removed at the following current of spraying drying district or counter-current operation and free-flowing materials, and removed steam diversion should use it for anything else in addition as process steam, yet, can be condensed and be recycled in the drying process to the steam diversion of this removal of small part with the wherein contained any useful material of from the loop, removing.
7. method as claimed in claim 6, wherein removed steam diversion before using it for anything else in addition, is being carried out the useful material that purifying is carried secretly with removal as process steam.
8. method as claimed in claim 1, it is characterized in that, aliphatic alcohol sulfate (FAS), fatty alcohol ether sulphate (FAFS), alkene and/or alkane sulfonate, fatty sulfonate, fatty acid sulfonate, succinic acid half-ester sulfonate, alpha-sulfonated fatty acid triglyceride level and/or glycerine/fatty acid part ester vitriol, and optional alkylbenzene sulfonate (ABS) is used as described component (a).
9. method as claimed in claim 8 is characterized in that, described fatty sulfonate is that alpha-sulfo-fatty acid lower alkyl esters and salt thereof, described fatty acid sulfonate are alpha-sulfo-fatty acid or its salt (disalt).
10. as the method for claim 8 or 9, it is characterized in that described washing and/or cleaning active anion surfactant are to use with the form of its basic metal and/or ammonium salt or organic alkali salt.
11. method as claimed in claim 1, it is characterized in that, as described component of mixture (b) but use monomeric, the oligomeric and/or polymeric component of mixture of soluble emulsification and/or swellable in water at room temperature, water-swellable and/or water-soluble oligomer and/or polymkeric substance.
12. method as claim 11, it is characterized in that, but described at room temperature in water monomeric, the oligomeric and/or polymeric component of mixture of soluble emulsification and/or swellable be glycerine, low Polyglycerine, polyoxyethylene glycol and/or polypropylene glycol, monomer and/or oligomeric glycosides or corresponding glycoside compound, described water-swellable and/or water-soluble oligomer and/or polymkeric substance are polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polycarboxylate and derivatived cellulose.
13. the method as claim 12 is characterized in that, described corresponding glycoside compound is washing and/or cleaning active alkylglycoside compound, and described derivatived cellulose is methylcellulose gum, carboxymethyl cellulose, hydroxy alkyl cellulose.
14. method as claimed in claim 1, it is characterized in that, use yellow soda ash, sodium sulfate and/or water glass (water glass), synthetic zeolite compound and/or particulate swelling property smectites leaf silicate as component (b), optionally be used in combination with the organic mixture component of mentioning.
15. the method as claim 14 is characterized in that, described synthetic zeolite compound is washing composition level zeolite-NaA.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4204035.3 | 1992-02-12 | ||
| DEP4204090.6 | 1992-02-12 | ||
| DEP4204033.3 | 1992-02-12 | ||
| DE4204033A DE4204033C2 (en) | 1992-02-12 | 1992-02-12 | Raised floor |
| DE19924204090 DE4204090A1 (en) | 1992-02-12 | 1992-02-12 | SIMPLIFIED DRYING PROCESS FOR RECYCLING MATERIALS AND RECYCLING MATERIALS FROM THE AREA OF DETERGENT AND CLEANING AGENTS WITH OVERHEATED WATER VAPOR |
| DEP42040906 | 1992-02-12 | ||
| DEP42060508 | 1992-02-27 | ||
| DEP4206050.8 | 1992-02-27 | ||
| DE19924206050 DE4206050A1 (en) | 1992-02-27 | 1992-02-27 | Drying wetting, washing and/or cleaning agent or component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1076723A CN1076723A (en) | 1993-09-29 |
| CN1046312C true CN1046312C (en) | 1999-11-10 |
Family
ID=27203392
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93101455A Expired - Fee Related CN1046312C (en) | 1992-02-12 | 1993-02-11 | A new powdered or granular non-dust surfactant concentrate of water-solubility improved |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1046312C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894117A (en) * | 1988-04-28 | 1990-01-16 | Colgate-Palmolive Company | Process for manufacturing high bulk density particulate fabric softening synthetic anionic organic detergent compositions |
| US4963226A (en) * | 1989-01-23 | 1990-10-16 | The Procter & Gamble Company | Process for spray-drying detergent compositions |
-
1993
- 1993-02-11 CN CN93101455A patent/CN1046312C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894117A (en) * | 1988-04-28 | 1990-01-16 | Colgate-Palmolive Company | Process for manufacturing high bulk density particulate fabric softening synthetic anionic organic detergent compositions |
| US4963226A (en) * | 1989-01-23 | 1990-10-16 | The Procter & Gamble Company | Process for spray-drying detergent compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1076723A (en) | 1993-09-29 |
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